Photosensitive or radiation-sensitive resin composition, photosensitive or radiation-sensitive film, pattern forming method, method for manufacturing electronic device, and method for manufacturing photomask

Abstract

According to the present application, there are provided a radiation-sensitive or radiation-sensitive resin composition, a radiation-sensitive or radiation-sensitive film using the above-mentioned composition, a pattern forming method, a manufacturing method of an electronic device, a radiation-sensitive or radiation-sensitive resin composition for manufacturing a photomask, and a manufacturing method of a photomask, the radiation-sensitive or radiation-sensitive resin composition containing a resin whose solubility in a developer changes by the action of an acid, a photoacid generator (A) having a group whose polarity changes by decomposition by the action of an acid, a photoacid generator (B) that generates an acid having a higher pKa than the acid generated by the photoacid generator (A), and a basic compound.

Description

Technical Field

[0001] This invention relates to a photosensitive linear or radiosensitive linear resin composition, a photosensitive linear or radiosensitive linear film, a patterning method, a method for manufacturing electronic devices, a photosensitive linear or radiosensitive linear resin composition for photomask manufacturing, and a method for manufacturing photomasks. More specifically, this invention relates to an ultra-micro lithography process applicable to manufacturing processes of large-scale integrated circuits (LSI) and high-capacity microwafers, nanoimprint molding processes, and high-density information recording media, as well as other photosensitive etching processes, preferably used in ultra-micro lithography processes, photosensitive linear or radiosensitive linear resin compositions, photosensitive linear or radiosensitive linear films, patterning methods, methods for manufacturing electronic devices, photosensitive linear or radiosensitive linear resin compositions for photomask manufacturing, and a method for manufacturing photomasks. Background Technology

[0002] Previously, in the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs, microfabrication based on photolithography using photoresist compositions was performed. In recent years, with the increasing integration of integrated circuits, the formation of ultra-fine patterns in sub-micron or quarter-micron regions is required. Consequently, there has been a trend towards shorter exposure wavelengths, such as from gamma rays to i-rays, and then to KrF excimer lasers. Currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as the light source has been developed. Furthermore, as a technique to further improve resolution, the so-called immersion method, which involves filling the space between the projection lens and the sample with a high-refractive-index liquid (hereinafter also referred to as "immersion liquid"), has been continuously developed.

[0003] Furthermore, in addition to excimer lasers, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) is also under development.

[0004] Patent Document 1 describes an anti-corrosion composition comprising a resin having an acid-decomposing group, a salt consisting of a specific organic cation and an organic sulfonic acid anion having an acid-decomposing group but not having a nitrogen atom, and a salt consisting of a specific organic cation and an organic sulfonic acid anion not having a nitrogen atom.

[0005] Previous technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2013-41257 Summary of the Invention

[0008] The technical problem to be solved by the invention

[0009] However, in recent years, with the further refinement of the formed patterns, there is a demand in pattern forming methods for photosensitive radioactive or radiosensitive linear resin compositions that can further improve resolution and reduce development defects. Furthermore, there is a demand for photosensitive radioactive or radiosensitive linear resin compositions that maintain high resolution and have few development defects even after a specified period following preparation.

[0010] The object of the present invention is to provide a photosensitive radioactive or radioactive linear resin composition that has high resolution and few development defects in a pattern forming method and also has high resolution and few development defects after a specified period of time following the preparation of the photosensitive radioactive or radioactive linear resin composition; a photosensitive radioactive or radioactive linear film using the above-mentioned photosensitive radioactive or radioactive linear resin composition; a pattern forming method; a method for manufacturing electronic devices; a photosensitive radioactive or radioactive linear resin composition for photomask manufacturing; and a method for manufacturing photomasks.

[0011] means for solving technical problems

[0012] Through in-depth research, the inventors discovered that the above-mentioned problem can be achieved through the following structure. [1]

[0014] A photosensitive or radiosensitive linear resin composition comprising:

[0015] The solubility of resin (P) in the developing solution changes due to the action of acid;

[0016] Compound (A) has a group (a) whose polarity changes upon decomposition by the action of an acid, and produces an acid (ac1) upon irradiation by photochemical rays or radiation.

[0017] Compound (B), which, upon irradiation with photochemical rays or radiation, produces an acid (ac2) with a pKa higher than that produced by the acid (ac1) from the aforementioned compound (A); and

[0018] Basic compound (C). [2]

[0020] According to the photosensitive radioactive or radiosensitive linear resin composition described in [1], wherein,

[0021] The pKa of the acid (ac2) is more than 1 higher than that of the acid (ac1). [3]

[0023] According to the photosensitive radioactive or radiosensitive linear resin composition described in [1] or [2], wherein,

[0024] The ratio of the content of the above-mentioned compound (B) to the content of the above-mentioned basic compound (C), i.e., (B) / (C) in molar ratio, is 1.1 or more and 10 or less. [4]

[0026] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [3], wherein,

[0027] The ratio of the sum of the contents of the above-mentioned compound (B) and the above-mentioned basic compound (C) to the sum of the contents of the above-mentioned compound (A) and the above-mentioned compound (B), i.e., [(B)+(C)] / [(A)+(B)], is 0.3 or more and 1.0 or less in molar ratio. [5]

[0029] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [4], wherein,

[0030] The content of the above-mentioned compound (A) is 5% by mass or more and 60% by mass or less relative to the total solid content of the above-mentioned photosensitive or radiosensitive linear resin composition. [6]

[0032] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [5], wherein,

[0033] The above compound (A) is represented by the following general formula (b1).

[0034] [Chemical Formula 1]

[0035]

[0036] In general formula (b1), L represents a single-bonded or divalent linker. When multiple Ls are present, they can be the same or different. A represents a group whose polarity changes through decomposition by acid (a). When multiple As are present, they can be the same or different. n represents an integer from 1 to 5. X represents a linker with a valence of n+1. M + This indicates a sulfonium ion or an iodonium ion. [7]

[0038] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [6], wherein,

[0039] The above compound (A) is represented by the following general formula (b3).

[0040] [Chemical Formula 2]

[0041]

[0042] In general formula (b3), L represents a single-bonded or divalent linker. When multiple Ls are present, they can be the same or different. A represents a group whose polarity changes through decomposition by acid (a). When multiple As are present, they can be the same or different. o, p, and q independently represent integers from 0 to 5. The sum of o, p, and q is greater than 1 and less than 5. M + This indicates a sulfonium ion or an iodonium ion. [8]

[0044] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [7], wherein,

[0045] The group (a) whose polarity changes due to decomposition by the action of acid is represented by the following general formula (T-1).

[0046] [Chemical Formula 3]

[0047]

[0048] In general formula (T-1),

[0049] R 11 It represents a hydrogen atom or an alkyl group.

[0050] R 12 It represents a hydrogen atom, alkyl, cycloalkyl, or aryl group, and the aforementioned alkyl and cycloalkyl groups may contain ether bonds or carbonyl bonds.

[0051] R 13 The alkyl, cycloalkyl, or aryl groups may contain ether or carbonyl bonds.

[0052] R 11 and R 12 They can bond together to form a ring.

[0053] R 12 and R 13 They can bond together to form a ring.

[0054] * indicates a link key. [9]

[0056] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [8], wherein,

[0057] The ratio of the content of compound (A) to the content of compound (B), i.e., (A) / (B) in molar ratio, is 0.2 or more and 2.0 or less.

[10]

[0059] A photosensitive radioactive or radioactive linear film is formed using any one of the photosensitive radioactive or radioactive linear resin compositions described in [1] to [9].

[11]

[0061] A method for forming a pattern, comprising:

[0062] In the resist film forming process, a resist film is formed using any one of [1] to [9] photosensitive or radiosensitive linear resin compositions;

[0063] The exposure process involves exposing the aforementioned resist film to light; and

[0064] In the developing process, the exposed resist film is developed using a developing solution.

[12]

[0066] A method for manufacturing an electronic device, comprising the pattern forming method described in

[11] .

[13]

[0068] A photosensitive radioactive or radioactive linear resin composition for photomask manufacturing, wherein the photosensitive radioactive or radioactive linear resin composition described in any one of [1] to [9] is used for photomask manufacturing.

[14]

[0070] A method for manufacturing a photomask, which uses the photosensitive radioactive or radiosensitive linear resin composition for photomask manufacturing described in

[13] .

[0071] Invention Effects

[0072] According to the present invention, it is possible to provide a photosensitive radioactive or radioactive linear resin composition that has high resolution and few development defects in a pattern forming method and also has high resolution and few development defects after a predetermined period following the preparation of the photosensitive radioactive or radioactive linear resin composition; a photosensitive radioactive or radioactive linear film using the above-mentioned photosensitive radioactive or radioactive linear resin composition; a pattern forming method; a method for manufacturing electronic devices; a photosensitive radioactive or radioactive linear resin composition for photomask manufacturing; and a method for manufacturing photomasks. Detailed Implementation

[0073] The present invention will now be described in detail.

[0074] The following description of the constituent elements is based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment.

[0075] In this specification, "photochemical rays" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet radiation (represented by excimer lasers), extreme ultraviolet (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" refers to photochemical rays or radiation. Unless otherwise stated, "exposure" in this specification includes not only exposures using the bright-line spectrum of a mercury lamp, far-ultraviolet radiation (represented by excimer lasers), extreme ultraviolet radiation, X-rays, and EUV, but also descriptions using particle beams such as electron beams and ion beams.

[0076] In this specification, “~” is used to indicate that the values ​​recorded before and after it are included as lower and upper limits.

[0077] In this specification, (meth)acrylate means at least one of acrylic acid and methacrylate. Furthermore, (meth)acrylic acid means at least one of acrylic acid and methacrylic acid.

[0078] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (also known as "molecular weight distribution") (Mw / Mn) of the resin are defined as polystyrene equivalents determined by GPC using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 °C, flow rate: 1.0 mL / min, detector: refractive index detector).

[0079] In this specification, the designations of groups (atomic groups) that do not specify substitution and unsubstitution include both substituent groups and substituted groups. For example, "alkyl" includes not only unsubstituent alkyl groups (unsubstituted alkyl groups) but also substituent alkyl groups (substituted alkyl groups). Furthermore, "organic group" in this specification refers to a group containing at least one carbon atom.

[0080] Furthermore, in this specification, the type, position, and number of substituents when "substituents may be present" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic groups other than hydrogen atoms, and can be selected from the following substituents T.

[0081] (Substituent T)

[0082] Examples of substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; 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 methyloxazoyl; alkylthioalkyl groups such as methylthioalkyl and tert-butylthioalkyl; arylthioalkyl groups such as phenylthioalkyl and p-tolylthioalkyl; alkyl; cycloalkyl; aryl; heteroaryl; hydroxyl; carboxyl; formyl; sulfonyl; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonamide; silyl; amino; monoalkylamino; dialkylamino; arylamino; nitro; formyl; and combinations thereof.

[0083] Unless otherwise specified, the bonding orientation of the divalent groups marked in this specification is not limited. For example, in a compound represented by the general formula "LMN", when M is -OCO-C(CN)=CH-, if the position bonded to the L side is set as *1 and the position bonded to the N side is set as *2, M can be either *1-OCO-C(CN)=CH-*2 or *1-CH=C(CN)-COO-*2.

[0084] The photosensitive radioactive or radiosensitive linear resin composition involved in this invention (hereinafter also referred to as "the composition of this invention") contains:

[0085] A photosensitive or radiosensitive linear resin composition comprising:

[0086] The solubility of resin (P) in the developing solution changes due to the action of acid;

[0087] Compound (A) has a group (a) whose polarity changes upon decomposition by the action of an acid, and produces an acid (ac1) upon irradiation by photochemical rays or radiation.

[0088] Compound (B), when irradiated with photochemical rays or radiation, produces an acid (ac2) with a higher pKa than the acid (ac1) produced by compound (A); and

[0089] Basic compound (C).

[0090] The composition of the present invention is preferably a photoresist composition, but it can also be a positive photoresist composition or a negative photoresist composition.

[0091] The compositions of the present invention can be resist compositions for alkaline developing or resist compositions for organic solvent developing.

[0092] The composition of the present invention is a positive resist composition, preferably a resist composition for alkaline development.

[0093] Furthermore, the composition of the present invention is preferably a chemically amplified resist composition, and more preferably a chemically amplified positive resist composition.

[0094] The mechanism by which the present invention can solve the above-mentioned problems is not yet fully understood, but the inventors speculate as follows.

[0095] It is believed that in the compound (A) contained in the composition of the present invention, which contains a group (a) whose polarity changes upon decomposition by the action of acid and which generates acid (ac1) upon irradiation by photochemical rays or radiation, the group (a) typically has a group whose polarity increases upon the action of acid. Therefore, the decomposition products of compound (A) after exposure and decomposition can be easily dissolved in alkaline developer, thus suppressing the generation of development defects. Furthermore, it is believed that the increased solubility of the developer in the exposed area can improve the dissolution contrast between the exposed and unexposed areas and improve the resolution of fine patterns. In addition, it is believed that by using compound (B) which generates an acid (ac2) with a pKa higher than that of the acid (ac1) generated from compound (A), the response of the acid-generating agent to exposure can be improved, further improving the resolution of fine patterns.

[0096] Furthermore, it is believed that the composition of the present invention, in addition to compounds (A) and (B), also contains a basic compound (C), thereby mitigating the acidity of the composition and inhibiting the decomposition of group (a) of compound (A) in the composition after a predetermined period following preparation. As a result, it is believed that aggregation based on the polar interaction between decomposition products after a predetermined period following preparation can be suppressed, and resolution degradation or worsening of development defects can be suppressed.

[0097] The same mechanism is also believed to be involved in the formation of negative patterns using resins and crosslinking agents whose solubility in alkaline developing solutions is reduced by crosslinking reactions through the action of acids.

[0098] [Resin (P) whose solubility in developer changes due to the action of acid]

[0099] This section describes resins (P) whose solubility in developer changes due to the action of acid (also simply referred to as "resin (P)").

[0100] One preferred method for resin (P) is to use a resin whose solubility in alkaline developing solution is increased by decomposition through the action of acid.

[0101] The resin (P) is preferably a resin having groups that increase polarity through decomposition by acid (also known as "acid-decomposable groups").

[0102] Acid-degradable resins have acid-degradable groups, thus increasing their solubility in alkaline developing solutions through decomposition by acid.

[0103] Furthermore, another preferred embodiment of the resin (P) is a resin whose solubility in alkaline developing solution is reduced by the action of acid. In this embodiment, the resin (P) is preferably a resin whose solubility in alkaline developing solution is reduced by a cross-linking reaction under the action of acid. Additionally, in this embodiment, the composition of the present invention preferably contains a cross-linking agent. The cross-linking agent will be described later.

[0104] The resin (P) preferably contains repeating units with acid-degradable groups.

[0105] As resin (P), known resins can be appropriately used. For example, as resin (P), known resins disclosed in paragraphs

[0055] to

[0191] of U.S. Patent Application Publication No. 2016 / 0274458A1, paragraphs

[0035] to

[0085] of U.S. Patent Application Publication No. 2015 / 0004544A1, and paragraphs

[0045] to

[0090] of U.S. Patent Application Publication No. 2016 / 0147150A1 are preferred.

[0106] The aforementioned acid-decomposable groups preferably have a structure protected by a group (detached group) that is decomposed and detached by the action of acid.

[0107] Examples of such polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tri(alkylcarbonyl)methylene groups, and tri(alkylsulfonyl)methylene groups (typically groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), as well as alcohol hydroxyl groups.

[0108] Furthermore, the alcohol hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, referring to hydroxyl groups other than those directly bonded to an aromatic ring group (phenolic hydroxyl groups). Aliphatic alcohols (e.g., hexafluoroisopropanol group) whose α-position is replaced by an electron-withdrawing group such as a fluorine atom are excluded. Preferably, the alcohol hydroxyl group has a pKa (acid dissociation constant) of 12 or more and 20 or less.

[0109] The preferred polar groups are carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups.

[0110] Examples of groups that are released by decomposition through the action of acid (release groups) include those represented by formulas (Y1) to (Y4).

[0111] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0112] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0113] Equation (Y3): -C(R) 36 (R) 37 (OR) 38 )

[0114] Equation (Y4): -C(Rn)(H)(Ar)

[0115] In formulas (Y1) and (Y2), Rx1 to Rx3 independently represent alkyl (straight-chain or branched) or cycloalkyl (monocyclic or polycyclic). Furthermore, when all of Rx1 to Rx3 are alkyl (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl.

[0116] Preferably, Rx1 to Rx3 represent straight-chain or branched alkyl groups, and more preferably, Rx1 to Rx3 represent straight-chain alkyl groups.

[0117] Two of Rx1 to Rx3 can also be bonded to form a single ring or multiple rings.

[0118] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0119] As for the cycloalkyl groups Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are preferred.

[0120] The cycloalkyl group formed by the bonding of two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0121] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0122] The group represented by formula (Y1) or formula (Y2) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0123] In formula (Y3), R 36 ~R 38 Each can be used independently to represent a hydrogen atom or a monovalent organic group. R 37 With R 38 They can bond with each other to form rings. Examples of monovalent organic groups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R 36 Hydrogen atoms are preferred.

[0124] As formula (Y3), it is preferably a group represented by the following formula (Y3-1).

[0125] [Chemical Formula 4]

[0126]

[0127] Here, L1 and L2 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, or groups formed by combining them (e.g., groups formed by combining alkyl and aryl).

[0128] M represents a single bond or a divalent linker.

[0129] Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (e.g., a group composed of alkyl and cycloalkyl groups).

[0130] In alkyl and cycloalkyl groups, for example, one of the methylene groups can be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0131] In addition, it is preferred that one of L1 and L2 is a hydrogen atom and the other is an alkyl, cycloalkyl, aryl, or a group composed of alkylene and aryl groups.

[0132] At least two of Q, M and L1 can be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0133] From the viewpoint of miniaturizing the pattern, L2 is preferably a secondary alkyl or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, or norbornyl, while examples of tertiary alkyl groups include tert-butyl or adamantyl. In these cases, the increased Tg (glass transition temperature) or activation energy ensures film strength and suppresses blurring.

[0134] In formula (Y4), Ar represents an aromatic cycloalgyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0135] The resin (P) preferably has an acetal structure.

[0136] The acid-degrading group preferably has an acetal structure. The acetal structure is, for example, a structure in which polar groups such as carboxyl groups, phenolic hydroxyl groups, and fluorinated alcohol groups are protected by groups represented by the above formula (Y3).

[0137] As a repeating unit having an acid-degradable group, it is preferably a repeating unit represented by the following general formula (A).

[0138] [Chemical Formula 5]

[0139]

[0140] In general formula (A), L1 represents a divalent linking group, R1 to R3 represent hydrogen atoms or monovalent substituents, and R4 represents a group that is decomposed and removed by the action of an acid.

[0141] L1 represents a divalent linker. Examples of divalent linkers include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups (e.g., alkylene, cycloalkylene, alkenyl, arylene, etc.) and linkers formed by linking multiple of them. Among these, -CO- and arylene are preferred as L1.

[0142] As an arylene group, phenylene is preferred.

[0143] The alkylene group can be linear or branched. There is no particular limitation on the number of carbon atoms in the alkylene group, but it is preferably 1 to 10, more preferably 1 to 3.

[0144] R1 through R3 each independently represent a hydrogen atom or a monovalent substituent. Examples of monovalent substituents include alkyl, cycloalkyl, or halogen atoms.

[0145] Alkyl groups can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in an alkyl group, but it is preferably 1 to 10, more preferably 1 to 3.

[0146] The cycloalkyl group can be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably set to 3 to 8.

[0147] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0148] R4 represents a group that is decomposed and released by the action of acid (a release group).

[0149] Among them, the groups represented by the above formulas (Y1) to (Y4) can be used as detaching groups, and the group represented by the above formula (Y3) is preferred.

[0150] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituents is preferably 8 or less.

[0151] As a repeating unit having an acid-decomposable group, it is also preferred to be a repeating unit represented by the general formula (AI).

[0152] [Chemical Formula 6]

[0153]

[0154] In the general formula (AI),

[0155] Xa1 represents a hydrogen atom or an alkyl group.

[0156] T represents a single bond or a divalent linker.

[0157] Rx1 to Rx3 each independently represent an alkyl group (straight-chain or branched) or a cycloalkyl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups.

[0158] Two of Rx1 to Rx3 can also be bonded together to form cycloalkyl groups (monocyclic or polycyclic).

[0159] As an alkyl group represented by Xa1, examples include methyl or alkyl groups represented by -CH2-R. 11 The group indicated by R. 11 The organic group representing a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group can be exemplified by alkyl groups having 5 or fewer carbon atoms and acyl groups having 5 or fewer carbon atoms, preferably alkyl groups having 3 or fewer carbon atoms, and more preferably methyl groups. As Xa1, hydrogen atoms, methyl groups, trifluoromethyl groups, or hydroxymethyl groups are preferred.

[0160] Examples of divalent linkers for T include alkylene groups, aromatic cycloalkanes, -COO-Rt- groups, and -O-Rt- groups. In these formulas, Rt represents an alkylene group or a cycloalkylene group.

[0161] T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0162] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0163] As for the cycloalkyl groups Rx1 to Rx3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl.

[0164] The cycloalkyl group formed by the bonding of two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. In addition, polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are also preferred. Among them, monocyclic cycloalkyl groups with 5 to 6 carbon atoms are preferred.

[0165] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0166] The repeating unit represented by the general formula (AI) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0167] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituents is preferably 8 or less.

[0168] As the repeating unit represented by the general formula (AI), the acid-degradable tertiary alkyl methacrylate repeating unit is preferred (Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond repeating unit).

[0169] The resin (P) may contain a single repeating unit with an acid-decomposable group, or it may contain two or more repeating units.

[0170] When the resin (P) contains repeating units with acid-degradable groups, the content of repeating units with acid-degradable groups in the resin (P) (total when there are multiple repeating units with acid-degradable groups) relative to all repeating units in the resin (P) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol%.

[0171] (Repeating units with lactone or sulcinolone groups)

[0172] The resin (P) may also contain repeating units having lactone groups or sulcinolone groups.

[0173] As a lactone group or sulfonolactone group, any group can be used as long as it has a lactone structure or sulfonolactone structure. Preferably, it is a group having a 5-7 membered ring lactone structure or a 5-7 membered ring sulfonolactone structure. More preferably, it is a group formed by fusing other ring structures with a 5-7 membered ring lactone structure in the form of a bicyclic or spirocyclic structure, or a group formed by fusing other ring structures with a 5-7 membered ring sulfonolactone structure in the form of a bicyclic or spirocyclic structure. More preferably, it has a repeating unit containing a group having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21) or a group having a sulfonolactone structure represented by any one of the following general formulas (SL1-1) to (SL1-3). Furthermore, the group having a lactone structure or a sulfonolactone structure can be directly bonded to the main chain. As a preferred structure, groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14) are preferred.

[0174] [Chemical Formula 7]

[0175]

[0176] The lactone or sulopentalide moiety may have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 4 to 7 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 1 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple Rb2 groups can be different, and the multiple Rb2 groups can bond together to form a ring.

[0177] As a repeating unit containing a group having a lactone structure or a sulcinolone structure, examples include repeating units represented by the following general formula (AII).

[0178] [Chemical Formula 8]

[0179]

[0180] In the general formula (AII), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

[0181] Preferred substituents that an alkyl group can have as Rb0 include hydroxyl groups and halogen atoms.

[0182] Examples of halogen atoms that can be represented by Rb0 include fluorine, chlorine, bromine, and iodine. Rb0 is preferably represented by hydrogen or methyl.

[0183] Ab represents a single bond, an alkylene group, a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group composed of combinations thereof. Preferably, it is a single bond or a linker represented by -Ab1-CO2-. Ab1 is a straight-chain or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably methylene, ethylene, cyclohexylene, adamantylene, or norbornylene.

[0184] V represents a group having a lactone or sulfonyl lactone structure.

[0185] The group of V having a lactone structure or a sulcinolone structure is preferably represented by any one of the general formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3).

[0186] Repeating units containing groups having lactone or sulfonyl lactone structures typically have optical isomers, but any optical isomer can be used. Furthermore, a single optical isomer can be used alone, or multiple optical isomers can be used in combination. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, more preferably 95 or higher.

[0187] The following are specific examples of repeating units containing groups having a lactone or sulfonyl lactone structure, but the invention is not limited to these. Additionally, in the formula, Rx represents H, CH3, CH2OH, or CF3.

[0188] [Chemical Formula 9]

[0189]

[0190] [Chemical Formula 10]

[0191]

[0192] The content of repeating units having lactone or sulopentalide groups relative to all repeating units in resin (P) is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 40 mol%.

[0193] (Repeating units with acid groups)

[0194] Resin (P) may also contain repeating units with acid groups.

[0195] As an acid group, it is preferred to have an acid dissociation constant (pKa) of 13 or less.

[0196] The pKa mentioned above has the same meaning as the pKa in the acid produced by the following compound (A) through irradiation with photochemical rays or radiation.

[0197] As a repeating unit having an acid group, the repeating unit represented by formula (B) is preferred.

[0198] [Chemical Formula 11]

[0199]

[0200] R3 represents a hydrogen atom or a monovalent organic group.

[0201] As a monovalent organic group, it is preferably a group represented by -L4-R8. L4 represents a single bond or an ester group. R8 can be an alkyl, cycloalkyl, aryl, or a combination of these groups.

[0202] R4 and R5 represent hydrogen atoms, halogen atoms, or alkyl groups, respectively.

[0203] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0204] L2 represents a single bond or ester group.

[0205] L3 represents an aromatic hydrocarbon cyclic group with a valence of (n+m+1) or an alicyclic hydrocarbon cyclic group with a valence of (n+m+1). Examples of aromatic hydrocarbon cyclic groups include benzene and naphthyl groups. Examples of alicyclic hydrocarbon cyclic groups include monocyclic and polycyclic groups, such as cycloalkyl groups.

[0206] R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Additionally, when R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon cyclic group with a (n+m+1) valence.

[0207] R7 represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0208] m represents an integer greater than or equal to 1. m is preferably an integer from 1 to 3, and more preferably an integer from 1 to 2.

[0209] n represents an integer of 0 or 1 or higher. n is preferably an integer between 1 and 4.

[0210] In addition, (n+m+1) is preferably an integer from 1 to 5.

[0211] As a repeating unit having an acid group, it is preferably a repeating unit represented by the following general formula (I).

[0212] The resin (P) contains repeating units represented by the following general formula (I), and when the composition of the present invention contains a crosslinking agent, the resin (P) reacts with the crosslinking agent by the action of acid, and the solubility of the resin (P) in the alkaline developing solution decreases.

[0213] [Chemical Formula 12]

[0214]

[0215] In general formula (I),

[0216] R 41 R 42 and R 43 Each of these groups independently represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group, or alkoxycarbonyl group. Wherein, R... 42 It can bond with Ar4 to form a ring, at which point R 42 Indicates a single bond or an alkylene group.

[0217] X4 indicates a single bond, -COO-, or -CONR. 64 -, R 64 It represents a hydrogen atom or an alkyl group.

[0218] L4 indicates a single bond or alkylene group.

[0219] Ar4 represents an aromatic ring group with an (n+1) valence, when it is combined with R 42 When bonded to form a ring, it represents an aromatic ring group with an (n+2) valence.

[0220] n represents an integer from 1 to 5.

[0221] R in general formula (I) 41 R 42 and R 43 The alkyl group is preferably an alkyl group with 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, more preferably an alkyl group with 8 or fewer carbon atoms, and even more preferably an alkyl group with 3 or fewer carbon atoms.

[0222] R in general formula (I) 41 R 42 and R 43 The cycloalkyl group can be monocyclic or polycyclic. Preferably, it is a monocyclic cycloalkyl group with 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, or cyclohexyl.

[0223] R in general formula (I) 41 R 42 and R 43 The halogen atom can be fluorine, chlorine, bromine, or iodine, with fluorine being the preferred atom.

[0224] R in general formula (I) 41 R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group is preferably a derivative of the above-mentioned R. 41 R 42 and R 43The alkyl group in the text is the same as the alkyl group in the text.

[0225] Preferred substituents among the aforementioned groups include, for example, alkyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxyl, carboxyl, halogen, alkoxy, thioether, acyl, acyloxy, alkoxycarbonyl, cyano, and nitro groups. The substituent preferably has 8 or fewer carbon atoms.

[0226] Ar4 represents an aromatic cyclic group with an (n+1) valence. When n is 1, the divalent aromatic cyclic group can have substituents, such as arylene groups with 6 to 18 carbon atoms, such as phenylene, tolylene group, naphthylene, and anthracene, or aromatic cyclic groups containing heterocycles, such as thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring.

[0227] As a specific example of an aromatic cyclic group with a valence of (n+1) when n is an integer greater than 2, a group formed by removing (n-1) arbitrary hydrogen atoms from the above specific examples of a divalent aromatic cyclic group can be given.

[0228] (n+1) valence aromatic cyclic groups can also have substituents.

[0229] Substituents that can be present as the above-mentioned alkyl, cycloalkyl, alkoxycarbonyl, alkylene, and (n+1) valence aromatic cyclic groups include, for example, R in general formula (I). 41 R 42 and R 43 The examples listed include alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy alkoxy groups; aryl groups such as phenyl groups; etc.

[0230] As represented by X4 -CONR 64 -(R 64 R in (representing hydrogen atom or alkyl group) 64 Alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, are alkyl groups with 20 or fewer carbon atoms, and preferably alkyl groups with 8 or fewer carbon atoms.

[0231] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0232] The alkylene group in L4 is preferably an alkylene group with 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene.

[0233] Ar4 is preferably an aromatic cyclic group with 6 to 18 carbon atoms, and more preferably a phenylalkyl, naphthyl, or biphenylene alkyl group.

[0234] The repeating unit represented by general formula (I) preferably has a hydroxystyrene structure. That is, Ar4 is preferably a benzenealkyl group.

[0235] As a repeating unit represented by general formula (I), it is preferred to be a repeating unit represented by the following general formula (1).

[0236] [Chemical Formula 13]

[0237]

[0238] In general formula (1),

[0239] A1 represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group.

[0240] R represents a halogen atom, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, alkoxy, alkylcarbonyloxy, alkylsulfonyloxy, alkoxycarbonyl, or aryloxycarbonyl. When multiple Rs are present, they can be the same or different. When multiple Rs are present, they can collectively form an alkyl group. Preferably, R is a hydrogen atom.

[0241] a represents an integer from 1 to 3.

[0242] b represents an integer from 0 to (3-a).

[0243] The following are specific examples of repeating units represented by general formula (I), but the present invention is not limited thereto. In the formula, a represents 1, 2, or 3.

[0244] [Chemical Formula 14]

[0245]

[0246] [Chemical Formula 15]

[0247]

[0248] [Chemical Formula 16]

[0249]

[0250] As the repeating unit having an acid group, the repeating unit specifically described below is preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 1, 2, or 3.

[0251] [Chemical Formula 17]

[0252]

[0253] [Chemical Formula 18]

[0254]

[0255] The content of repeating units having acid groups is preferably 10 to 80 mol% relative to all repeating units in resin (P), more preferably 15 to 75 mol%, and even more preferably 20 to 70 mol%.

[0256] In addition to the repeating structural units mentioned above, resin (P) may also have various repeating units for purposes such as adjusting dry etching resistance, compatibility with standard developer, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0257] Resin (P) can be synthesized by conventional methods (e.g., free radical polymerization). Common synthesis methods include (1) batch polymerization in which monomers and initiators are dissolved in a solvent and then heated for polymerization, and (2) dropwise polymerization in which a solution containing monomers and initiators is added dropwise to a heated solvent over 1 to 10 hours.

[0258] The weight-average molecular weight (Mw) of the resin (P) is preferably 1,000 to 200,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 25,000. The dispersity (Mw / Mn) is typically 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.

[0259] Resin (P) can be used alone or in combination with two or more types.

[0260] In the compositions of the present invention, the content of resin (P) is generally 20% by mass or more relative to the total solids content, preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more. There is no particular upper limit, but it is preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less.

[0261] In addition, the total solids content of the composition of the present invention refers to the components other than the solvent (components capable of forming photosensitive radioactive or radiosensitive linear films).

[0262] [A compound (A) has a group (a) that changes polarity through decomposition by the action of an acid and produces an acid (ac1) upon irradiation by photochemical rays or radiation.]

[0263] The composition of the present invention contains a compound (A) that has a group (a) whose polarity changes upon decomposition by the action of an acid and that produces an acid (ac1) upon irradiation by photochemical rays or radiation (also referred to simply as "compound (A)" or "photoacid generator (A)").

[0264] Compound (A) is a compound that produces acid by exposure to photochemical rays or radiation (photoacid generator).

[0265] The molecular weight of compound (A) is not particularly limited, for example, it is 5000 or less, preferably 3000 or less, and more preferably 2000 or less.

[0266] Compound (A) is preferably a compound that does not have repeating units.

[0267] The compound (A) contains a group (a) whose polarity changes upon decomposition by acid (also simply referred to as "group (a)"). Preferably, the group whose polarity increases upon decomposition by acid (acid-decomposing group).

[0268] When compound (A) has a group (a) that is acid-decomposable, compound (A) is decomposed by acid, thereby increasing its solubility in alkaline developer.

[0269] The aforementioned acid-decomposable groups preferably have a structure protected by a group (detached group) that is decomposed and detached by the action of acid.

[0270] Examples of such polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tri(alkylcarbonyl)methylene groups, and tri(alkylsulfonyl)methylene groups (typically groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), as well as alcohol hydroxyl groups.

[0271] Furthermore, the alcohol hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, referring to hydroxyl groups other than those directly bonded to an aromatic ring group (phenolic hydroxyl groups). Aliphatic alcohols (e.g., hexafluoroisopropanol group) whose α-position is replaced by an electron-withdrawing group such as a fluorine atom are excluded. Preferably, the alcohol hydroxyl group has a pKa (acid dissociation constant) of 12 or more and 20 or less.

[0272] The preferred polar groups are carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups.

[0273] Examples of groups that are released by decomposition through the action of acid (release groups) include those represented by formulas (Y1) to (Y4).

[0274] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0275] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0276] Equation (Y3): -C(R) 36 (R) 37 (OR) 38 )

[0277] Equation (Y4): -C(Rn)(H)(Ar)

[0278] In formulas (Y1) and (Y2), Rx1 to Rx3 independently represent alkyl (straight-chain or branched) or cycloalkyl (monocyclic or polycyclic). Furthermore, when all of Rx1 to Rx3 are alkyl (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl.

[0279] Preferably, Rx1 to Rx3 represent straight-chain or branched alkyl groups, and more preferably, Rx1 to Rx3 represent straight-chain alkyl groups.

[0280] Two of Rx1 to Rx3 can also be bonded to form a single ring or multiple rings.

[0281] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0282] As for the cycloalkyl groups Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are preferred.

[0283] The cycloalkyl group formed by the bonding of two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0284] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0285] The group represented by formula (Y1) or formula (Y2) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0286] In formula (Y3), R 36 ~R 38 Each can be used independently to represent a hydrogen atom or a monovalent organic group. R 37 With R 38 They can bond with each other to form rings. Examples of monovalent organic groups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R 36 Hydrogen atoms are preferred.

[0287] As formula (Y3), it is preferably a group represented by the following formula (Y3-1).

[0288] [Chemical Formula 19]

[0289]

[0290] Here, L1 and L2 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, or groups formed by combining them (e.g., groups formed by combining alkyl and aryl).

[0291] M represents a single bond or a divalent linker.

[0292] Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (e.g., a group composed of alkyl and cycloalkyl groups).

[0293] In alkyl and cycloalkyl groups, for example, one of the methylene groups can be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0294] In addition, it is preferred that one of L1 and L2 is a hydrogen atom and the other is an alkyl, cycloalkyl, aryl, or a group composed of alkylene and aryl groups.

[0295] At least two of Q, M and L1 can be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0296] From the viewpoint of miniaturizing the pattern, L2 is preferably a secondary alkyl or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, or norbornyl, while examples of tertiary alkyl groups include tert-butyl or adamantyl. In these cases, the increased Tg (glass transition temperature) or activation energy ensures film strength and suppresses blurring.

[0297] In formula (Y4), Ar represents an aromatic cycloalgyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0298] The group (a) in compound (A) preferably has an acetal structure.

[0299] An acetal structure is, for example, a structure in which polar groups such as carboxyl, phenolic hydroxyl, and fluorinated alcohol are protected by groups represented by the above formula (Y3).

[0300] The group (a) in compound (A) is particularly preferably a group represented by the following general formula (T-1).

[0301] [Chemical Formula 20]

[0302]

[0303] In general formula (T-1),

[0304] R 11 It represents a hydrogen atom or an alkyl group.

[0305] R 12 It represents a hydrogen atom, alkyl, cycloalkyl, or aryl group, and the aforementioned alkyl and cycloalkyl groups may contain ether bonds or carbonyl bonds.

[0306] R 13 The alkyl, cycloalkyl, or aryl groups may contain ether or carbonyl bonds.

[0307] R 11 and R 12 They can bond together to form a ring.

[0308] R 12 and R 13 They can bond together to form a ring.

[0309] * indicates a link key.

[0310] The groups represented by the general formula (T-1) will be described later.

[0311] Compound (A) is preferably a compound represented by the following general formula (b1).

[0312] [Chemical Formula 21]

[0313]

[0314] In general formula (b1), L represents a single-bonded or divalent linker. When multiple Ls are present, they can be the same or different. A represents a group whose polarity changes through decomposition by acid (a). When multiple As are present, they can be the same or different. n represents an integer from 1 to 5. X represents a linker with a valence of n+1. M + This indicates a sulfonium ion or an iodonium ion.

[0315] In general formula (b1), X represents an n+1 valence linking basis.

[0316] The linking group represented by X is not particularly limited. Examples include aliphatic groups (which can be linear, branched, or cyclic), aromatic groups, -O-, -CO-, -COO-, -OCO-, and groups composed of two or more of these.

[0317] As the aforementioned aliphatic group, it is preferred to form a group formed by removing n hydrogen atoms from an alkyl group (which can be straight-chain or branched, preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 10 carbon atoms) and a group formed by removing n hydrogen atoms from a cycloalkyl group (which can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 5 to 10 carbon atoms).

[0318] The aforementioned aliphatic group may have substituents, such as the aforementioned substituent T.

[0319] The aforementioned aliphatic groups can have heteroatoms (such as sulfur atoms, oxygen atoms, nitrogen atoms, etc.) between carbon-carbon atoms.

[0320] As the aforementioned aromatic group, it is preferable to form a group by removing n hydrogen atoms from the aryl group (preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 10 carbon atoms).

[0321] The aforementioned aromatic group may have substituents, such as the aforementioned substituent T.

[0322] The aforementioned aromatic groups may have heteroatoms (such as sulfur atoms, oxygen atoms, nitrogen atoms, etc.) between carbon atoms.

[0323] X is preferably an aromatic group with an n+1 valence.

[0324] In general formula (b1), n ​​represents an integer from 1 to 5, preferably an integer from 1 to 3, more preferably 2 or 3, and even more preferably 3.

[0325] In general formula (b1), L represents a single bond or a divalent linker.

[0326] The divalent linker represented by L is not particularly limited. Examples include aliphatic groups (which can be linear, branched, or cyclic), aromatic groups, -O-, -CO-, -COO-, -OCO-, and groups formed by combining two or more of these groups.

[0327] As the aforementioned aliphatic group, alkylene groups (which can be linear or branched, preferably alkylene groups with 1 to 20 carbon atoms, more preferably alkylene groups with 1 to 10 carbon atoms) and cycloalkylene groups (which can be monocyclic or polycyclic, preferably cycloalkylene groups with 3 to 20 carbon atoms, more preferably cycloalkylene groups with 5 to 10 carbon atoms) are preferred.

[0328] The aforementioned aliphatic group may have substituents, such as the aforementioned substituent T.

[0329] The aforementioned aliphatic groups can have heteroatoms (such as sulfur atoms, oxygen atoms, nitrogen atoms, etc.) between carbon-carbon atoms.

[0330] As the aforementioned aromatic group, a arylene group is preferred (preferably a arylene group with 6 to 20 carbon atoms, more preferably a arylene group with 6 to 10 carbon atoms).

[0331] The aforementioned aromatic group may have substituents, such as the aforementioned substituent T.

[0332] The aforementioned aromatic groups may have heteroatoms (such as sulfur atoms, oxygen atoms, nitrogen atoms, etc.) between carbon atoms.

[0333] L is preferably a aryl group.

[0334] In general formula (b1), A represents a group (a) whose polarity changes upon decomposition by the action of an acid, and preferably represents an acid-decomposable group. Specific examples and preferred ranges of acid-decomposable groups are as described above.

[0335] A is particularly preferably selected from at least one group represented by the following general formula (T-1) and the following general formula (T-2), and most preferably a group represented by the following general formula (T-1).

[0336] [Chemical Formula 22]

[0337]

[0338] In general formula (T-1),

[0339] R 11 It represents a hydrogen atom or an alkyl group.

[0340] R 12 It represents a hydrogen atom, alkyl, cycloalkyl, or aryl group, and the aforementioned alkyl and cycloalkyl groups may contain ether bonds or carbonyl bonds.

[0341] R 13 The alkyl, cycloalkyl, or aryl groups may contain ether or carbonyl bonds.

[0342] R 11 and R 12They can bond together to form a ring.

[0343] R 12 and R 13 They can bond together to form a ring.

[0344] * indicates a link key.

[0345] In general formula (T-2),

[0346] R 21 R 22 and R 23 Alkyl groups are represented independently.

[0347] R 21 ~R 23 Two of them can bond together to form a ring.

[0348] * indicates a link key.

[0349] In general formula (T-1), R 11 It represents a hydrogen atom or an alkyl group.

[0350] When R 11 When referring to an alkyl group, the alkyl group can be either straight-chain or branched, preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably alkyl groups having 1 to 3 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, and octyl.

[0351] The alkyl group described above may have substituents, such as the substituent T mentioned above.

[0352] R 11 Preferably, it is an alkyl group having 1 to 3 carbon atoms, and more preferably, it is a hydrogen atom.

[0353] In general formula (T-1), R 12 It represents a hydrogen atom, alkyl, cycloalkyl, or aryl group.

[0354] When R 12 When referring to an alkyl group, the alkyl group can be either straight-chain or branched, preferably having 1 to 10 carbon atoms, and more preferably having 1 to 5 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, and octyl.

[0355] The alkyl group described above may have substituents, such as the substituent T mentioned above.

[0356] The alkyl group mentioned above may contain ether bonds or carbonyl bonds.

[0357] When R 12When referring to a cycloalkyl group, it can be a monocyclic or polycyclic compound, preferably with 3 to 20 carbon atoms, more preferably with 5 to 15 carbon atoms, and even more preferably with 5 to 10 carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, norbornyl, isobornyl, camphenyl, dicyclopentyl, α-pinel, tricyclodecyl, tetracyclododecyl, and androstyl.

[0358] The aforementioned cycloalkyl groups may have substituents, such as the aforementioned substituent T.

[0359] The aforementioned cycloalkyl groups may contain ether bonds or carbonyl bonds.

[0360] When R 12 When representing an aryl group, it is preferred that the aryl group has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of aryl groups include phenyl and naphthyl groups.

[0361] The aryl group mentioned above may have substituents, such as the substituent T mentioned above.

[0362] Preferred R 12 It is an alkyl group having 1 to 5 hydrogen atoms or carbon atoms.

[0363] In general formula (T-1), R 13 It indicates alkyl, cycloalkyl, or aryl.

[0364] R 13 The alkyl, cycloalkyl, or aryl groups represented are related to the above R. 12 The group represented is the same as the alkyl, cycloalkyl, or aryl group recorded.

[0365] R 13 Preferably, it is an alkyl group having 1 to 5 carbon atoms.

[0366] R 11 and R 12 They can bond together to form a ring.

[0367] As R 11 and R 12 The rings formed by bonding together are preferably aliphatic rings.

[0368] The aliphatic ring is preferably a cycloalkane with 3 to 20 carbon atoms, and more preferably a cycloalkane with 5 to 15 carbon atoms. The cycloalkane can be monocyclic or polycyclic.

[0369] The aforementioned aliphatic ring may have substituents, such as the aforementioned substituent T.

[0370] The aforementioned aliphatic rings can have heteroatoms (such as sulfur atoms, oxygen atoms, nitrogen atoms, etc.) between carbon atoms.

[0371] R 12 and R 13 They can bond together to form a ring.

[0372] As R 12 and R 13 The rings formed by bonding together are preferably aliphatic rings whose ring members contain oxygen atoms.

[0373] The aliphatic ring described above preferably has 3 to 20 carbon atoms, more preferably 5 to 15 carbon atoms. The aliphatic ring can be a monocyclic or polycyclic ring.

[0374] The aforementioned aliphatic ring may have substituents, such as the aforementioned substituent T.

[0375] The aforementioned aliphatic rings may have heteroatoms other than oxygen atoms (such as sulfur atoms, nitrogen atoms, etc.) between carbon-carbon atoms.

[0376] In general formula (T-1), R 11 and R 12 They do not bond with each other, and R 12 and R 13 One of the preferred embodiments of the present invention is the method of bonding together to form a ring.

[0377] In general formula (T-2), R 21 R 22 and R 23 Alkyl groups are represented independently.

[0378] When R 21 R 22 and R 23 When referring to an alkyl group, there is no particular limitation on what constitutes an alkyl group; it can be either straight-chain or branched. For example, alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl, are preferred.

[0379] The alkyl group described above may have substituents. Examples of substituents include aryl (e.g., 6 to 15 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (e.g., 1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (e.g., 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0380] R 21 ~R 23 Two of them can bond together to form a ring.

[0381] When R 21 ~R23 When two of them bond together to form a ring, R is preferred. 21 ~R 23 Two atoms in the cycloalkyl group are bonded together to form a cycloalkyl group. The cycloalkyl group can be a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, or adamantyl. Preferably, it is a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0382] In the aforementioned cycloalkyl groups, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0383] In general formula (b1), M + This indicates a sulfonium ion or an iodonium ion.

[0384] M + The sulfonium ion or iodonium ion represented preferably does not have a nitrogen atom.

[0385] M + There are no particular limitations, but cations represented by the following general formula (ZIA) or general formula (ZIIA) are preferred.

[0386] [Chemical Formula 23]

[0387]

[0388] In the above general formula (ZIA),

[0389] R 201 R 202 and R 203 Each organic group can be represented independently.

[0390] As R 201 R 202 and R 203 The number of carbon atoms in the organic groups is generally 1 to 30, preferably 1 to 20.

[0391] Furthermore, R 201 ~R 203 The two atoms in the ring can bond together to form a ring structure, or the ring can contain oxygen atoms, sulfur atoms, ester bonds, amide bonds, or carbonyl groups. As R... 201 ~R 203 Examples of groups formed by the bonding of two molecules include alkylene groups (e.g., butylene, pentylene) and -CH2-CH2-O-CH2-CH2-.

[0392] Preferred cations of the general formula (ZIA) include cations (ZI-11), cation (ZI-12), cation (ZI-13) represented by the general formula (ZI-13) and cation (ZI-14) represented by the general formula (ZI-14).

[0393] When n is 2 or more, a cation with a valence of 2 or higher can be a cation having multiple structures represented by the general formula (ZIA). Examples of such cations include R, which has a cation represented by the general formula (ZIA). 201 ~R 203 At least one of them has an R with another cation represented by the general formula (ZIA). 201 ~R 203 At least one of the divalent cations in the structure formed by bonding via a single bond or a linker group.

[0394] First, the cation (ZI-11) will be explained.

[0395] The cation (ZI-11) is R of the above general formula (ZIA). 201 ~R 203 At least one of them is an aryl cation, i.e., an arylsulfonium cation.

[0396] In arylsulfonium cations, R can be 201 ~R 203 All are aryl, or can be R 201 ~R 203 One part of it is aryl, and the rest is alkyl or cycloalkyl.

[0397] Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0398] The aryl group contained in the arylsulfonium cation is preferably phenyl or naphthyl, more preferably phenyl. The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom, nitrogen atom, or sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups can be the same or different.

[0399] The alkyl or cycloalkyl group of the arylsulfonium cation is preferably a straight-chain alkyl group with 1 to 15 carbon atoms, a branched alkyl group with 3 to 15 carbon atoms, or a cycloalkyl group with 3 to 15 carbon atoms. Examples include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

[0400] R 201 ~R 203 The aryl, alkyl, and cycloalkyl groups may each independently have alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 14 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), halogen atom, hydroxyl, lactone cyclogroup, or phenylthio group as substituents.

[0401] As a lactone cyclic group, examples include groups obtained by removing hydrogen atoms from any of the structures represented by (KA-1-1) to (KA-1-17) described below.

[0402] Next, the cation (ZI-12) will be explained.

[0403] The cation (ZI-12) is R in formula (ZIA). 201 ~R 203 Each of these refers independently to a compound that does not have an aromatic ring. Here, the aromatic ring also includes aromatic rings containing heteroatoms.

[0404] As R 201 ~R 203 Organic groups that do not have aromatic rings, typically have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0405] R 201 ~R 203 Each of the following is preferably alkyl, cycloalkyl, allyl, or vinyl, more preferably linear or branched 2-oxoalkyl, 2-oxocycloalkyl, or alkoxycarbonylmethyl, and even more preferably linear or branched 2-oxoalkyl.

[0406] As R 201 ~R 203 The alkyl and cycloalkyl groups in the form of alkyl groups are preferably straight-chain alkyl groups with 1 to 10 carbon atoms or branched alkyl groups with 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups with 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0407] R 201 ~R 203 It can be further substituted by halogen atoms, alkoxy groups (e.g., carbon atoms of 1 to 5), hydroxyl groups, cyano groups, or nitro groups.

[0408] Next, the cation (ZI-13) will be explained.

[0409] [Chemical Formula 24]

[0410]

[0411] In general formula (ZI-13), Q1 represents alkyl, cycloalkyl, or aryl, and when it has a ring structure, the ring structure may include at least one of oxygen atom, sulfur atom, ester bond, amide bond, and carbon-carbon double bond. R 6c and R 7c Each can independently represent a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group, or aryl group. R 6c With R 7c They can bond together to form a ring. R x and R y Each can be independently represented as alkyl, cycloalkyl, or alkenyl. R x and R y They can bond together to form a ring. Furthermore, they are selected from Q1 and R. 6c and R 7c At least two of them can bond together to form a ring structure, which may contain carbon-carbon double bonds.

[0412] In general formula (ZI-13), the alkyl and cycloalkyl groups represented by Q1 are preferably straight-chain alkyl groups with 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), branched alkyl groups with 3 to 15 carbon atoms (preferably 3 to 10 carbon atoms), or cycloalkyl groups with 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Specifically, examples include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclohexyl, and norbornyl.

[0413] The aryl group represented by Q1 is preferably phenyl or naphthyl, more preferably phenyl. The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom or a sulfur atom, etc. Examples of heterocyclic structures include furan rings, thiophene rings, benzofuran rings, and benzothiophene rings.

[0414] The aforementioned Q1 may further have substituents. For example, benzyl groups can be used as Q1.

[0415] In addition, when Q1 has a ring structure, the ring structure may include at least one of oxygen atom, sulfur atom, ester bond, amide bond and carbon-carbon double bond.

[0416] As a result of R 6c and R 7c The alkyl, cycloalkyl, and aryl groups represented can be the same groups as those in Q1 above, and their preferred methods are also the same. Furthermore, R... 6c With R 7c They can bond together to form a ring.

[0417] As a result of R 6c and R 7c Halogen atoms can be represented by, for example, fluorine, chlorine, bromine, and iodine atoms.

[0418] As a result of R x and R y The alkyl and cycloalkyl groups represented can be the same groups as those in Q1 above, and their preferred methods are also the same.

[0419] As a result of R x and R y The alkenyl group represented is preferably allyl or vinyl.

[0420] The above R x and R y It can further have substituents. In this way, for example, as R... x and R y Examples include 2-oxoalkyl or alkoxycarbonylalkyl.

[0421] As a result of R x and R y The 2-oxoalkyl group can be exemplified by groups having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), specifically 2-oxopropyl and 2-oxobutyl.

[0422] As a result of R x and R y The alkoxycarbonyl alkyl group represented can be, for example, a group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Furthermore, R x With R y They can bond together to form a ring.

[0423] R x With R y The ring structure formed by interconnected elements can contain oxygen atoms, sulfur atoms, ester bonds, amide bonds, or carbon-carbon double bonds.

[0424] In general formula (ZI-13), Q1 and R 6c They can bond together to form ring structures, and the formed ring structures can contain carbon-carbon double bonds.

[0425] The cation (ZI-13) is preferably a cation (ZI-13A).

[0426] The cation (ZI-13A) is a benzoylmethylsulfonium cation represented by the following general formula (ZI-13A).

[0427] [Chemical Formula 25]

[0428]

[0429] In general formula (ZI-13A),

[0430] R 1c ~R 5cEach of these can be independently represented as a hydrogen atom, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio, or arylthio.

[0431] As R 6c and R 7c R in the above general formula (ZI-13) 6c and R 7c The meanings are the same, and their preferred methods are also the same.

[0432] As R x and R y R in the above general formula (ZI-13) x and R y The meanings are the same, and their preferred methods are also the same.

[0433] R 1c ~R 5c Any two or more of them, R x With R y They can bond together to form ring structures, which can independently contain oxygen atoms, sulfur atoms, ester bonds, amide bonds, or carbon-carbon double bonds. Furthermore, R... 5c and R 6c R 5c and R x They can bond together to form ring structures, each of which can independently contain carbon-carbon double bonds. Furthermore, R... 6c With R 7c They can bond together to form a ring structure.

[0434] Examples of the aforementioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of ring structures include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0435] As R 1c ~R 5c Any two or more of them, R 6c With R 7c and R x With R y Examples of groups formed by bonding include butylene and pentylene.

[0436] As R 5c With R 6c and R 5c With R x The bonded group is preferably a single bond or an alkylene group. Examples of alkylene groups include methylene and ethylene.

[0437] Next, the cation (ZI-14) will be explained.

[0438] The cation (ZI-14) is represented by the following general formula (ZI-14).

[0439] [Chemical Formula 26]

[0440]

[0441] In general formula (ZI-14),

[0442] 1 represents an integer from 0 to 2.

[0443] r represents an integer from 0 to 8.

[0444] R 13 This refers to a group containing a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may also have substituents.

[0445] When there are multiple R 14 When used independently, these groups represent alkyl, cycloalkyl, alkoxy, alkylsulfonyl, cycloalkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, or alkoxy groups having a monocyclic or polycyclic cycloalkyl skeleton. These groups may also have substituents.

[0446] R 15 Each group can independently represent an alkyl, cycloalkyl, or naphthyl group. These groups may also have substituents. Two R groups 15 They can bond together to form a ring. When two Rs 15 When bonds are formed into a ring, heteroatoms such as oxygen or nitrogen atoms can be contained within the ring framework. In one embodiment, two R atoms are preferred. 15 They are alkylene groups and are bonded together to form a ring structure.

[0447] In general formula (ZI-14), R 13 R 14 and R 15 The alkyl group is either straight-chain or branched. The alkyl group preferably has 1 to 10 carbon atoms. More preferably, it is methyl, ethyl, n-butyl, or tert-butyl.

[0448] Next, the general formula (ZIIA) will be explained.

[0449] In general formula (ZIIA), R 204 and R 205 Each can be represented independently as aryl, alkyl, or cycloalkyl.

[0450] As R 204 and R 205 The aryl group is preferably phenyl or naphthyl, more preferably phenyl.204 and R 205 The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of aryl groups with heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0451] As R 204 and R 205 Alkyl and cycloalkyl groups, preferably straight-chain alkyl groups with 1 to 10 carbon atoms or branched alkyl groups with 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl) or cycloalkyl groups with 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0452] R 204 and R 205 The aryl, alkyl, and cycloalkyl groups can each independently have substituents. As R 204 ~R 207 The aryl, alkyl, and cycloalkyl groups may have substituents, such as alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 15 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), halogen atom, hydroxyl, lactone cyclogroup, and phenylthio group.

[0453] As a lactone cyclic group, examples include groups obtained by removing hydrogen atoms from the structures represented by any one of (KA-1-1) to (KA-1-17) below.

[0454] [Chemical Formula 27]

[0455]

[0456] Structures containing the above-described lactone ring structure may or may not have substituents. Examples of substituents include the aforementioned substituent T.

[0457] The following shows M + These are preferred examples, but the invention is not limited to these. Me represents methyl, and Bu represents n-butyl.

[0458] [Chemical Formula 28]

[0459]

[0460] [Chemical Formula 29]

[0461]

[0462] [Chemical Formula 30]

[0463]

[0464] [Chemical Formula 31]

[0465]

[0466] Compound (A) is preferably represented by the following general formula (b2).

[0467] [Chemical Formula 32]

[0468]

[0469] In general formula (b2), L represents a single-bonded or divalent linker. When multiple Ls are present, they can be the same or different. A represents a group whose polarity changes through decomposition by acid (a). When multiple As are present, they can be the same or different. n represents an integer from 1 to 5. M + This indicates a sulfonium ion or an iodonium ion.

[0470] L, A, n and M in general formula (b2) + Corresponding to L, A, n and M in the aforementioned general formula (b1) respectively + same.

[0471] Compound (A) is particularly preferred to be represented by the following general formula (b3).

[0472] [Chemical Formula 33]

[0473]

[0474] In general formula (b3), L represents a single-bonded or divalent linker. When multiple Ls are present, they can be the same or different. A represents a group whose polarity changes through decomposition by acid (a). When multiple As are present, they can be the same or different. o, p, and q independently represent integers from 0 to 5. The sum of o, p, and q is greater than 1 and less than 5. M + This indicates a sulfonium ion or an iodonium ion.

[0475] L, A and M in general formula (b3) + respectively with L, A and M in the above general formula (b1) + same.

[0476] In general formula (b3), o, p and q preferably represent integers from 0 to 3 independently, more preferably integers from 0 to 2, and even more preferably 0 or 1.

[0477] The following are preferred examples of the anionic moiety of compound (A), but the invention is not limited to these.

[0478] [Chemical Formula 34]

[0479]

[0480] [Chemical Formula 35]

[0481]

[0482] [Chemical Formula 36]

[0483]

[0484] Compound (A) produces an acid (ac1) when exposed to photochemical rays or radiation.

[0485] The pKa of the acid (ac1) is preferably -12 or more and 0 or less, more preferably -5 or more and 0 or less, and even more preferably -2 or more and 0 or less.

[0486] In addition, compound (A) has a group (a) whose polarity changes upon decomposition by the action of an acid. However, when the acid (ac1) has the group (a), the pKa of the acid (ac1) is the pKa of the group (a) before it is decomposed by the action of the acid.

[0487] In this specification, pKa (acid dissociation constant) refers to the pKa in aqueous solution, specifically, a value calculated using software package 1 described below from a database of Hammett substituent constants and known literature values. Except as otherwise provided, all pKa values ​​described in this specification are values ​​calculated using software package 1.

[0488] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007ACD / Labs).

[0489] On the other hand, pKa can also be determined using molecular orbital algorithms. As a specific example of this method, calculating H₂ in the solvent based on thermodynamic cycles can be used. + The method for calculating the dissociation free energy (in addition, in this specification, water is usually used as the solvent mentioned above, and DMSO (dimethyl sulfoxide) is used when pKa cannot be determined by water).

[0490] Regarding H + Methods for calculating the dissociation free energy include, for example, the density functional method (DFT), but various other methods have been reported in the literature and are not limited to this. Furthermore, several software programs exist capable of implementing the DFT, such as Gaussian16.

[0491] As mentioned above, pKa in this specification refers to the value obtained by using software package 1 to calculate a database of substituent constants based on Hammett and known literature values. However, when pKa cannot be calculated by this method, the value obtained by Gaussian16 based on DFT (density functional method) is used.

[0492] As a preferred example of compound (A), the compounds used in the examples and compounds formed by combining the above-mentioned anions and cations can be cited.

[0493] Compound (A) can be synthesized, for example, by using a coupling reaction.

[0494] Coupling reactions, for example, can be applied using Suzuki coupling. Countercations can be converted into the desired cations, for example, by anion exchange methods or conversion methods based on ion exchange resins, as described in Japanese Patent Application Publication No. 6-184170.

[0495] Compound (A) can be used alone or in combination with two or more compounds.

[0496] In the composition of the present invention, the content of compound (A) (total when multiple compounds are present) is based on the total solid content of the composition of the present invention, preferably 5 to 60% by mass, more preferably 10 to 50% by mass, further preferably 15 to 50% by mass, and especially preferably 15 to 40% by mass.

[0497] [Compound (B) produces an acid (ac2) with a higher pKa than the acid (ac1) produced by compound (A) mentioned above, through irradiation with photochemical rays or radiation.]

[0498] The composition of the present invention contains a compound (B) (also referred to simply as "compound (B)" or "photoacid generator (B)") that, upon irradiation with photochemical rays or radiation, produces an acid (ac2) with a pKa higher than that produced by the acid (ac1) from the compound (A) described above.

[0499] Compound (B) is a compound that produces acid by exposure to photochemical rays or radiation (photoacid generator).

[0500] The pKa of the acid (ac2) produced by compound (B) is higher than that of the acid (ac1) produced by compound (A).

[0501] The pKa of the acid (ac2) produced by compound (B) is preferably 1 or more higher than the pKa of the acid (ac1) produced by compound (A).

[0502] The difference between the pKa of acid (ac2) and the pKa of acid (ac1) is preferably 2 or more and 17 or less, more preferably 2 or more and 9 or less, and even more preferably 3 or more and 5 or less.

[0503] The pKa of the acid (ac2) is preferably -0.5 or more and 10 or less, more preferably 2 or more and 8 or less, and even more preferably 3 or more and 5 or less.

[0504] Compound (B) is preferably a compound represented by the following general formula (B-1).

[0505] [Chemical Formula 37]

[0506]

[0507] In general formula (B-1), R 51 M represents a monovalent organic group. + This indicates a sulfonium cation or an iodonium cation.

[0508] R in general formula (B-1) 51 The monovalent organic group represented is preferably alkyl, cycloalkyl, aryl, or heterocyclic, and preferably aryl.

[0509] When R 51 When referring to an alkyl group, the alkyl group can be either straight-chain or branched, preferably having 1 to 10 carbon atoms, and more preferably having 1 to 5 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, and octyl.

[0510] The alkyl group described above may have substituents, such as the substituent T mentioned above.

[0511] The alkyl group mentioned above may contain ether bonds or carbonyl bonds.

[0512] When R 51 When referring to a cycloalkyl group, it can be a monocyclic or polycyclic compound, preferably with 3 to 20 carbon atoms, more preferably with 5 to 15 carbon atoms, and even more preferably with 5 to 10 carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, norbornyl, isobornyl, camphenyl, dicyclopentyl, α-pinel, tricyclodecyl, tetracyclododecyl, and androstyl.

[0513] The aforementioned cycloalkyl groups may have substituents, such as the aforementioned substituent T.

[0514] The aforementioned cycloalkyl groups may contain ether bonds or carbonyl bonds.

[0515] When R 51When representing an aryl group, it is preferred that the aryl group has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of aryl groups include phenyl and naphthyl, with phenyl being the most preferred.

[0516] The aryl group mentioned above may have substituents, such as the substituent T mentioned above.

[0517] When R 51 When referring to a heterocyclic group, it is preferred that the heterocyclic group has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms. Examples of heteroatoms present in the heterocyclic group include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0518] The aforementioned heterocyclic group may have substituents, such as the aforementioned substituent T.

[0519] M in general formula (B-1) + M in the above general formula (b1) + The meanings are the same, and the specific examples and preferred ranges are also the same.

[0520] Compound (B) can be used alone or in combination with two or more compounds.

[0521] In the compositions of the present invention, the content of compound (B) (total when multiple compounds are present) is based on the total solid content of the compositions of the present invention, preferably 1 to 30% by mass, more preferably 2 to 30% by mass, further preferably 5 to 15% by mass, and especially preferably 5 to 10% by mass.

[0522] In the composition of the present invention, the molar ratio of compound (A) to compound (B), i.e., (A) / (B), is preferably 0.2 or more and 2.0 or less, more preferably 0.2 or more and 1.5 or less. By setting the molar ratio of (A) / (B) to 0.2 or more and 2.0 or less, it is possible to obtain a composition with minimal performance degradation even after a certain period of time following preparation, while simultaneously achieving improved resolution and reduced development defects based on compound (B).

[0523] [Basic compound (C)]

[0524] The basic compound (C) (also simply referred to as "compound (C)") contained in the compositions of the present invention will be described.

[0525] Basic compounds (C) can function as acid diffusion control agents.

[0526] The acid diffusion control agent acts as a quencher, which captures the acid generated by photoacid generators during exposure and inhibits the reaction of acid-decomposing resin in the unexposed area due to excessive acid production.

[0527] The basic compound (C) is preferably a nitrogen-containing compound.

[0528] The basic compound (C) is preferably a compound having a structure represented by any one of the following general formulas (c1) to (c5).

[0529] [Chemical Formula 38]

[0530]

[0531] In general formulas (c1) and (c5),

[0532] R 200 R 201 and R 202 They can be the same or different, and each can independently represent a hydrogen atom, an alkyl group (preferably with 1 to 20 carbon atoms), a cycloalkyl group (preferably with 3 to 20 carbon atoms), or an aryl group (with 6 to 20 carbon atoms). R 201 With R 202 They can bond together to form a ring.

[0533] R 203 R 204 R 205 and R 206 They can be the same or different, and each can independently represent an alkyl group having 1 to 20 carbon atoms.

[0534] The alkyl groups in general formulas (c1) and (c5) may have substituents or may not be substituted.

[0535] Regarding the aforementioned alkyl group, as an 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 are preferred.

[0536] The alkyl groups in general formulas (c1) and (c5) are more preferably unsubstituted.

[0537] As a basic compound (C), preferably it is a thiazole, benzothiazole, oxazole, benzoxazole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, or a compound having these structures. More preferably it is a compound having a thiazole structure, a benzothiazole structure, an oxazole structure, a benzoxazole structure, an imidazole structure, a diazabicyclic structure, a ium hydroxide structure, a ium 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, etc.

[0538] A basic compound (C) can be a basic compound (CB) whose basicity is reduced or eliminated by irradiation with photochemical rays or radiation (hereinafter, also simply referred to as "compound (CB)"). A compound (CB) is a compound that has a proton acceptor functional group and whose proton acceptor properties are reduced, eliminated, or changed from proton acceptor to acidic by irradiation with photochemical rays or radiation.

[0539] A proton acceptor functional group is a functional group that has a group or electrons capable of electrostatically interacting with a proton. For example, it may represent 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. A nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure as shown in the following formula.

[0540] [Chemical Formula 39]

[0541]

[0542] Preferred partial structures for proton acceptor functional groups include, for example, crown ether structures, azacrown ether structures, primary amine structures, secondary amine structures, tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures.

[0543] Compound (CB) can decompose upon exposure to photochemical rays or radiation, thereby reducing or eliminating its proton acceptor property, or transforming it from proton acceptor property to acidic property. Here, the reduction or elimination of proton acceptor property, or the transformation from proton acceptor property to acidic property, is a change in proton acceptor property resulting from the addition of a proton to a proton acceptor functional group. Specifically, this means that when a proton adduct is formed from a compound (CB) having a proton acceptor functional group and a proton, the equilibrium constant in this chemical equilibrium decreases.

[0544] Proton acceptor properties can be confirmed by pH measurement.

[0545] The pKa of the compound produced by the decomposition of compound (CB) by irradiation with photochemical rays or radiation preferably satisfies pKa < -1, more preferably satisfies -13 < pKa < -1, and even more preferably satisfies -13 < pKa < -3.

[0546] The basic compound (C) can be a low-molecular-weight compound (CD) having a nitrogen atom and a group that can be removed by the action of an acid (hereinafter also referred to as "compound (CD)"). The compound (CD) is preferably an amine derivative having a group that can be removed by the action of an acid on the nitrogen atom.

[0547] The group that is removed by the action of acid is preferably an acetal group, carbonate group, carbamate group, tertiary ester group, tertiary hydroxyl group or hemiacetal ether group, more preferably a carbamate group or hemiacetal ether group.

[0548] The molecular weight of the compound (CD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.

[0549] Compound (CD) may also have a urethane group with a protecting group on the nitrogen atom. The protecting group constituting the urethane group is represented by the following general formula (d-1).

[0550] [Chemical Formula 40]

[0551]

[0552] In general formula (d-1),

[0553] Rb can independently represent a hydrogen atom, an alkyl group (preferably with 1 to 10 carbon atoms), a cycloalkyl group (preferably with 3 to 30 carbon atoms), an aryl group (preferably with 3 to 30 carbon atoms), an aralkyl group (preferably with 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably with 1 to 10 carbon atoms). Rb can bond with each other to form a ring.

[0554] The alkyl, cycloalkyl, aryl, and aralkyl groups represented by Rb can be independently substituted by functional groups such as hydroxyl, amino, pyrrolidyl, piperidinyl, morpholino, oxo, alkoxy, or halogen atoms. The same applies to the alkoxyalkyl groups represented by Rb.

[0555] As Rb, it is preferably a straight-chain or branched alkyl, cycloalkyl, or aryl group, more preferably a straight-chain or branched alkyl or cycloalkyl group.

[0556] Examples of rings formed by two interconnected Rb groups include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and their derivatives.

[0557] As a specific structure of a group represented by the general formula (d-1), examples can be found in paragraph

[0466] of the specification in U.S. Patent Publication US2012 / 0135348A1, but it is not limited thereto.

[0558] The compound (CD) preferably has a structure represented by the following general formula (6).

[0559] [Chemical Formula 41]

[0560]

[0561] In general formula (6),

[0562] 1 represents an integer from 0 to 2, m represents an integer from 1 to 3, and l + m = 3.

[0563] Ra represents a hydrogen atom, alkyl, cycloalkyl, aryl, or aralkyl group. When 1 is 2, the two Ra atoms can be the same or different, and the two Ra atoms can also be connected to each other to form a heterocycle together with the nitrogen atom in the formula. The heterocycle may also contain heteroatoms other than the nitrogen atom in the formula.

[0564] The meaning of Rb is the same as that of Rb in the above general formula (d-1), and the preferred examples are also the same.

[0565] In general formula (6), the alkyl, cycloalkyl, aryl and aralkyl groups that are Ra can be substituted by the same groups as the groups mentioned above, and the groups that are alkyl, cycloalkyl, aryl and aralkyl groups that are Rb can be substituted.

[0566] As specific examples of the alkyl, cycloalkyl, aryl, and aralkyl groups of Ra (these groups can be substituted by the above groups), the same groups as those in the specific examples for Rb can be cited.

[0567] As a particularly preferred example of the compound (DD) in this invention, one can cite the compound disclosed in paragraph

[0475] of U.S. Patent Application Publication No. 2012 / 0135348A1, but it is not limited thereto.

[0568] The basic compound (C) can be an onium salt compound (CE) having a nitrogen atom in the cation portion (hereinafter also referred to as "compound (CE)"). The compound (CE) 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. Further preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferable that electron-withdrawing functional groups (carbonyl, sulfonyl, cyano, and halogen atoms, etc.) are not directly connected to the nitrogen atom.

[0569] As a preferred specific example of a compound (CE), one may cite the compound disclosed in paragraph

[0203] of U.S. Patent Application Publication No. 2015 / 0309408A1, but it is not limited thereto.

[0570] The following are preferred examples of basic compounds (C), but the invention is not limited to these. Me represents methyl.

[0571] [Chemical Formula 42]

[0572]

[0573] [Chemical Formula 43]

[0574]

[0575] [Chemical Formula 44]

[0576]

[0577] [Chemical Formula 45]

[0578]

[0579] A basic compound (C) can be used alone or in combination with two or more.

[0580] In the composition of the present invention, the content of the basic compound (C) in the composition of the present invention (total when multiple compounds are present) is preferably 0.001 to 20% by mass relative to the total solid content of the composition, more preferably 0.01 to 10% by mass.

[0581] In the composition of the present invention, the molar ratio of compound (B) to the content of basic compound (C), i.e., (B) / (C), is preferably 1.1 or more and 10 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 4 or less. By setting the molar ratio of (B) / (C) to 1.1 or more and 10 or less, it is possible to obtain a composition with minimal performance degradation even after a certain period of time following preparation, while simultaneously achieving improved resolution and reduced development defects based on compound (B).

[0582] In the composition of the present invention, the ratio of the sum of the contents of compound (B) and the basic compound (C) to the sum of the contents of compound (A) and compound (B), i.e., [(B)+(C)] / [(A)+(B)], is preferably 0.3 or more and 1.0 or less in molar ratio, more preferably 0.3 or more and 0.8 or less, and even more preferably 0.5 or more and 0.8 or less. By setting the molar ratio of [(B)+(C)] / [(A)+(B)] to 0.3 or more and 1.0 or less, it is possible to achieve a composition with minimal performance degradation even after a certain period of time following preparation, while simultaneously obtaining the effects of improved resolution and reduced development defects based on compound (B).

[0583] [solvent]

[0584] The compositions of the present invention preferably contain a solvent.

[0585] In the compositions of the present invention, known resist solvents can be suitably used. For example, solvents disclosed in paragraphs

[0665] to

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

[0210] to

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

[0424] to

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

[0357] to

[0366] of U.S. Patent Application Publication No. 2016 / 0274458A1 are preferred.

[0586] Examples of solvents that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylic esters, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionate esters, cyclic lactones (preferably with 4 to 10 carbon atoms), monoketone compounds that may have rings (preferably with 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetic acid esters, and alkyl pyruvate esters.

[0587] As an organic solvent, a mixed solvent can be used, which is a mixture of solvents having hydroxyl groups in the structure and solvents not having hydroxyl groups.

[0588] The above-described exemplary compounds can be appropriately selected as solvents containing or without hydroxyl groups. However, as solvents containing hydroxyl groups, alkylene glycol monoalkyl ethers or alkyl lactates are preferred, and propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate are more preferred. Furthermore, as solvents without hydroxyl groups, alkylene glycol monoalkyl ether acetates, alkyl alkoxypropionates, monoketone compounds that may have rings, cyclic lactones, or alkyl acetates are preferred. Among these, propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate are more preferred. Propylene carbonate is also preferred as a solvent without hydroxyl groups.

[0589] The mixing ratio (mass ratio) of the solvent containing hydroxyl groups to the solvent without hydroxyl groups 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 solvent without hydroxyl groups is preferred.

[0590] The solvent preferably contains propylene glycol monomethyl ether acetate. It can be a single solvent containing propylene glycol monomethyl ether acetate or a mixture of two or more solvents containing propylene glycol monomethyl ether acetate.

[0591] [surfactant]

[0592] The compositions of the present invention may further comprise surfactants. By containing surfactants, when using an exposure light source with a wavelength of 250 nm or less, especially 220 nm or less, it is possible to form patterns with good sensitivity and resolution and fewer development defects.

[0593] Fluorinated and / or silicone surfactants are particularly preferred as surfactants.

[0594] As fluorinated and / or silicone surfactants, examples include those described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. Furthermore, Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431, or 4430 (manufactured by Sumitomo 3MLimited); Megaface F171, F173, F176, F189, F113, F110, F177, F120, or R08 (manufactured by DICCORPORATION); Surflon S-382, SC101, 102, 103, 104, 105, or 106 (manufactured by ASAHI GLASS CO.,LTD.); TroySol S-366 (manufactured by Troy Chemical Industries Inc.); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.); and Surflon S-393 (manufactured by SEIMI CHEMICAL) can be used. (manufactured by Gemco Co., Ltd.); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions Inc.); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Corporation). Alternatively, as a silicone-based surfactant, the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used.

[0595] Furthermore, in addition to the known surfactants described above, surfactants can also be synthesized using fluorinated aliphatic compounds manufactured by telomerization (also known as short-chain polymer telomerization) or oligomerization (also known as oligomerization). Specifically, polymers possessing fluorinated aliphatic groups derived from the fluorinated aliphatic compound can be used as surfactants. These fluorinated aliphatic compounds can be synthesized using, for example, the method described in Japanese Patent Application Publication No. 2002-90991.

[0596] Furthermore, surfactants other than those fluorinated and / or silicone surfactants described in

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

[0597] Surfactants can be used alone or in combination of two or more.

[0598] When the composition of the present invention contains a surfactant, its content, based on the total solids content of the composition, is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and even more preferably 0.0005 to 1% by mass.

[0599] [Cross-linking agent]

[0600] The compositions of the present invention may contain a compound (crosslinking agent) that crosslinks the resin (P) by the action of an acid. Known compounds can be suitably used as crosslinking agents. For example, compounds disclosed in paragraphs

[0379] to

[0431] of U.S. Patent Application Publication No. 2016 / 0147154A1 and paragraphs

[0064] to

[0141] of U.S. Patent Application Publication No. 2016 / 0282720A1 are preferred as crosslinking agents.

[0601] Crosslinking agents are compounds that have crosslinking groups that enable resins to crosslink. Examples of crosslinking groups include hydroxymethyl, alkoxymethyl, acylmethyl, alkoxymethyl ether, ethylene oxide ring, and oxetane ring.

[0602] The crosslinking group is preferably hydroxymethyl, alkoxymethyl, ethylene oxide ring, or oxobutane ring.

[0603] The crosslinking agent is preferably a compound having two or more crosslinking groups (including resins).

[0604] The crosslinking agent is more preferably a phenol derivative having hydroxymethyl or alkoxymethyl, a urea compound (a compound having a urea structure), or a melamine compound (a compound having a melamine structure).

[0605] Crosslinking agents can be used alone or in combination with two or more.

[0606] When the composition of the present invention contains a crosslinking agent, the content of the crosslinking agent relative to the total solid content of the composition of the present invention is preferably 1 to 50% by mass, preferably 3 to 40% by mass, and more preferably 5 to 30% by mass.

[0607] [Other Additives]

[0608] In addition to the components described above, the compositions of the present invention may appropriately contain carboxylic acids, carboxylic acid salts, dissolution inhibitors with a molecular weight of 3000 or less as described in Proceeding of SPIE, 2724, 355 (1996), dyes, plasticizers, photosensitizers, light absorbers, antioxidants, etc.

[0609] In particular, carboxylic acids can be appropriately used to improve performance. Preferably, aromatic carboxylic acids such as benzoic acid and naphtholic acid are preferred.

[0610] When the composition of the present invention contains carboxylic acid, the content of carboxylic acid relative to the total solid content of the composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 3% by mass.

[0611] From the viewpoint of improving resolution, the photosensitive radioactive or radiosensitive linear resin composition of the present invention is preferably used with a film thickness of 10 to 250 nm, more preferably with a film thickness of 20 to 200 nm, and even more preferably with a film thickness of 30 to 100 nm. By setting the concentration of the solid components in the composition within an appropriate range to give it an appropriate viscosity, the coatability and film-forming properties are improved, thereby enabling the formation of such a film thickness.

[0612] The solid content concentration of the photosensitive or radiosensitive linear resin composition in this invention is typically 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly coated on the substrate, thereby forming a resist pattern with excellent line width roughness.

[0613] Solid component concentration is the mass percentage of the components other than the solvent relative to the total mass of the photosensitive or radiosensitive linear resin composition.

[0614] [use]

[0615] The compositions of the present invention relate to photosensitive or radiosensitive linear resin compositions whose properties change upon reaction with photosensitive rays or radiation. More specifically, the compositions of the present invention relate to photosensitive or radiosensitive linear resin compositions used in semiconductor manufacturing processes such as ICs (Integrated Circuits), the manufacture of circuit boards such as liquid crystals or thermal heads, the fabrication of die-casting structures, other photosensitive etching processes, or the manufacture of lithographic printing plates or acid-curing compositions. The patterns formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring processes, and MEMS (Micro Electro Mechanical Systems).

[0616] [Photosensitive X-ray or radiation-sensitive linear membrane]

[0617] The present invention also relates to a photosensitive or radiosensitive linear film (preferably a resist film) formed from the photosensitive or radiosensitive linear composition of the present invention. Such a film is formed, for example, by coating the composition of the present invention onto a support such as a substrate. The thickness of the film is preferably 0.02 to 0.1 μm. As a method of coating onto the substrate, suitable coating methods such as spin coating, roll coating, flow coating, dip coating, spray coating, and blade coating are used, but spin coating is preferred, with a rotation speed preferably of 1000 to 3000 rpm (rotations per minute). The coated film is pre-baked at 60 to 150°C for 1 to 20 minutes, preferably at 80 to 120°C for 1 to 10 minutes to form a thin film.

[0618] The materials constituting the substrate being processed and its outermost layer include, for example, silicon wafers in the case of semiconductor wafers. Examples of materials that can be used as the outermost layer include Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective films, etc.

[0619] An anti-reflective film can be pre-coated on the substrate before the resist film is formed.

[0620] As an antireflective film, any of the following can be used: inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and organic film types composed of light absorbers and polymer materials. Furthermore, as an organic antireflective film, commercially available organic antireflective films such as the DUV30 series and DUV-40 series manufactured by Brewer Science Inc., and AR-2, AR-3, and AR-5 manufactured by Shipley Company can also be used.

[0621] Alternatively, in the pattern forming method of the present invention, a top coating layer may also be formed on the upper layer of the resist film. Preferably, the top coating layer is not mixed with the resist film and can be further uniformly coated on the upper layer of the resist film.

[0622] There are no particular limitations on the top coating. A conventionally known top coating can be formed by conventionally known methods. For example, the top coating can be formed based on the content described in paragraphs 0072 to 0082 of Japanese Patent Application Publication No. 2014-059543.

[0623] For example, it is preferable to form a top coating containing an alkaline compound, such as that described in Japanese Patent Application Publication No. 2013-61648, on the resist film. Specific examples of alkaline compounds that the top coating may contain are the same as those described above for acid diffusion inhibitors.

[0624] Furthermore, the top coating preferably comprises a compound containing at least one group or bond selected from the group consisting of ether, thioether, hydroxyl, thiol, carbonyl and ester bonds.

[0625] Furthermore, the top coating preferably contains a resin. There are no particular limitations on the resin that can be contained in the top coating, and the same hydrophobic resin that can be contained in the photosensitive or radiosensitive linear composition can be used.

[0626] Regarding hydrophobic resins, reference can be made to the descriptions in Japanese Patent Application Publication No. 2013-61647

[0017] to

[0023] (corresponding to U.S. Patent Publication No. 2013 / 244438

[0017] to

[0023] ) and Japanese Patent Application Publication No. 2014-56194

[0016] to

[0165] , which are incorporated herein by reference.

[0627] The top coating preferably contains a resin with repeating units having aromatic rings. By containing repeating units with aromatic rings, especially during electron beam or EUV exposure, the efficiency of secondary electron generation and the acid generation efficiency of compounds that generate acids through photochemical rays or radiation are improved, and high sensitivity and high resolution effects can be expected during pattern formation.

[0628] When the topcoat comprises multiple resins, it is preferable to include at least one resin (XA) having fluorine atoms and / or silicon atoms. More preferably, the topcoat composition comprises at least one resin (XA) having fluorine atoms and / or silicon atoms and a resin (XB) having a fluorine atom and / or silicon atom content less than that of the resin (XA). Thus, when forming the topcoat film, since the resin (XA) is unevenly distributed on the surface of the topcoat film, properties such as developing characteristics and liquid immersion followability can be improved.

[0629] Furthermore, the top coating may contain acid-generating agents and cross-linking agents.

[0630] The topcoat is typically formed from a topcoat forming composition.

[0631] The composition for forming the top coating is preferably prepared by dissolving each component in a solvent and then filtering it through a filter. As the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon with a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less is preferred. Furthermore, when the concentration of solid components in the composition is high (e.g., 25% by mass or more), the pore size of the filter used for filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. This filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In the filter filtration process, as disclosed in, for example, Japanese Patent Application Publication No. 2002-62667, multiple filters can be used for circulation filtration, or multiple filters can be connected in series or parallel for filtration. Furthermore, the composition can be filtered multiple times. Additionally, the composition can be degassed before and after filtration.

[0632] The composition for forming the top coating preferably does not contain impurities such as metals. The content of metal components contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, even more preferably 1 ppm or less, and especially preferably substantially free (below the detection limit of the measuring device).

[0633] In order to reduce the content of metallic impurities in the resist composition to a small amount (e.g., at the ppm level by mass), it is preferable to perform partial or complete glass lining treatment within the apparatus used in the manufacturing process (synthetic raw material process, etc.) of the raw materials (resin and photoacid generator, etc.) of the resist composition. This method is described, for example, in the Chemical Industry Daily on December 21, 2017.

[0634] When the exposure described later is set as immersion exposure, the top coating also functions as a layer disposed between the resist film and the immersion liquid without directly contacting the resist film with the immersion liquid. In this case, preferred characteristics of the top coating (top coating forming composition) are good coating suitability for the resist film, transparency to radiation, especially 193 nm, and low solubility in the immersion liquid (preferably water). Furthermore, the top coating preferably does not mix with the resist film and can be further uniformly coated on the surface of the resist film.

[0635] Furthermore, in order to uniformly coat the topcoat forming composition without dissolving the resist film on its surface, the topcoat forming composition preferably contains a solvent that does not dissolve the resist film. As the solvent that does not dissolve the resist film, it is even more preferable to use a solvent with components different from those of a developer (organic developer) containing an organic solvent, which will be described in detail later.

[0636] There are no particular limitations on the coating method of the composition for forming the top coating layer, and conventionally known methods such as spin coating, spraying, roller coating, and dipping can be used.

[0637] There is no particular limitation on the thickness of the top coating. From the viewpoint of transparency to the exposure light source, it is usually formed with a thickness of 5nm to 300nm, preferably 10nm to 300nm, more preferably 20nm to 200nm, and even more preferably 30nm to 100nm.

[0638] After the top coating is formed, the substrate (PB) is heated as needed.

[0639] From a resolution perspective, the refractive index of the top coating is preferably close to that of the resist film.

[0640] The top coating is preferably insoluble in the immersion liquid, and more preferably insoluble in water.

[0641] From the viewpoint of liquid immersion follow-through, the retreat contact angle of the top coating relative to the retreat contact angle (23°C) of the liquid immersion of the top coating is preferably 50 to 100 degrees, more preferably 80 to 100 degrees.

[0642] In immersion exposure, the immersion liquid needs to move on the wafer at high speed following the exposure head to scan and form an exposure pattern. Therefore, the contact angle of the immersion liquid in a dynamic state becomes important for the top coating. In order to obtain better resist performance, a receding contact angle with the above range is preferred.

[0643] When stripping the top coating, an organic developer or a stripping agent can be used. As a stripping agent, a solvent with low penetration into the resist film is preferred. From the viewpoint that the top coating can be stripped simultaneously with the development of the resist film, the top coating is preferably stripped using an organic developer. As for the organic developer used for stripping, there are no particular limitations as long as it can dissolve and remove the low-exposure areas of the resist film.

[0644] From the viewpoint of stripping with an organic developer, the dissolution rate of the top coating to the organic developer is preferably 1 to 300 nm / sec, more preferably 10 to 100 nm / sec.

[0645] Here, the dissolution rate of the top coating to the organic developer is the rate at which the film thickness decreases when the top coating is exposed to the developer after being formed into a film. In this invention, it is set as the rate when the film is immersed in butyl acetate at 23°C.

[0646] By setting the dissolution rate of the top coating to the organic developer to 1 / sec or more, preferably 10 nm / sec or more, the occurrence of development defects after developing the resist film can be reduced. Furthermore, by setting it to 300 nm / sec or less, preferably 100 nm / sec, the uneven exposure during immersion exposure may be reduced, thereby further improving the edge roughness of the pattern after developing the resist film.

[0647] The top coating can also be removed using other known developing solutions, such as alkaline aqueous solutions. Specifically, an aqueous solution of tetramethylammonium hydroxide can be used as an example of an alkaline aqueous solution.

[0648] [Pattern Formation Method]

[0649] The present invention also relates to a pattern forming method, comprising: a resist film forming step, wherein a resist film is formed using a photosensitive radioactive or radiosensitive linear resin composition of the present invention; an exposure step, wherein the resist film is exposed; and a developing step, wherein the exposed resist film is developed using a developing solution.

[0650] In this invention, the above exposure is preferably performed using an electron beam, an ArF excimer laser, or extreme ultraviolet light, and more preferably using an electron beam or extreme ultraviolet light.

[0651] In the manufacture of precision integrated circuit components, the first step in the exposure (patterning process) of the resist film is preferably to irradiate the resist film of the present invention in a patterned manner with an ArF excimer laser, an electron beam, or extreme ultraviolet (EUV). Regarding the exposure amount, in the case of an ArF excimer laser, it is typically 1 to 100 mJ / cm². 2 The optimal value is 20–60 mJ / cm². 2 Around 0.1–20 μC / cm under electron beam conditions. 2 Around 3 to 10 μC / cm 2 Around 0.1–20 mJ / cm² under extreme ultraviolet radiation. 2 The optimal value is approximately 3–15 mJ / cm². 2 Exposure is performed in a left-right manner.

[0652] Next, the material is exposed to a hot plate at 60°C to 150°C for 5 seconds to 20 minutes (post-exposure baking), more preferably at 80°C to 120°C for 15 seconds to 10 minutes (post-exposure baking), and even more preferably at 80°C to 120°C for 1 to 10 minutes (post-exposure baking). Following this, development, rinsing, and drying are performed to form a pattern. Here, the post-exposure heating is appropriately adjusted based on the acidity of the repeating units in the resin (P) containing acid-degradable groups. When the acidity is low, it is also preferable that the post-exposure heating temperature is 110°C or higher, and the heating time is 45 seconds or higher.

[0653] The developer can be appropriately selected, preferably an alkaline developer (typically an alkaline aqueous solution) or a developer containing organic solvents (also known as an organic developer). When the developer is an alkaline aqueous solution, a 0.1–5% (by mass), preferably 2–3% (by mass) alkaline aqueous solution of tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), etc., is used for development for 0.1–3 minutes, preferably 0.5–2 minutes, using conventional methods such as dip, puddle, or spray. An appropriate amount of alcohol and / or surfactant can be added to the alkaline developer. In this way, during the formation of a negative pattern, the unexposed areas of the film dissolve, while the exposed areas are difficult to dissolve in the developer; similarly, during the formation of a positive pattern, the exposed areas of the film dissolve, while the unexposed areas are difficult to dissolve in the developer, thereby forming the target pattern on the substrate.

[0654] When the pattern forming method of the present invention includes a step of developing with an alkaline developer, the alkaline developer can be, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alkanolamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, tetraalkylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, quaternary ammonium salts such as dimethylbis(2-hydroxyethyl)ammonium hydroxide, cyclic amines such as pyrrole and piperidine, etc.

[0655] In addition, appropriate amounts of alcohols and surfactants can be added to the above-mentioned alkaline aqueous solution for use.

[0656] The alkali concentration of alkaline developing solutions is typically 0.1–20% by mass.

[0657] The pH of alkaline developing solutions is typically 10.0 to 15.0.

[0658] In particular, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide is preferred.

[0659] As a rinsing solution in the rinsing process following alkaline development, pure water can be used with the addition of an appropriate amount of surfactant.

[0660] Furthermore, after the developing or rinsing process, it is possible to remove the developing or rinsing solution adhering to the pattern using supercritical fluid.

[0661] When the pattern forming method of the present invention includes a step of developing with a developer containing an organic solvent, the developer in the above step (hereinafter also referred to as an organic developer) can be a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, or an ether solvent, as well as a hydrocarbon solvent.

[0662] In this invention, ester solvents refer to solvents having an ester group within the molecule, ketone solvents refer to solvents having a ketone group within the molecule, alcohol solvents refer to solvents having an alcoholic hydroxyl group within the molecule, amide solvents refer to solvents having an amide group within the molecule, and ether solvents refer to solvents having an ether bond within the molecule. Among these, there are also solvents having multiple of the above-mentioned functional groups within a single molecule; however, in this case, they are considered to be solvents equivalent to any type of solvent containing the functional groups possessed by that solvent. For example, diethylene glycol monomethyl ether is equivalent to either an alcohol solvent or an ether solvent in the above classification. Furthermore, hydrocarbon solvents refer to hydrocarbon solvents without substituents.

[0663] In particular, a developing solution containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents and ether solvents is preferred.

[0664] From the viewpoint of being able to suppress the swelling of the resist film, the developer preferably uses an ester solvent with 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and 2 or fewer heteroatoms.

[0665] The heteroatoms in the aforementioned ester solvents are atoms other than carbon and hydrogen atoms, such as oxygen, nitrogen, and sulfur atoms. The number of heteroatoms is preferably 2 or less.

[0666] Preferred examples of ester solvents having 7 or more carbon atoms and 2 or fewer heteroatoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, amyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, and isobutyl isobutyrate, with isoamyl acetate or isobutyl isobutyrate being particularly preferred.

[0667] The developer can be a mixture of the above-mentioned ester solvents and hydrocarbon solvents, or a mixture of the above-mentioned ketone solvents and hydrocarbon solvents, instead of the ester solvents having 7 or more carbon atoms and 2 or fewer heteroatoms. In this case, it is also effective in suppressing the swelling of the resist film.

[0668] When using an ester-based solvent in combination with a hydrocarbon-based solvent, isoamyl acetate is preferably used as the ester-based solvent. Furthermore, from the viewpoint of adjusting the solubility of the resist film, a saturated hydrocarbon solvent (e.g., octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is preferred as the hydrocarbon-based solvent.

[0669] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylpentyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone-acetone, ionone, diacetonyl alcohol, acetoethanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, etc., with diisobutyl ketone and 2,5-dimethyl-4-hexanone being particularly preferred.

[0670] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl 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 butyrate, and methyl 2-hydroxyisobutyrate.

[0671] Examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, 4-methyl-2-pentanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, n-decanol, etc.; diol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; and ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, etc., which are ethylene glycol ether-based solvents.

[0672] Examples of ether solvents, besides the ethylene glycol ether solvents mentioned above, include anisole, dioxane, and tetrahydrofuran.

[0673] As amide solvents, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamine, 1,3-dimethyl-2-imidazolium ketone, etc. can be used.

[0674] Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane.

[0675] Furthermore, aliphatic hydrocarbon solvents, used as hydrocarbon solvents, can be mixtures of compounds with the same number of carbon atoms but different structures. For example, when decane is used as an aliphatic hydrocarbon solvent, compounds with the same number of carbon atoms but different structures, such as 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane, can be included in the aliphatic hydrocarbon solvent.

[0676] Furthermore, the compounds with the same number of carbon atoms but different structures mentioned above may contain only one type, or they may contain multiple types as described above.

[0677] It can be mixed with various of the above-mentioned solvents, or with solvents other than those mentioned above, or with water. However, in order to fully realize the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of water.

[0678] The concentration of organic solvents (total when multiple solvents are mixed) in the organic developer is preferably 50% by mass or more, more preferably 50-100% by mass, even more preferably 85-100% by mass, even more preferably 90-100% by mass, and particularly preferably 95-100% by mass. Most preferably, it consists substantially only of organic solvents. Furthermore, "consistently consisting substantially only of organic solvents" refers to the case that includes trace amounts of surfactants, antioxidants, stabilizers, defoamers, etc.

[0679] In particular, the organic developer is preferably a developer containing at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents.

[0680] The vapor pressure of the organic developer at 20°C is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the organic developer to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, the temperature uniformity within the wafer surface is improved, and consequently, the dimensional uniformity within the wafer surface is improved.

[0681] Specific examples of solvents with vapor pressures below 5 kPa include ketones such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl pentyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenyl acetone, and methyl isobutyl ketone; butyl 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, butyl formate, propyl formate, ethyl lactate, and butyl lactate. Ester solvents such as esters and propyl lactate; alcohol solvents such as n-propyl alcohol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, and n-decanol; diol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol; ether solvents such as tetrahydrofuran; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene; and aliphatic hydrocarbon solvents such as octane and decane.

[0682] Specific examples of vapor pressures with a particularly preferred range, i.e., below 2 kPa, include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and phenylacetone; butyl 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; ethyl lactate; butyl lactate; and lactic acid. Ester solvents such as propyl ester; alcohol solvents such as n-butanol, sec-butanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, and n-decanol; diol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide; aromatic hydrocarbon solvents such as xylene; and aliphatic hydrocarbon solvents such as octane, decane, and undecane.

[0683] Organic developing solutions may contain basic compounds. Specific examples and preferred examples of basic compounds that may be contained in the developing solution used in this invention are the same as the specific examples and preferred examples of basic compounds that may be contained in the aforementioned photosensitive or radiosensitive linear compositions.

[0684] An appropriate amount of surfactant can be added to organic developing solutions as needed.

[0685] There are no particular limitations on the surfactant used; for example, ionic or nonionic fluorinated and / or silicone surfactants can be used. Examples of such fluorinated and / or silicone surfactants include Japanese Patent Application Publication Nos. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, 7-230165, 8-62834, and 9-54432. The surfactants described in U.S. Patent No. 5988, U.S. Patent No. 5405720, U.S. Patent No. 5360692, U.S. Patent No. 5529881, U.S. Patent No. 5296330, U.S. Patent No. 5436098, U.S. Patent No. 5576143, U.S. Patent No. 5294511, and U.S. Patent No. 5824451 are preferably nonionic surfactants. There are no particular limitations on the nonionic surfactant, but fluorinated surfactants or silicone surfactants are further preferred.

[0686] The amount of surfactant used relative to the total amount of developer is preferably 0.0001 to 2% by mass, more preferably 0.0001 to 1% by mass, and especially preferably 0.0001 to 0.1% by mass.

[0687] As a developing method, it can be applied to, for example, the following methods: immersing the substrate in a tank filled with developing solution for a certain time (dip method); developing the substrate by causing the developing solution to bulge on the substrate surface through surface tension and letting it stand for a certain time (puddle method); spraying developing solution onto the substrate surface (spray method); and continuously spraying developing solution onto a substrate rotating at a certain speed while scanning the developing solution nozzle at a certain speed (dynamic dispense method), etc.

[0688] When the above-mentioned developing methods include a step of ejecting developer from the developing nozzle of the developing apparatus toward the resist film, the ejection pressure of the ejected developer (the flow rate of the ejected developer per unit area) is preferably 2 mL / sec / mm. 2 The following is more preferably 1.5 mL / sec / mm 2 Hereinafter, 1 mL / sec / mm is further preferred. 2The following applies. There is no particular lower limit to the flow rate, but considering production volume, 0.2 mL / sec / mm is preferred. 2 above.

[0689] By setting the ejection pressure of the developer solution within the aforementioned range, defects in the pattern caused by resist residue after development can be significantly reduced.

[0690] While the details of this mechanism are uncertain, it can be assumed that the reason is that by setting the ejection pressure to the aforementioned range, the pressure exerted by the developer on the resist film is reduced, thus suppressing the unintentional removal or damage of the resist film / pattern.

[0691] Additionally, the developer discharge pressure (mL / sec / mm) 2 ) is the value at the outlet of the developing nozzle in the developing apparatus.

[0692] Methods for adjusting the discharge pressure of the developer include, for example, adjusting the discharge pressure using a pump or the method of changing the pressure by adjusting the supply from a pressurizing tank.

[0693] Furthermore, after the development process using a developer containing organic solvents, a process can be performed where the development is stopped while replacing the solvent with another solvent.

[0694] A rinsing process can be included after the developing process using a developer containing organic solvents. However, from the perspective of production volume (productivity) and rinsing fluid usage, the rinsing process can be omitted.

[0695] As for the rinsing solution used in the rinsing process after the development process using a developer containing an organic solvent, there are no particular restrictions as long as it does not dissolve the resist pattern, and a solution containing a common organic solvent can be used. As the rinsing solution mentioned above, it is preferable to use a rinsing solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0696] Specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include solvents that are the same as those described in the developing solution containing organic solvents, and butyl acetate and methyl isobutyl methanol are particularly preferred examples.

[0697] After the development step using a developer containing an organic solvent, it is more preferable to perform a cleaning step using a rinsing solution containing at least one organic solvent selected from ester solvents, alcohol solvents, and hydrocarbon solvents. It is even more preferable to perform a cleaning step using a rinsing solution containing an alcohol solvent or a hydrocarbon solvent.

[0698] As the organic solvent contained in the rinsing solution, a hydrocarbon solvent is preferred, and an aliphatic hydrocarbon solvent is more preferred. From the viewpoint of further improving its effectiveness, the aliphatic hydrocarbon solvent used in the rinsing solution is preferably an aliphatic hydrocarbon solvent with 5 or more carbon atoms (e.g., pentane, hexane, octane, decane, undecane, dodecane, and hexadecane), preferably an aliphatic hydrocarbon solvent with 8 or more carbon atoms, and more preferably an aliphatic hydrocarbon solvent with 10 or more carbon atoms.

[0699] Furthermore, there is no particular limitation on the upper limit of the number of carbon atoms in the aforementioned aliphatic hydrocarbon solvents. For example, 16 or less is acceptable, preferably 14 or less, and more preferably 12 or less.

[0700] Among the above-mentioned aliphatic hydrocarbon solvents, decane, undecane, and dodecane are particularly preferred, with undecane being the most preferred.

[0701] Thus, by using hydrocarbon solvents (especially aliphatic hydrocarbon solvents) as the organic solvent contained in the rinsing solution, the developer that has slightly penetrated into the resist film after development is rinsed out, further suppressing swelling and enhancing the effect of suppressing pattern collapse.

[0702] The above-mentioned components can be mixed in multiple ways, or used in combination with organic solvents other than those mentioned above.

[0703] The water content in the rinsing solution is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good developing characteristics can be obtained.

[0704] The vapor pressure of the rinsing solution used after the developing process using a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less at 20°C, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinsing solution to 0.05 kPa or more and 5 kPa or less, the temperature uniformity within the wafer surface is improved, thereby suppressing swelling caused by the penetration of the rinsing solution and improving the dimensional uniformity within the wafer surface.

[0705] An appropriate amount of surfactant can also be added to the rinsing solution for use.

[0706] In the rinsing process, a rinsing solution containing the aforementioned organic solvent is used to clean the wafer that has been developed using a developer containing an organic solvent. The cleaning method is not particularly limited; for example, methods such as continuously spraying rinsing solution onto a substrate rotating at a certain speed (spin coating), immersing the substrate in a tank filled with rinsing solution for a certain time (immersion method), and spraying rinsing solution onto the substrate surface (spray coating) are preferred. Among these, a spin coating method is preferred, where the substrate is rotated at 2000 rpm to 4000 rpm after cleaning to remove the rinsing solution from the substrate. Furthermore, a post-bake process is preferably included after the rinsing process. Baking removes residual developer and rinsing solution between and within the patterns. The post-bake process is typically performed at 40–160°C, preferably 70–95°C, for 10 seconds to 3 minutes, preferably 30 to 90 seconds.

[0707] In cases where a cleaning process using a rinsing solution is not required, for example, the developing process method described in paragraphs

[0014] to

[0086] of Japanese Patent Application Publication No. 2015-216403 can be used.

[0708] Furthermore, the pattern forming method of the present invention can include a developing step using an organic developer and a developing step using an alkaline developer. The weakly exposed areas are removed by developing with an organic developer, and the strongly exposed areas are also removed by developing with an alkaline developer. Thus, by performing a multiple developing process, pattern forming can be achieved only in the intermediate areas of high exposure intensity without dissolving, thereby enabling the formation of finer patterns than usual (the same mechanism as paragraph

[0077] of Japanese Patent Application Publication No. 2008-292975).

[0709] The photosensitive rays or photosensitive linear compositions used in this invention, as well as the various materials used in the pattern forming method of this invention (e.g., resist solvents, developers, rinsing solutions, compositions for forming antireflective films, compositions for forming top coatings, etc.), preferably do not contain impurities such as metals, metal salts containing halogens, or components containing acids, bases, sulfur atoms, or phosphorus atoms. Examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or their salts.

[0710] The content of impurities contained in these materials is preferably less than 1 ppm, more preferably less than 1 ppb (parts per billion), even more preferably less than 100 ppt (parts per trillion), especially preferably less than 10 ppt, and most preferably substantially non-existent (below the detection limit of the measuring device).

[0711] As a method for removing impurities such as metals from various materials, filtration using a filter can be cited as an example. Regarding the filter pore size, a pore size of 10 nm or less is preferred, more preferably 5 nm or less, and even more preferably 3 nm or less is preferred. Regarding the filter material, filters made of polytetrafluoroethylene, polyethylene, or nylon are preferred. The filter can be a composite material combining these materials and an ion exchange medium. The filter can be 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. When using multiple filters, filters with different pore sizes and / or materials can be used in combination. Furthermore, various materials can be filtered multiple times; the multiple filtration process can be a circulating filtration process.

[0712] Furthermore, as methods to reduce impurities such as metals contained in various materials, examples include selecting raw materials with low metal content as constituent materials, filtering the constituent materials using filters, and performing distillation under conditions that minimize contamination, such as lining the apparatus with Teflon (registered trademark). The preferred conditions for filtering the constituent materials are the same as those described above.

[0713] Besides filtration, impurities can be removed using adsorption materials, and a combination of filtration and adsorption materials can also be used. As adsorption materials, well-known adsorption materials can be used, such as inorganic adsorption materials like silica gel and zeolite, and organic adsorption materials like activated carbon.

[0714] Furthermore, as a method for reducing impurities such as metals contained in the organic processing liquid of the present invention, examples include selecting raw materials with low metal content as constituent materials, filtering the raw materials constituting the various materials, and performing distillation under conditions that minimize contamination, such as lining the apparatus with Teflon (registered trademark). The preferred conditions for filtering the raw materials constituting the various materials are the same as those described above.

[0715] Besides filtration, impurities can be removed using adsorption materials, and a combination of filtration and adsorption materials can also be used. As adsorption materials, well-known adsorption materials can be used, such as inorganic adsorption materials like silica gel and zeolite, and organic adsorption materials like activated carbon.

[0716] [Containment Container]

[0717] As an organic solvent (also called "organic processing solution") that can be used in developing and rinsing solutions, it is preferable to use a solvent stored in a container for patterning organic processing solution of resist film, which has a receiving section. For example, such a container is preferably a container for patterning organic processing solution of resist film where the inner wall of the receiving section in contact with the organic processing solution is made of a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or is made of metal that has undergone rust-preventing and metal leaching-preventing treatment. The receiving section of this container contains the predetermined organic solvent used as patterning organic processing solution for resist film, and the organic solvent discharged from the receiving section can be used during resist film patterning.

[0718] In the case where the aforementioned containment container further has a sealing portion for sealing the aforementioned containment portion, the sealing portion is preferably formed of a resin different from one or more resins selected from polyethylene resin, polypropylene resin and polyethylene-polypropylene resin, or of metal that has undergone rust-proofing and metal leaching-proofing treatment.

[0719] Here, a sealing part refers to a component that can block the receiving part from the outside air, and preferably includes a seal, an O-ring, etc.

[0720] The resin that is different from one or more resins selected from polyethylene resin, polypropylene resin and polyethylene-polypropylene resin is preferably a perfluorinated resin.

[0721] Examples of perfluorinated resins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene-ethylene copolymer resin (ETFE), trifluorochloroethylene-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), trifluorochloroethylene copolymer resin (PCTFE), and fluoroethylene resin (PVF).

[0722] Examples of particularly preferred perfluorinated resins include tetrafluoroethylene resins, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, and tetrafluoroethylene-hexafluoropropylene copolymers and resins.

[0723] Examples of metals that have undergone rust-proofing and anti-metal leaching treatment include carbon steel, alloy steel, nickel-chromium steel, nickel-chromium-molybdenum steel, chromium steel, chromium-molybdenum steel, and manganese steel.

[0724] For rust prevention and metal leaching prevention treatment, film technology is preferred.

[0725] In coating technology, there are roughly three types: metal coating (various plating), inorganic coating (various chemical conversion treatments, glass, concrete, ceramics, etc.), and organic coating (rust-preventive oil, coatings, rubber, plastics).

[0726] Preferred coating technologies include surface treatments using rust-preventive oils, rust inhibitors, corrosion inhibitors, chelating compounds, stretchable plastics, and lining agents.

[0727] The preferred materials include various chromates, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acids, and naphthenic acids, corrosion inhibitors such as carboxylic acid metal soaps, sulfonates, amine salts, and esters (glycerol esters or phosphate esters of higher fatty acids), chelating compounds such as ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, and diethylenetriaminepentaacetic acid, and fluororesin linings. Phosphate treatment and fluororesin linings are particularly preferred.

[0728] Furthermore, although it cannot directly prevent rust compared to direct coating treatment, it is still preferable to use "pretreatment" as a stage before rust prevention treatment as a method to extend the rust prevention period through coating treatment.

[0729] As a specific example of such pretreatment, a preferred method is to remove various corrosive agents such as chlorides or sulfates present on the metal surface by cleaning or grinding.

[0730] The following are specific examples of containment containers.

[0731] • FluoroPure PFA composite roller (wetted inner surface; PFA resin liner) manufactured by Entegris

[0732] JFE manufactures steel cylindrical tanks (with liquid-contacting inner surface; zinc phosphate coating).

[0733] Furthermore, as a container that can be used in this invention, the containers described in Japanese Patent Application Publication No. 11-021393

[0013] to

[0030] and Japanese Patent Application Publication No. 10-45961

[0012] to

[0024] can also be cited.

[0734] To prevent malfunctions in the chemical solution piping and various components (filters, O-rings, hoses, etc.) caused by static electricity and subsequent electrostatic discharge, the organic processing solution of the present invention may contain a conductive compound. There are no particular limitations on the conductive compound; methanol is an example. The amount added is not particularly limited, but from the viewpoint of maintaining preferred development characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less. Regarding the components of the chemical solution piping, various pipes coated with SUS (stainless steel) or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) that have undergone antistatic treatment can be used. Similarly, for filters and O-rings, polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) that have undergone antistatic treatment can also be used.

[0735] In addition, developer and rinsing solutions are typically collected in waste tanks via piping after use. However, if a hydrocarbon-based solvent is used as the rinsing solution, to prevent the resist dissolved in the developer from precipitating and adhering to the back of the wafer or the sides of the piping, there is a method to re-pass the solvent containing the dissolved resist through the piping. Examples of such methods include rinsing with the rinsing solution followed by rinsing with the solvent containing the dissolved resist, and then rinsing through the back and sides of the substrate; or passing the solvent containing the dissolved resist through the piping without contacting the resist.

[0736] As for the solvent used in the piping, there are no particular limitations as long as it can dissolve the photoresist. Examples of suitable organic solvents include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, and acetone. Among these, PGMEA, PGME, and cyclohexanone are preferred.

[0737] Manufacturing methods for electronic devices

[0738] Furthermore, the present invention also relates to a method for manufacturing an electronic device including the above-described pattern forming method. Electronic devices manufactured by the method of the present invention are preferably mounted in electrical and electronic equipment (e.g., home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, and communication equipment).

[0739] [Photosensitive radioactive or radiosensitive linear resin composition for photomask manufacturing, and method for manufacturing photomasks]

[0740] One preferred embodiment of the composition of the present invention is a photosensitive radioactive or radiosensitive linear resin composition for manufacturing photomasks.

[0741] Furthermore, the present invention also relates to a method for manufacturing a photomask using the above-described photomask to manufacture a photosensitive radioactive or radiosensitive linear resin composition.

[0742] Example

[0743] The present invention will now be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be construed as limited to the embodiments shown below.

[0744] <Resin (P)>

[0745] The following shows the structure of the repeating units of the resin (P) used, their content (molar ratio), weight-average molecular weight (Mw), and dispersion (Mw / Mn).

[0746] [Chemical Formula 46]

[0747]

[0748] [Chemical Formula 47]

[0749]

[0750] [Chemical Formula 48]

[0751]

[0752] [Chemical Formula 49]

[0753]

[0754] [Chemical Formula 50]

[0755]

[0756] [Chemical Formula 51]

[0757]

[0758] [Chemical Formula 52]

[0759]

[0760] [Chemical Formula 53]

[0761]

[0762] [Chemical Formula 54]

[0763]

[0764] <Photo-acid generator (A)>

[0765] The structure of the photoacid generator (A) used is shown below.

[0766] [Chemical Formula 55]

[0767]

[0768] [Chemical Formula 56]

[0769]

[0770] [Chemical Formula 57]

[0771]

[0772] [Chemical Formula 58]

[0773]

[0774] [Chemical Formula 59]

[0775]

[0776] [Chemical Formula 60]

[0777]

[0778] [Chemical Formula 61]

[0779]

[0780] [Chemical Formula 62]

[0781]

[0782] [Chemical Formula 63]

[0783]

[0784] [Chemical Formula 64]

[0785]

[0786] A-11 and A-12 below are not photoacid generators (A), but are used as photoacid generators in the reference examples.

[0787] [Chemical Formula 65]

[0788]

[0789] [Chemical Formula 66]

[0790]

[0791] <Photo-acid generator (B)>

[0792] The structure of the photoacid generator (B) used is shown below.

[0793] [Chemical Formula 67]

[0794]

[0795] [Chemical Formula 68]

[0796]

[0797] <Alkaline compound (C)>

[0798] The structure of the basic compound (C) used is shown below.

[0799] [Chemical Formula 69]

[0800]

[0801] <Cross-linking agent>

[0802] The structure of the crosslinking agent used is shown below.

[0803] [Chemical Formula 70]

[0804]

[0805] <Solvent>

[0806] The solvents used are shown below. PGMEA: Propylene glycol monomethyl ether acetate; PGME: Propylene glycol monomethyl ether.

[0807] EL: Ethyl lactate

[0808] [Preparation and application of the resist composition]

[0809] (1) Preparation of the support body

[0810] An 8-inch wafer with Cr nitride oxide deposited on it was prepared (the material to be treated with the shielding film used in a typical blank photomask).

[0811] (2) Preparation of the corrosion resist composition

[0812] The components shown in Tables 1 and 2 were dissolved in the solvents shown in Tables 1 and 2 to prepare a solution with the solid content (total solid content) shown in Tables 1 and 2. The solution was then filtered through a polyethylene filter with a pore size of 0.03 μm to prepare the resist composition.

[0813] (3) Preparation of resist film

[0814] A resist composition was applied to the aforementioned 8-inch wafer using a Tokyo Electron Ltd. Mark 8 spin coater, and dried on a hot plate at 120°C for 600 seconds to obtain a resist film with a thickness of 50 nm. Thus, a resist-coated wafer was obtained.

[0815] In Tables 1 and 2, the content (mass %) of each component other than the solvent refers to the percentage of the resist composition relative to the total solids content. Furthermore, Table 1 below shows the percentage (mass %) of the solvent used relative to all solvents.

[0816]

[0817]

[0818] [EB Exposure and Development]

[0819] (4) Creation of resist patterns

[0820] The resist film obtained in (3) above was patterned using an electron beam irradiation apparatus (ADVANTEST CORPORATION; F7000S, accelerating voltage 50 keV). After irradiation, it was heated at 100°C on a hot plate for 600 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and then dried.

[0821] [evaluate]

[0822] (5) Evaluation of resist pattern

[0823] (Evaluation of resolution when using the freshly prepared resist composition)

[0824] The following evaluation was conducted on the resist patterns made using the freshly prepared resist composition.

[0825] The irradiation energy required to resolve 1:1 lines and spatial patterns with a linewidth of 50 nm is defined as the sensitivity (Eop1). The limiting resolution (the smallest linewidth at which line and spatial (line:space = 1:1) separation can be resolved) of the exposure amount representing the sensitivity (Eop1) is set as the resolution (also known as "r1") when using the freshly prepared resist composition (unit: nm).

[0826] (Evaluation of resolution when using a resist composition that has been prepared for a certain period of time)

[0827] After preparation, the sensitivity (Eop1) was determined using a resist composition stored at 40°C for one month, following the same steps as described above. The limiting resolution of the exposure, which represents the sensitivity (Eop1), was evaluated and set as the resolution (also known as "r2") when using the resist composition after a certain period of time following preparation (unit: nm).

[0828] (Evaluation of resolution changes of the resist composition before and after time)

[0829] The resolution change of the resist composition over time (also known as "Δr") is calculated by comparing the resolution (r2) obtained above when using the resist composition after a certain period of time with the resolution (r1) obtained immediately after preparation. Specifically, Δr is calculated using Equation 1 below.

[0830] △r=r2-r1 Equation 1

[0831] The smaller the value of Δr, the less the performance of the resist composition deteriorates over time, and the better its performance.

[0832] (Development defects when using freshly prepared resist composition)

[0833] The following evaluation was conducted on the resist patterns made using the freshly prepared resist composition.

[0834] Using the KLA2360 defect inspection device (trade name) manufactured by KLA Corporation, with the pixel size of the defect inspection device set to 0.13 μm and the threshold set to 20, defects (number / cm) were extracted from the difference between the 1:1 line and spatial pattern with a linewidth of 50 nm formed at the above sensitivity (Eop1) and the comparison image through the overlap of pixel units. 2 ), calculate the number of defects per unit area (defects / cm²) 2 Then, by performing a defect review, development defects are extracted from all defects and the number of development defects per unit area (also known as "d1") is calculated when using the freshly prepared resist composition. (Unit: defects / cm²) 2).

[0835] (Development defects when using a resist composition that has been prepared for a certain period of time)

[0836] After preparation, using a resist composition stored at 40°C for one month, the number of development defects per unit area (also known as "d2") was calculated using the same steps as described above when using the resist composition after a certain period of preparation. (Unit: defects / cm) 2 The value of the number of development defects per unit area is set as A, 0.5 or higher but less than 1.0 as B, 1.0 or higher but less than 5.0 as C, and 5.0 or higher as D. The smaller the value, the better the performance.

[0837] (Evaluation of the changes in development defect properties of the resist composition before and after time)

[0838] The change in development defect performance of the resist composition before and after a certain period of time is calculated by the difference between the number of development defects per unit area (d2) when using the resist composition after a certain period of time and the number of development defects per unit area (d1) when using the resist composition immediately after preparation (also known as "Δd"). Specifically, Δd is calculated using Equation 2 below.

[0839] △d=d2-d1 Equation 2

[0840] The smaller the value of Δd, the less the performance of the resist composition deteriorates over time, and the better its performance.

[0841] Let A be the case where △d is less than 1.0, B be the case where △d is greater than 1.0 and less than 2.0, C be the case where △d is greater than 2.0 and less than 3.0, and D be the case where △d is greater than 3.0.

[0842] The results of resolution (r2), number of development defects per unit area (d2), resolution change (Δr), and development defect performance change (Δd) of the resist composition after a certain period of preparation are shown in Tables 3 and 4 below.

[0843] Furthermore, Tables 3 and 4 below also record the molar ratio (B) / (C) of the content of photoacid generator (B) to the content of basic compound (C), the molar ratio (A) / (B) of the sum of the contents of photoacid generator (B) and basic compound (C) to the sum of the contents of photoacid generator (A) and photoacid generator (B), the molar ratio (A) / (B) of the sum of the contents of photoacid generator (B) and basic compound (C).

[0844] [Table 3]

[0845]

[0846] [Table 4]

[0847]

[0848] As can be seen from the results of the examples, the resist composition of the present invention has high resolution and few development defects, and the resolution remains high and the development defects remain few even after a certain period of time after preparation.

[0849] In the reference example, the resolution was worse than that of the example because the photoacid generator (A) of the present invention was not used. Furthermore, a comparison between the reference example and the example shows that the problems of resolution reduction and worsening of development defects after a certain period of preparation are unlikely to occur in the reference example where the photoacid generator (A) is not used.

[0850] Industrial availability

[0851] According to the present invention, it is possible to provide a photosensitive radioactive or radioactive linear resin composition that has high resolution and few development defects in a pattern forming method and also has high resolution and few development defects after a predetermined period following the preparation of the photosensitive radioactive or radioactive linear resin composition; a photosensitive radioactive or radioactive linear film using the above-mentioned photosensitive radioactive or radioactive linear resin composition; a pattern forming method; a method for manufacturing electronic devices; a photosensitive radioactive or radioactive linear resin composition for photomask manufacturing; and a method for manufacturing photomasks.

[0852] The present invention has been described in detail with reference to specific embodiments, but various changes or modifications can be made without departing from the spirit and scope of the invention, which will be apparent to those skilled in the art.

[0853] This application is based on Japanese patent application filed on March 30, 2020 (Japanese Patent Application 2020-061655), the contents of which are incorporated herein by reference.

Claims

1. A photosensitive or radiosensitive linear resin composition, comprising: The solubility of resin (P) in developer changes due to the action of acid; Compound (A) has a group (a) whose polarity changes upon decomposition by the action of an acid, and produces an acid (ac1) upon irradiation by photochemical rays or radiation. Compound (B), which, upon irradiation with photochemical rays or radiation, produces an acid (ac2) with a higher pKa than the acid (ac1) produced by compound (A); and Basic compound (C) The compound (B) is a compound represented by the following general formula (B-1). In general formula (B-1), R 51 M represents an alkyl group optionally having substituents and optionally containing an ether or carbonyl bond, a cycloalkyl group optionally having substituents and optionally containing an ether or carbonyl bond, an aryl group optionally having substituents, or a heterocyclic group optionally having substituents. + Indicates sulfonium cation or iodonium cation. The compound (A) is represented by the following general formula (b3), In general formula (b3), L represents a single bond or a divalent linker. When multiple Ls are present, they may be the same or different. A represents a group whose polarity changes due to decomposition by acid (a). When multiple As are present, they may be the same or different. o, p, and q independently represent integers from 0 to 5. The sum of o, p, and q is greater than 1 and less than 5, M + This indicates a sulfonium ion or an iodonium ion.

2. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1, wherein, The pKa of the acid (ac2) is more than 1 higher than that of the acid (ac1).

3. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The ratio of the content of compound (B) to the content of the basic compound (C), i.e., (B) / (C) in molar ratio, is 1.1 or more and 10 or less.

4. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The ratio of the sum of the contents of compound (B) and the basic compound (C) to the sum of the contents of compound (A) and the contents of compound (B), i.e., [(B) + (C)] / [(A) + (B)], is 0.3 or more and 1.0 or less in molar ratio.

5. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The content of compound (A) is 5% by mass or more and 60% by mass or less relative to the total solids content of the photosensitive radioactive or radiosensitive linear resin composition.

6. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The group (a) whose polarity changes due to decomposition by the action of acid is a group represented by the following general formula (T-1). In general formula (T-1), R 11 Indicates a hydrogen atom or an alkyl group. R 12 The symbol represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, wherein the alkyl and cycloalkyl groups optionally contain an ether bond or a carbonyl bond. R 13 The alkyl, cycloalkyl, or aryl group may optionally contain an ether or carbonyl bond. R 11 and R 12 They can be arbitrarily bonded together to form a ring. R 12 and R 13 They can be arbitrarily bonded together to form a ring. * indicates a link key.

7. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The ratio of the content of compound (A) to the content of compound (B), i.e., (A) / (B) in molar ratio, is 0.2 or more and 2.0 or less.

8. A photosensitive radioactive or radioactive linear film formed using any one of the photosensitive radioactive or radioactive linear resin compositions according to claims 1 to 7.

9. A method for forming a pattern, comprising: The resist film forming process uses the photosensitive radioactive or radiosensitive linear resin composition according to any one of claims 1 to 7 to form the resist film; The exposure process involves exposing the resist film to light. and In the developing process, the exposed resist film is developed using a developing solution.

10. A method for manufacturing an electronic device, comprising the pattern forming method of claim 9.

11. A photosensitive radioactive or radioactive linear resin composition for photomask manufacturing, wherein the photosensitive radioactive or radioactive linear resin composition according to any one of claims 1 to 7 is used in photomask manufacturing.

12. A method for manufacturing a photomask, using the photosensitive radioactive or radiosensitive linear resin composition for photomask manufacturing as described in claim 11.

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