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

Abstract

The present invention aims to provide an actinic ray- or radiation-sensitive resin composition capable of forming a pattern with excellent LWR performance even after long-term storage. Furthermore, the present invention aims to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the actinic ray- or radiation-sensitive resin composition. The actinic ray- or radiation-sensitive resin composition of the present invention comprises a resin that decomposes to increase its polarity by the action of an acid and a compound that generates an acid upon irradiation with actinic rays or radiation, wherein the compound that generates an acid upon irradiation with actinic rays or radiation comprises one or more compounds selected from compounds (I) and (III).

Description

Technical Field

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

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

[0003] To further miniaturize semiconductor devices, the wavelength of exposure light sources has been shortened, and the numerical aperture (NA) of projection lenses has been increased. Currently, exposure systems using ArF excimer lasers with a wavelength of 193nm as light sources are being developed. Furthermore, research is also underway into patterning methods using extreme ultraviolet (EUV) light and electron beams (EB) as light sources.

[0004] Under such circumstances, various structures have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.

[0005] For example, Patent Document 1 discloses an acid generator containing a salt represented by the following formula (I-114) as a component used in a resist composition.

[0006] [Chemical Formula 1]

[0007]

[0008] Previous technical literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2019-24989 Summary of the Invention

[0011] Technical issues to be solved by the invention

[0012] The present inventors have studied the resist composition described in Patent Document 1 and have found that the LWR (line width roughness) performance of the pattern may deteriorate when the resist composition is stored for a long period (eg, 3 months) after production and then used.

[0013] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent LWR performance even after long-term storage.

[0014] Furthermore, the present invention aims to provide a resist film, a pattern forming method, and a method for producing an electronic device related to the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.

[0015] Means for solving technical problems

[0016] The present inventors have discovered that the above-mentioned problems can be solved by the following configuration.

[0017] [1] An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin which decomposes to increase polarity by the action of an acid and a compound which generates an acid by irradiation with actinic rays or radiation,

[0018] The compound that generates an acid upon irradiation with actinic rays or radiation includes at least one of the compounds (I) and (II) described below.

[0019] [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [2], wherein

[0020] The acid-decomposable group refers to a group represented by the formula (1) or (2) described later.

[0021] [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [2], wherein

[0022] The acid-decomposable group refers to a group represented by the above formula (1).

[0023] [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein

[0024] In the above compound (I), the above cationic site M1 + and the above-mentioned cationic site M2 + At least one of the compounds has the acid-decomposable group, and in the compound (II), the cationic site M1 + At least one of them has the above-mentioned acid-decomposable group.

[0025] [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein

[0026] The above anion site A2 - It shows the structure represented by any of the formulae (BB-1) to (BB-3) described later.

[0027] [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein

[0028] The anion site A1 - It shows the structure represented by any of the formulae (AA-1) and (AA-3) described later.

[0029] [7] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6].

[0030] [8] A pattern forming method comprising the following steps:

[0031] A step of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to [6];

[0032] a step of exposing the resist film; and

[0033] A step of developing the exposed resist film using a developer.

[0034] [9] A method for manufacturing an electronic device, comprising the pattern forming method described in [8].

[0035] Effects of the Invention

[0036] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent LWR performance even after long-term storage.

[0037] Furthermore, the present invention can provide a resist film, a pattern forming method, and a method for producing an electronic device related to the actinic ray-sensitive or radiation-sensitive resin composition. DETAILED DESCRIPTION

[0038] Hereinafter, the present invention will be described in detail.

[0039] The constituent elements described below will be described based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0040] In the marking of groups (atomic groups) in this specification, unless it is contrary to the purpose of the present invention, the marking that does not describe substitution and unsubstituted includes not only groups without substitution but also groups with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl) but also alkyl groups with substitution (substituted alkyl). Furthermore, "organic group" in this specification refers to a group containing at least one carbon atom.

[0041] Unless otherwise specified, the substituent is preferably a monovalent substituent.

[0042] "Actinic rays" or "radiation" as used herein include, for example, the bright-line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB). "Light" as used herein refers to actinic rays or radiation.

[0043] Unless otherwise specified, "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer laser, extreme ultraviolet light, X-rays and EUV light, but also drawing using particle beams such as electron beams and ion beams.

[0044] In this specification, “to” is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0045] Unless otherwise specified, the bonding direction of divalent groups indicated in this specification is not limited. For example, when Y in a compound represented by the formula "XYZ" is -COO-, Y can be either -CO-O- or -O-CO-. Furthermore, the above compound can be either "X-OO-OZ" or "XO-CO-Z."

[0046] In the present specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic acid means acrylic acid and methacrylic acid.

[0047] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (also referred to as molecular weight distribution) (Mw / Mn) of the resin are defined as polystyrene-equivalent values ​​obtained by GPC measurement using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0048] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, is a value obtained by calculation using the following software package 1 based on a database of Hammett's substituent constants and known literature values. The pKa values ​​described in this specification are all values ​​obtained by calculation using this software package.

[0049] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0050] On the other hand, pKa can also be calculated by molecular orbital algorithm. As a specific method, the calculation of H in aqueous solution based on thermodynamic cycle can be cited. + The method of calculating the dissociation free energy. + The calculation method of dissociation free energy can be performed by DFT (density functional theory), but various other methods have been reported in the literature, etc., and the present invention is not limited to this. In addition, there are many software programs that can implement DFT, for example, Gaussian16 can be cited.

[0051] As described above, the pKa in this specification refers to a value obtained by calculation using Software Package 1 based on Hammett's substituent constant and a database of known literature values. However, when the pKa cannot be calculated using this method, a value obtained using Gaussian 16 based on DFT (density functional theory) is used.

[0052] As described above, the pKa in this specification refers to "pKa in aqueous solution." However, when the pKa in aqueous solution cannot be calculated, the "pKa in dimethyl sulfoxide (DMSO) solution" is used.

[0053] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0054] [Actinic ray or radiation-sensitive resin composition]

[0055] Characteristic features of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "resist composition") include a resin that decomposes and increases in polarity by the action of an acid (hereinafter also referred to as "acid-decomposable resin" or "resin (A)"), and a compound that generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as "photoacid generator"), and the composition includes one or more of the compounds (I) and (II) described below (hereinafter also referred to as "specific compound").

[0056] With the above-mentioned structure, the resist composition of the present invention can form a pattern having excellent LWR even when used after long-term storage after production.

[0057] Hereinafter, the presumed mechanism of action of the resist composition of the present invention will be described in comparison with the compound disclosed in Patent Document 1.

[0058] The present inventors have now discovered that, when a resist composition is prepared and stored for a long period of time, the compound disclosed in Patent Document 1 readily cleaves the acetal structure in the linker connecting the two anionic sites under the action of an acid, thereby deteriorating the LWR performance of the resulting pattern. Furthermore, it is presumed that the acid is generated by the decomposition of the photoacid generator or the resin during storage of the resist composition.

[0059] In contrast, since the specific compound has a structure in which the linking site connecting the anion sites and / or the linking site between the anion site and the structural site Z is not cut under the action of an acid (Condition IB, Condition IIB), the LWR performance of the pattern formed is excellent even when the resist composition is stored for a long time after production and then used.

[0060] On the other hand, the specific compound has an acid-decomposable group (hereinafter also referred to as "acid-decomposable group") formed by protecting a polar group by a leaving group that is detached by the action of an acid, at a position that does not cut off the connection site connecting the anion sites to each other or the connection site between the anion site and the structural site Z. The above-mentioned acid-decomposable group in the specific compound can be decomposed by acid during exposure and expose the polar group. That is, the resist film containing the specific compound can increase the solubility of the resist film in the exposed area to the alkaline developer. As a result, the resist film has an excellent dissolution contrast between the exposed area and the unexposed area, and the formed pattern shows excellent LWR performance.

[0061] It is estimated that the resist composition of the present invention can form a pattern excellent in LWR performance even when used after long-term storage after production due to the synergistic effect of the above-mentioned action mechanism.

[0062] In addition, hereinafter, even when a resist composition is produced and then stored for a long period of time before use, the fact that a pattern having more excellent LWR performance can be formed is also referred to as “the effect of the present invention is more excellent”.

[0063] Hereinafter, the resist composition of the present invention will be described in detail.

[0064] The resist composition may be a positive-working resist composition or a negative-working resist composition, and may be a resist composition for alkaline development or a resist composition for organic solvent development.

[0065] The resist composition is typically a chemically amplified resist composition.

[0066] First, various components of the resist composition will be described in detail below.

[0067] 〔Photoacid generator〕

[0068] The resist composition contains one or more compounds (specific compounds) selected from compounds (I) and (II) as a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation.

[0069] In addition, as described later, the resist composition may further contain another photoacid generator (hereinafter also referred to as "photoacid generator B") other than the specific compound.

[0070] Hereinafter, first, the specific compounds (compounds (I) and (II)) will be described.

[0071] <Compound (I)>

[0072] Compound (I): having one or more structural sites X and one or more structural sites Y as described below, and an acid-decomposable group formed by protecting a polar group with a leaving group that is released by the action of an acid, and generating an acid comprising the following first acidic site derived from the following structural site X and the following second acidic site derived from the following structural site Y upon irradiation with actinic rays or radiation.

[0073] Structural site X: Anionic site A1 - and cationic site M1 + and the first acidic site represented by HA1 is formed by irradiation with actinic rays or radiation.

[0074] Structural site Y: Anionic site A2 - and cationic site M2+ and forms a second acidic site represented by HA2 by irradiation with actinic rays or radiation.

[0075] Among them, compound (I) satisfies the following conditions IA and IB.

[0076] Condition IA: In the above compound (I), H + Substituting the cationic site M1 in the structural site X + and the cationic site M2 in the structural site Y + The compound PI has the following acid dissociation constant: a1, which comes from the acid dissociation constant a1. + Substituting the cationic site M1 in the structural site X + The acidic site represented by HA1; and the acid dissociation constant a2, which is derived from the acidic site represented by H + Substituting the cationic site M2 in the structural site Y + The acidic site represented by HA2 is formed, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0077] The following describes the condition IA in more detail.

[0078] When compound (I) is a compound that generates an acid having one of the first acidic sites derived from the structural site X and one of the second acidic sites derived from the structural site Y, compound PI corresponds to a "compound having HA1 and HA2".

[0079] Regarding the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI, more specifically, when the acid dissociation constant of the compound PI is determined, the compound PI becomes "having A1 - and HA2" is the acid dissociation constant a1, and the above "compound with A1 - and HA2" becomes "compound with A1 - and A2 - The pKa of the compound is the acid dissociation constant a2.

[0080] Furthermore, when compound (I) is a compound that produces an acid having two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y, compound PI corresponds to a "compound having two HA1s and one HA2".

[0081] When the acid dissociation constant of compound PI is calculated, compound PI becomes "having 1 A1 - , 1 HA1 and 1 HA2" and the acid dissociation constant of "compound with 1 A1- , 1 HA1 and 1 HA2" becomes "a compound having 2 A1 - The acid dissociation constant for the compound having 1 HA2 corresponds to the above-mentioned acid dissociation constant a1. - and 1 HA2" becomes a "compound with 2 A1 - and A2 - The acid dissociation constant of the compound "corresponds to the acid dissociation constant a2. That is, as in the compound PI, there are multiple + Substituting the cationic site M1 in the structural site X + When the acid dissociation constant of the acidic site represented by HA1 is obtained, the value of the acid dissociation constant a2 is greater than the largest value among the multiple acid dissociation constants a1. In addition, compound PI is referred to as "having one A1 - , 1 HA1 and 1 HA2” is the acid dissociation constant, and the “compound with 1 A1 - , 1 HA1 and 1 HA2" becomes "a compound having 2 A1 - When the acid dissociation constant of a compound with 1 HA2 is set to ab, the relationship between aa and ab satisfies aa <ab。

[0082] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the above-mentioned method for measuring the acid dissociation constant.

[0083] When compound (I) is irradiated with actinic rays or radiation, the above-mentioned compound PI corresponds to the acid generated.

[0084] When compound (I) has two or more structural parts X, the structural parts X may be the same or different. - and 2 or more of the above M1 + They can be the same or different.

[0085] Furthermore, in compound (I), the above-mentioned A1 - and A2 above - , and the above-mentioned M1 + and the above M2 + They can be the same or different, but the above A1 - and A2 above - Preferably they are different.

[0086] From the perspective of achieving superior LWR performance of the resulting pattern, in the compound PI, the difference between the acid dissociation constant a1 (the maximum value when multiple acid dissociation constants a1 exist) and the acid dissociation constant a2 is preferably 0.10 or greater, and more preferably 0.50 or greater. The upper limit of the difference between the acid dissociation constant a1 (the maximum value when multiple acid dissociation constants a1 exist) and the acid dissociation constant a2 is not particularly limited, and is, for example, 20.00 or less.

[0087] Furthermore, from the viewpoint of further improving the LWR performance of the formed pattern, in the compound PI, the acid dissociation constant a2 is, for example, 15.00 or less, preferably 12.00 or less. The lower limit of the acid dissociation constant a2 is preferably -4.00 or more.

[0088] Furthermore, from the viewpoint of achieving superior LWR performance of the formed pattern, the acid dissociation constant a1 of the compound PI is preferably 1.00 or less, more preferably 0.50 or less. The lower limit of the acid dissociation constant a1 is preferably -12.00 or greater.

[0089] Condition IB: The compound (I) is connected to one or more anionic sites A1 in the structural site X under the action of an acid. - With one or more anionic sites A2 in the structural site Y - The structure where the site (hereinafter also referred to as "connection site") is not cut. - With anionic site A2 - The linking site of compound (I) is not cut off under the action of acid. - With anionic site A2 - That is, when compound (I) is a compound represented by formula (Ia-1) described later, it means that the linking group represented by L1 is not cut under the action of acid, and when compound (I) is a compound represented by formula (Ia-2) to (Ia-4) described later, it means that the linking group represented by L1 is not cut under the action of acid. 21 、L 22 、L 31 、L 32 and L 41 The structure in which the linking group is not cut off by the action of acid.

[0090] As the linking site that is cut by the action of acid, specifically, there can be mentioned a structure containing a polar group protected by a leaving group that is separated by the action of acid, and the leaving group is separated (including decomposition) by the action of acid, thereby cutting the organic linking group of the linking site. For example, the compound disclosed in Patent Document 1 decomposes the acetal structure site connecting two anions by the action of acid and decomposes into a dihydroxy compound and a ketone compound. In compound (I), the anion site A1 - With anionic site A2 - The connection site of the compound (I) does not include a structure in which the polar group is protected by a leaving group that is separated by the action of an acid. - With anionic site A2 - The polar group protected by a leaving group that is detached by the action of an acid may be substituted for the connecting site of the resin (A) at a position that does not sever the connecting site. The structure of the polar group protected by a leaving group that is detached by the action of an acid will be described later together with the acid-decomposable group contained in the resin (A).

[0091] Anionic site A1 - and anionic site A2 - It is a structural part containing a negatively charged atom or atomic group, and examples thereof include structural parts selected from the following formulas (AA-1) to (AA-3) and (BB-1) to (BB-5). - , preferably an acidic site having a small acid dissociation constant, preferably formulas (AA-1) to (AA-3), more preferably any of formulas (AA-1) and (AA-3). - , preferably can form an acid dissociation constant greater than the anion site A1 - The acidic site is preferably any of the formulas (BB-1) to (BB-5), and more preferably any of the formulas (BB-1) to (BB-3) from the viewpoint of a better effect of the present invention. In addition, in the following formulas (AA-1) to (AA-3) and (BB-1) to (BB-5), * represents a bonding position. And, R A It represents a monovalent organic group.

[0092] [Chemical Formula 2]

[0093]

[0094] Furthermore, the cationic site M1 + and cationic site M2 +It is a structural part containing a positively charged atom or atomic group, and an example thereof can be an organic cation having a charge of 1. In addition, there is no particular limitation on the organic cation, and an example thereof can be an organic cation having the same charge as M in the formula (Ia-1) described later. 11 + and M 12 + The organic cation represented by is the same organic cation.

[0095] Compound (I) has an acid-decomposable group (hereinafter also referred to as "acid-decomposable group") formed by protecting a polar group with a leaving group that is released by the action of an acid. In compound (I), the position of the acid-decomposable group is as long as it does not cut the anion site A1 in the structural site X. - With the anion site A2 in the structural site Y - The position of the connection is not particularly limited. From the viewpoint of achieving a better effect of the present invention, the acid-decomposable group is preferably located at the cationic site M1. + and cationic site M2 + At least one of .

[0096] The acid-decomposable group will be described later together with the acid-decomposable group contained in the resin (A), and among them, an acid-decomposable group represented by the following formula (1) or (2) is preferred.

[0097] [Chemical Formula 3]

[0098]

[0099] In formula (1), R 11 ~R 13 Each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. In addition, the alkyl group and the alkenyl group may be either linear or branched. Furthermore, the cycloalkyl group and the aryl group may be either monocyclic or polycyclic.

[0100] In addition, R 11 ~R 13 Two of them may be bonded to each other to form a ring.

[0101] *Indicates bonding position.

[0102] When R 11 ~R 13 When all are alkyl groups (straight chain or branched), it is preferred that R 11 ~R 13 At least two of them are methyl groups.

[0103] As R 11 ~R 13 The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.

[0104] As R 11 ~R 13 The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0105] As R 11 ~R 13 The aryl group is preferably an aryl group having 6 to 10 carbon atoms.

[0106] As R 11 ~R 13 The alkenyl group is preferably a vinyl group.

[0107] As R 11 ~R 13 The cycloalkyl group formed by the two bonds in the group may be either a monocyclic or polycyclic group, wherein a monocyclic cycloalkyl group is preferred, and a 5-membered or 6-membered monocyclic cycloalkyl group is more preferred. 11 ~R 13 In a cycloalkyl group formed by bonding two of the methylene groups in the ring, for example, one of the methylene groups constituting the ring may be substituted by a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be substituted by vinylene.

[0108] And, by R 11 ~R 13 The alkyl, cycloalkyl, alkenyl, and aryl groups represented by may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms).

[0109] In formula (2), R2 represents an alkyl group or a cycloalkyl group, and R3 represents a hydrogen atom, an alkyl group or a cycloalkyl group. 11 The alkyl and cycloalkyl groups represented have the same meanings and preferred embodiments are also the same.

[0110] In addition, R2 and R3 can be bonded to each other to form a ring. The ring formed by the bonding of R2 and R3 can be any one of a monocyclic ring and a polycyclic ring, preferably a monocyclic ring, more preferably a 5-membered or 6-membered monocyclic ring. As the above-mentioned ring, an alicyclic ring is preferred.

[0111] *Indicates bonding position.

[0112] The acid-decomposable group is preferably introduced into the compound (I) in the form of a monovalent group represented by, for example, the following formula (1L) or the following formula (2L).

[0113] Formula (1L)*-LX-RX1

[0114] Formula (2L)*-LX-RX2

[0115] In the above formula (1L) and formula (2L), LX represents a single bond or a divalent linking group.

[0116] There is no particular limitation on the divalent linking group, and examples thereof include -CO-, -O-, -SO-, -SO2-, -S-, alkylene groups (preferably having 1 to 6 carbon atoms. Can be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring groups (preferably 6-10 membered rings, more preferably 6 membered rings), and divalent linking groups formed by combining a plurality of them.

[0117] Furthermore, the above-mentioned alkylene group, the above-mentioned cycloalkylene group, and the divalent aromatic hydrocarbon ring group may be substituted by a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).

[0118] In the above formula (1L) and formula (2L), RX1 represents the acid-decomposable group represented by the above formula (1), and RX2 represents the acid-decomposable group represented by the above formula (2).

[0119] The number of acid-decomposable groups possessed by compound (I) is not particularly limited, and is, for example, 1 to 10, preferably 1 to 9, and more preferably 1 to 6.

[0120] Furthermore, as described above, in compound (I), the acid-decomposable group is only required to be arranged in the anion site A1 in the structural site X without cleaving the anion site A1. - With the anion site A2 in the structural site Y - The position of the connection is not particularly limited, but is preferably arranged at the cationic site M1 from the viewpoint of better effects of the present invention. + and cationic site M2 + When the acid-decomposable group is located at the cationic site M1 + and cationic site M2 + When at least one of the above is present, it is preferred that one cationic site has 1 to 3 acid-decomposable groups.

[0121] The specific structure of compound (I) is not particularly limited, and examples thereof include compounds represented by formula (Ia-1) to formula (Ia-4) described later.

[0122] First, the compound represented by formula (Ia-1) is described below. The compound represented by formula (Ia-1) is as follows.

[0123] M 11 +A 11 - -L1-A 12 - M 12 + (Ia)

[0124] Compound (Ia-1) generates HA by irradiation with actinic rays or radiation. 11 -L1-A 12 H represents an acid.

[0125] In formula (Ia-1), M 11 + and M 12 + Each independently represents an organic cation.

[0126] A 11 - and A 12 - Each independently represents a monovalent anionic functional group.

[0127] L1 represents a divalent linking group.

[0128] M 11 + and M 12 + They can be the same or different.

[0129] A 11 - and A 12 - They may be the same or different, but are preferably different from each other.

[0130] In the above formula ([a-1]), when H + Replaced by M 11 + and M 12 + Compound Pia(HA 11 -L1-A 12 H), derived from A 12 The acid dissociation constant a2 of the acidic site represented by H is greater than that of the acidic site represented by HA 11 The acid dissociation constant a1 of the acidic site represented by is represented by . The preferred values ​​of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. Furthermore, compound PIa is the same as the acid generated by the compound represented by formula (Ia-1) upon irradiation with actinic rays or radiation.

[0131] And, M 11 + 、M 12+ 、A 11 - 、A 12 - and at least one of L1 has an acid-decomposable group as a substituent.

[0132] In addition, when A 11 - 、A 12 - When at least one of L1 and L2 has an acid-decomposable group as a substituent, in the above formula (Ia-1), H + Replaced by M 11 + and M 12 + In a compound in which a leaving group in an acid-decomposable group is substituted with a hydrogen atom (i.e., in the case of the acid-decomposable group represented by the above formula (1), it is a carboxyl group), the acid dissociation constant of the site derived from the site derived from the site derived from the site derived from the site derived from the acid-decomposable group is preferably greater than that derived from the site derived from A 12 The acid dissociation constant a2 of the acidic site represented by H.

[0133] In formula (Ia-1), M1 + and M2 + The organic cations represented are as follows.

[0134] By A 11 - The monovalent anionic functional group represented by - A is a monovalent group. 12 - The monovalent anionic functional group represented by the formula (A) is a group containing the anionic portion A2. - A monovalent group.

[0135] As a 11 - and A 12 - The monovalent anionic functional group represented by A is preferably a monovalent anionic functional group containing an anion portion of any of the above formulas (AA-1) to (AA-3) and (BB-1) to (BB-5), and more preferably a monovalent anionic functional group selected from the group consisting of formulas (AX-1) to (AX-3) and (BX-1) to (BX-6). 11 -A univalent anionic functional group represented by A is preferably a univalent anionic functional group represented by any one of formulas (AX-1) to (AX-3), and more preferably a univalent anionic functional group represented by any one of formulas (AX-1) and (AX-3). 12 - The monovalent anionic functional group represented by the formula (BX-1) to (BX-6) is preferred, and from the viewpoint of better effects of the present invention, the monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-4) is more preferred.

[0136] [Chemical Formula 4]

[0137]

[0138] In formulas (AX-1) to (AX-3), R A1 and R A2 Each independently represents a monovalent organic group. * represents a bonding position.

[0139] As R A1 The monovalent organic group represented by the present invention includes cyano, *-SO2R A11 Base, *-COR A11 Ji et al.

[0140] As the above R A11 , preferably a linear, branched or cyclic alkyl group which may have a substituent.

[0141] The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

[0142] The alkyl group may have a substituent. As the substituent, preferably a monovalent group represented by the above formula (1L) or formula (2L), a fluorine atom, or a cyano group, more preferably a fluorine atom or a cyano group. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0143] As R A2 The monovalent organic group represented by is preferably a linear, branched or cyclic alkyl group or aryl group.

[0144] The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

[0145] The alkyl group may have a substituent. As the substituent, preferably a monovalent group represented by the above formula (1L) or formula (2L), a fluorine atom, or a cyano group, more preferably a fluorine atom or a cyano group. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0146] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

[0147] The aryl group may have a substituent. The substituent is preferably a monovalent group represented by the above formula (1L) or formula (2L), a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), or a cyano group, and more preferably a fluorine atom, an iodine atom, a perfluoroalkyl group, or a cyano group.

[0148] In formulas (B-1) to (B-6), R B represents a monovalent organic group. * represents a bonding position.

[0149] As R B The monovalent organic group represented by is preferably a linear, branched or cyclic alkyl group or aryl group.

[0150] The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

[0151] The alkyl group may have a substituent. The substituent is not particularly limited, but is preferably a monovalent group represented by the above formula (1L) or formula (2L), a fluorine atom, or a cyano group, and more preferably a fluorine atom or a cyano group. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0152] In addition, the carbon atom that serves as a bonding position in the alkyl group (for example, in the case of formulas (BX-1) and (BX-4), it corresponds to the carbon atom that directly bonds to -CO- as indicated in the formula in the alkyl group; in the case of formulas (BX-2) and (BX-3), it corresponds to the carbon atom that directly bonds to -SO2- as indicated in the formula in the alkyl group; in the case of formula (BX-6), it corresponds to the carbon atom that directly bonds to -N- as indicated in the formula in the alkyl group) - - a carbon atom to which the carbon atom is directly bonded.) When the carbon atom has a substituent, the substituent is preferably a fluorine atom or a cyano group.

[0153] Furthermore, in the above-mentioned alkyl group, a carbon atom may be substituted by a carbonyl carbon.

[0154] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

[0155] The aryl group may have a substituent. The substituent is preferably a monovalent group represented by the above formula (1L) or formula (2L), a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a cyano group, an alkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkoxy group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), or an alkoxycarbonyl group (for example, preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms). More preferably, it is a fluorine atom, an iodine atom, a perfluoroalkyl group, a cyano group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.

[0156] In formula (I), the divalent linking group represented by L1 is not particularly limited, and examples thereof include -CO-, -NR-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), a divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, and even more preferably a 6-membered ring), and divalent linking groups obtained by combining a plurality thereof. R includes a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably an alkyl group (preferably having 1 to 6 carbon atoms).

[0157] Furthermore, the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may be substituted with a substituent. Examples of the substituent include a monovalent group represented by the above formula (1L) or formula (2L) and a halogen atom (preferably a fluorine atom).

[0158] As the divalent linking group represented by L1, a divalent linking group represented by formula (L1) is particularly preferred.

[0159] [Chemical Formula 5]

[0160]

[0161] In formula (L1), L 111 represents a single bond or a divalent linking group.

[0162] As L 111The divalent linking group represented by is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO2-, an alkylene group which may have a substituent (preferably having 1 to 6 carbon atoms and may be linear or branched), a cycloalkylene group which may have a substituent (preferably having 3 to 15 carbon atoms), an arylene group which may have a substituent (preferably having 6 to 10 carbon atoms), and a divalent linking group formed by combining a plurality of these. The substituent is not particularly limited, and examples thereof include a monovalent group represented by the above formula (1L) or formula (2L) and a halogen atom.

[0163] p represents an integer of 0 to 3, and preferably represents an integer of 1 to 3.

[0164] Xf1 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0165] Xf2 each independently represents a hydrogen atom, an alkyl group optionally having a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. As Xf2, a fluorine atom or an alkyl group substituted with at least one fluorine atom is preferred, and a fluorine atom or a perfluoroalkyl group is more preferred.

[0166] Among them, Xf1 and Xf2 are preferably each independently a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, it is further preferred that both Xf1 and Xf2 are fluorine atoms.

[0167] *Indicates bonding position.

[0168] When L1 in formula (Ia-1) represents a divalent linking group represented by formula (L1), L in formula (L1) 111 The connecting bond (*) on the side is preferably the same as that of A in formula (Ia-1) 12 - bonding.

[0169] In formula (I), 11 + and M 12 + Preferred embodiments of the organic cation represented by hereinafter are described in detail.

[0170] By M 11 + and M 12 + The organic cations represented are each independently preferably an organic cation represented by formula (ZaI) (cation (ZaI)) or an organic cation represented by formula (ZaII) (cation (ZaII)).

[0171] [Chemical Formula 6]

[0172]

[0173] R 204 -I + -R 205 (ZaII)

[0174] In the above formula (ZaI),

[0175] R 201 、R 202 and R 203 Each independently represents an organic group.

[0176] As R 201 、R 202 and R 203 The number of carbon atoms of the organic group is usually 1 to 30, preferably 1 to 20. 201 ~R 203 Two of them may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester group, an amide group or a carbonyl group in the ring. 201 ~R 203 Examples of the group formed by bonding two of the groups include an alkylene group (e.g., a butylene group and a pentylene group) and -CH2-CH2-O-CH2-CH2-.

[0177] Preferred forms of the organic cation in formula (ZaI) include the cation (ZaI-1) and cation (ZaI-2) described later, the organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and the organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)).

[0178] First, the cation (ZaI-1) will be described.

[0179] The cation (ZaI-1) is R in the above formula (ZaI) 201 ~R 203 At least one of the arylsulfonium cations is an aryl group.

[0180] In the arylsulfonium cation, R 201 ~R 203 All are aryl, or R 201 ~R 203 Part of the alkyl group is an aryl group, and the rest are an alkyl group or a cycloalkyl group.

[0181] And, R 201 ~R 203 One of them is an aryl group, R201 ~R 203 The remaining two of R may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group in the ring. 201 ~R 203 In the group formed by two bonds, for example, one or more methylene groups may be substituted by an oxygen atom, a sulfur atom, an ester group, an amide group and / or a carbonyl group (for example, a butylene group, a pentylene group or -CH2-CH2-O-CH2-CH2-).

[0182] Examples of the arylsulfonium cation include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0183] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.

[0184] The alkyl group or cycloalkyl group that the arylsulfonium cation may have as needed is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group, and cyclohexyl group.

[0185] As R 201 ~R 203 The substituents that the aryl, alkyl and cycloalkyl groups may have are preferably each independently a monovalent group (a group including an acid-decomposable group) represented by the above formula (1L) or formula (2L), an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom (e.g., fluorine, iodine), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, a phenylthio group, and the like.

[0186] The above-mentioned substituents may further have a substituent if possible. For example, the above-mentioned alkyl group may have a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.

[0187] Next, the cation (ZaI-2) will be described.

[0188] The cation (ZaI-2) is R in the formula (ZaI)201 ~R 203 Each independently represents a cation of an organic group that does not have an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.

[0189] As R 201 ~R 203 The organic group having no aromatic ring usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0190] R 201 ~R 203 Each independently is preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0191] As R 201 ~R 203 The alkyl and cycloalkyl groups in the alkyl group include, for example, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl).

[0192] R 201 ~R 203 It may be further substituted by a monovalent group represented by the above formula (1L) or formula (2L), a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0193] Next, the cation (ZaI-3b) will be described.

[0194] The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0195] [Chemical Formula 7]

[0196]

[0197] In formula (ZaI-3b),

[0198] R 1c ~R 5c Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, an arylthio group, or a monovalent group represented by the above formula (1L) or formula (2L).

[0199] R 6c and R 7cEach independently represents a hydrogen atom, an alkyl group (such as a tert-butyl group), a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

[0200] R x and R y Each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

[0201] R 1c ~R 5c Any two or more of R 5c With R 6c 、R 6c With R 7c 、R 5c With R x and R x With R y They may be bonded to each other to form a ring, and the ring may independently contain an oxygen atom, a sulfur atom, a keto group, an ester bond, or an amide bond.

[0202] Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0203] As R 1c ~R 5c Any two or more of R 6c With R 7c and R x With R y Examples of the group formed by the bonding include alkylene groups such as butylene and pentylene. The methylene group in the alkylene group may be substituted with a heteroatom such as an oxygen atom.

[0204] As R 5c With R 6c and R 5c With R x The group formed by the bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0205] R 1c ~R 5c 、R 6c 、R 7c 、R x 、R y , and R 1c ~R 5c Any two or more of R 5c With R 6c 、R 6c With R 7c 、R5c With R x and R x With R y The ring formed by bonding each other may have a monovalent group represented by the above-mentioned formula (1L) or formula (2L) as a substituent.

[0206] Next, the cation (ZaI-4b) will be described.

[0207] The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0208] [Chemical Formula 8]

[0209]

[0210] In formula (ZaI-4b),

[0211] l represents an integer from 0 to 2.

[0212] r represents an integer from 0 to 8.

[0213] R 13 represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a haloalkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent, and examples of the substituent include monovalent groups represented by the above-mentioned formula (1L) or formula (2L).

[0214] And, as R 13 In one embodiment, it is also possible to select a monovalent group represented by the above formula (1L) or formula (2L).

[0215] R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), an alkyl group, a haloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent, and examples of the substituent include monovalent groups represented by the above formula (1L) or formula (2L). When there are multiple R 14 , each independently represents the above-mentioned groups such as hydroxyl group.

[0216] And, as R 14 In one embodiment, it is also possible to select a monovalent group represented by the above formula (1L) or formula (2L).

[0217] R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. 15Can bond to each other to form a ring. 15 When they are bonded to each other to form a ring, heteroatoms such as oxygen atoms and nitrogen atoms may be contained in the ring skeleton. 15 are alkylene groups, and are bonded to each other to form a ring structure. 15 The ring formed by bonding with each other may have a substituent, and examples of the substituent include monovalent groups represented by the above-mentioned formula (1L) or formula (2L).

[0218] In formula (ZaI-4b), as R 13 、R 14 and R 15 The alkyl group is preferably linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. More preferred alkyl groups are methyl, ethyl, n-butyl, tert-butyl, and the like.

[0219] Next, formula (ZaII) will be described.

[0220] In formula (ZaII), R 204 and R 205 Each independently represents an aryl group, an alkyl group or a cycloalkyl group.

[0221] As R 204 and R 205 R is an aryl group, preferably a phenyl group or a naphthyl group, more preferably a phenyl group. 204 and R 205 The aryl group may be an aryl group containing a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group containing a heterocyclic ring include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0222] As R 204 and R 205 The alkyl group and cycloalkyl group are preferably a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl or norbornyl).

[0223] R 204 and R 205 The aryl group, alkyl group and cycloalkyl group of R may each independently have a substituent. 204 and R 205The substituents that the aryl, alkyl and cycloalkyl groups may have include, for example, a monovalent group represented by the above formula (1L) or formula (2L), an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group.

[0224] Next, formulas (Ia-2) to (Ia-4) are described.

[0225] [Chemical Formula 9]

[0226]

[0227] In formula (Ia-2), A 21a - and A 21b - Each independently represents a monovalent anionic functional group. 21a - and A 21b - The monovalent anionic functional group represented by - As a monovalent group composed of 21a - and A 21b - The monovalent anionic functional group represented by is not particularly limited, and examples thereof include one or more monovalent anionic functional groups selected from the above formulae (AX-1) to (AX-3).

[0228] A 22 - Indicates a divalent anionic functional group. 22 - The divalent anionic functional group represented by the formula (A) is a functional group containing the anionic portion A2. - As a divalent group composed of 22 - Examples of the divalent anionic functional group represented by include divalent anionic functional groups represented by the following formulae (BX-7) to (BX-9).

[0229] [Chemical Formula 10]

[0230]

[0231] M 21a + 、M 21b + and M 22 +Each independently represents an organic cation. 21a + 、M 21b + and M 22 + The organic cation represented by M1 + The meaning is the same and the preferred method is also the same.

[0232] L 21 and L 22 Each independently represents a divalent organic group.

[0233] Furthermore, in the above formula (Ia-2), when H + Replaced by M 21a + 、M 21b + and M 22 + In the compound PIa-2 composed of an organic cation represented by A 22 The acid dissociation constant a2 of the acidic site represented by H is greater than that of the acid site represented by A 21a The acid dissociation constant a1-1 of H and its origin from A 21b The acid dissociation constant a1-2 of the acidic site represented by H. In addition, the acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the above-mentioned acid dissociation constant a1.

[0234] In addition, A 21a - and A 21b - They may be the same or different from each other. 21a + 、M 21b + and M 22 + They can be the same or different from each other.

[0235] And, M 21a + 、M 21b + 、M 22 + 、A 21a - 、A 21b - 、A 22 - 、L 21 and L 22 At least one of them has an acid-decomposable group as a substituent.

[0236] In addition, when A 21a- 、A 21b - 、A 22 - , L 21 and L 22 When at least one of the substituents has an acid-decomposable group, in the above formula (Ia-2), H + Replaced by M 21a + 、M 21b + and M 22 + In a compound in which a leaving group in an acid-decomposable group is substituted with a hydrogen atom (i.e., a carboxyl group in the case of the acid-decomposable group represented by the above formula (1)), the acid dissociation constant of the site derived from the site derived from the site derived from the site derived from the acid-decomposable group substituted with a hydrogen atom is preferably greater than that derived from the site derived from the acid-decomposable group represented by A 22 The acid dissociation constant a2 of the acidic site represented by H.

[0237] In formula (Ia-3), A 31a - and A 32 - Each independently represents a monovalent anionic functional group. 31a - The definition of the monovalent anionic functional group represented by 21a - and A 21b - The meaning is the same and the preferred method is also the same.

[0238] By A 32 - The monovalent anionic functional group represented by the formula (A) is a group containing the anionic portion A2. - As a monovalent group composed of 32 + The monovalent anionic functional group represented is not particularly limited, and examples thereof include one or more monovalent anionic functional groups selected from the above-mentioned formulas (BX-1) to (BX-6). From the viewpoint of achieving a better effect of the present invention, one or more monovalent anionic functional groups selected from the above-mentioned formulas (BX-1) to (BX-4) are preferred.

[0239] A 31b - Indicates a divalent anionic functional group. 31b - The divalent anionic functional group represented by the formula (A1) refers to a group containing the anionic portion A1 - As a divalent group composed of31b - Examples of the divalent anionic functional group represented by include a divalent anionic functional group represented by the following formula (AX-4).

[0240] [Chemical Formula 11]

[0241]

[0242] M 31a + 、M 31b + and M 32 + Each independently represents a monovalent organic cation. 31a + 、M 31b + and M 32 + The organic cation represented by M1 + The meaning is the same and the preferred method is also the same.

[0243] L 31 and L 32 Each independently represents a divalent organic group.

[0244] Furthermore, in the above formula (Ia-3), when H + Replaced by M 31a + 、M 31b + and M 32 + Among the compounds PIa-3 composed of organic cations represented by 32 The acid dissociation constant a2 of the acidic site represented by H is greater than that of the acidic site represented by A 31a The acid dissociation constant a1-3 of the acidic site represented by H and the acid dissociation constant a1-3 derived from A 31b The acid dissociation constant a1-4 of the acidic site represented by H. In addition, the acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the above-mentioned acid dissociation constant a1.

[0245] In addition, A 31a - and A 32 - They may be the same or different from each other. 31a + 、M 31b + and M 32 + They can be the same or different from each other.

[0246] And, M31a + 、M 31b + 、M 32 + 、A 31a - 、A 31b - 、A 32 - , L 31 and L 32 At least one of them has an acid-decomposable group as a substituent.

[0247] In addition, when A 31a - 、A 31b - 、A 32 - , L 33 and L 32 When at least one of the substituents has an acid-decomposable group, in the above formula (Ia-3), H + Replaced by M 31a + 、M 31b + and M 32 + In a compound in which a leaving group in an acid-decomposable group is substituted with a hydrogen atom (i.e., a carboxyl group in the case of the acid-decomposable group represented by the above formula (1)), the acid dissociation constant of the site derived from the site derived from the site derived from the site derived from the acid-decomposable group substituted with a hydrogen atom is preferably greater than that derived from the site derived from the acid-decomposable group represented by A 32 The acid dissociation constant a2 of the acidic site represented by H.

[0248] In formula (Ia-4), A 41a - 、A 41b - and A 42 - Each independently represents a monovalent anionic functional group. 41a - and A 41b - The definition of the monovalent anionic functional group represented by 21a - and A 21b - The meaning is the same. And, by A 42 - The definition of the monovalent anionic functional group represented by 32 -The meaning is the same and the preferred method is also the same.

[0249] M 41a + 、M 41b + and M 42 + Each independently represents an organic cation.

[0250] L 41 It represents a trivalent organic group.

[0251] Furthermore, in the above formula (Ia-4), when H + Replaced by M 41a + 、M 41b + and M 42 + Among the compounds PIa-4 composed of organic cations represented by 42 The acid dissociation constant a2 of the acidic site represented by H is greater than that of the acidic site represented by A 41a The acid dissociation constant a1-5 of the acidic site represented by H and the acid dissociation constant a1-5 derived from A 41b The acid dissociation constant a1-6 of the acidic site represented by H. In addition, the acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the above-mentioned acid dissociation constant a1.

[0252] In addition, A 41a - 、A 41b - and A 42 - They may be the same or different from each other. 41a + 、M 41b + and M 42 + They can be the same or different from each other.

[0253] And, M 41a + 、M 41b + 、M 42 + 、A 41a - 、A 41b - 、A 42 - and L 41 At least one of them has an acid-decomposable group as a substituent.

[0254] In addition, when A 41a- 、A 41b - 、A 42 - and L 41 When at least one of the substituents has an acid-decomposable group, in the above formula (Ia-4), H + Replaced by M 41a + 、M 41b + 、M 42 + In a compound in which a leaving group in an acid-decomposable group is substituted with a hydrogen atom (i.e., a carboxyl group in the case of the acid-decomposable group represented by the above formula (1)), the acid dissociation constant of the site derived from the site derived from the site derived from the site derived from the acid-decomposable group substituted with a hydrogen atom is preferably greater than that derived from the site derived from the acid-decomposable group represented by A 42 The acid dissociation constant a2 of the acidic site represented by H.

[0255] As L in formula (Ia-2) 21 and L 22 , and L in formula (Ia-3) 31 and L 32 The divalent organic group represented by is not particularly limited, and examples thereof include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms, which may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), divalent aromatic heterocyclic groups (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), divalent aromatic hydrocarbon ring groups (preferably a 6- to 10-membered ring, and even more preferably a 6-membered ring), and divalent organic groups obtained by combining a plurality thereof. R includes a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably an alkyl group (preferably having 1 to 6 carbon atoms).

[0256] Furthermore, the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may be substituted with a substituent. Examples of the substituent include a monovalent group represented by the above formula (1L) or formula (2L) and a halogen atom (preferably a fluorine atom).

[0257] As L in formula (Ia-2)21 and L 22 , and L in formula (Ia-3) 31 and L 32 The divalent organic group represented by , for example, may be a divalent organic group represented by the following formula (L2).

[0258] [Chemical Formula 12]

[0259]

[0260] In formula (L2), q represents an integer of 1 to 3. * represents a bonding position.

[0261] Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0262] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 . In particular, it is further preferred that both Xf are fluorine atoms.

[0263] L A represents a single bond or a divalent linking group.

[0264] As L A The divalent linking group represented is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms. Can be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring groups (preferably 6-10 membered rings, more preferably 6 membered rings), and divalent linking groups formed by combining a plurality of them.

[0265] Furthermore, the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may be substituted by a substituent. Examples of the substituent include a monovalent group represented by the above formula (1L) or formula (2L) and a halogen atom (preferably a fluorine atom).

[0266] Examples of the divalent organic group represented by formula (L2) include *-CF2-*, *-CF2-CF2-*, *-CF2-CF2-CF2-*, *-Ph-O-SO2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, and *-Ph-O-SO2-CF2-CF2-CF2-*. Ph represents a phenylene group which may have a substituent, preferably a 1,4-phenylene group. The substituent is not particularly limited, but examples thereof include a monovalent group represented by formula (1L) or formula (2L), an alkyl group (e.g., preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkoxy group (e.g., preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), or an alkoxycarbonyl group (e.g., preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms).

[0267] When L in formula (Ia-2) 21 and L 22 When L represents a divalent organic group represented by formula (L2), L in formula (L2) A The connecting bond (*) on the side is preferably the same as that of A in formula (Ia-2) 22 - bonding.

[0268] Furthermore, when L in formula (Ia-3) 32 When L represents a divalent organic group represented by formula (L2), L in formula (L2) A The connecting bond (*) on the side is preferably the same as that of A in formula (Ia-3) 32 - bonding.

[0269] As L in formula (Ia-4) 41 The trivalent organic group represented by is not particularly limited, and examples thereof include a trivalent organic group represented by the following formula (L3).

[0270] [Chemical Formula 13]

[0271]

[0272] In formula (L3), L B represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group. * represents a bonding position.

[0273] The hydrocarbon ring group may be an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The number of carbon atoms contained in the hydrocarbon ring group is preferably 6 to 18, more preferably 6 to 14.

[0274] The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group. The heterocyclic ring is preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring.

[0275] As L B , wherein a trivalent hydrocarbon ring group is preferred, and a benzene ring group or an adamantane ring group is more preferred. The benzene ring group or the adamantane ring group may have a substituent. The substituent is not particularly limited, and examples thereof include a monovalent group represented by the above formula (1L) or formula (2L) and a halogen atom (preferably a fluorine atom).

[0276] Furthermore, in formula (L3), L B1 ~L B3 Each independently represents a single bond or a divalent linking group. B1 ~L B3 The divalent linking group represented by is not particularly limited, and examples thereof include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene (preferably having 1 to 6 carbon atoms. It may be linear or branched), alkylene (preferably having 1 to 6 carbon atoms. It may be linear or branched), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic group (preferably having at least one The above R may be a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom, more preferably a 5- to 7-membered ring, and further preferably a 5- to 6-membered ring. ), a divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and further preferably a 5- to 6-membered ring.), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, and further preferably a 6-membered ring.), and a divalent linking group formed by combining a plurality of these. The above R may be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, and for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred.

[0277] Furthermore, the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may be substituted with a substituent. Examples of the substituent include a monovalent group represented by the above formula (1L) or formula (2L) and a halogen atom (preferably a fluorine atom).

[0278] As L B1 ~L B3Among the above-mentioned divalent linking groups, preferably -CO-, -NR-, -O-, -S-, -SO-, -SO2-, an alkylene group which may have a substituent, and a divalent linking group formed by combining a plurality of these groups.

[0279] As L B1 ~L B3 Among them, the divalent linking group represented by formula (L3-1) is more preferable.

[0280] [Chemical Formula 14]

[0281]

[0282] In formula (L3-1), L B11 represents a single bond or a divalent linking group.

[0283] As L B11 The divalent linking group represented by is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO2-, an alkylene group which may have a substituent (preferably having 1 to 6 carbon atoms and may be linear or branched), and a divalent linking group formed by combining a plurality thereof. The substituent is not particularly limited, and examples thereof include a monovalent group represented by the above formula (1L) or formula (2L) and a halogen atom.

[0284] r represents an integer of 1 to 3.

[0285] Xf has the same meaning as Xf in the above formula (L2), and preferred aspects are also the same.

[0286] *Indicates bonding position.

[0287] As L B1 ~L B3 Examples of the divalent linking group represented by *-O-*, *-O-SO2-CF2-*, *-O-SO2-CF2-CF2-*, *-O-SO2-CF2-CF2-CF2-* and *-COO-CH2-CH2-* can be cited.

[0288] L in formula (Ia-4) 41 Contains a divalent organic group represented by formula (L3-1), and the divalent organic group represented by formula (L3-1) and A 42 - When bonding, the connecting bond (*) on the carbon atom side indicated in formula (L3-1) is preferably connected to the A in formula (Ia-4). 42 - bonding.

[0289] Furthermore, L in formula (Ia-4) 41Contains a divalent organic group represented by formula (L3-1), and the divalent organic group represented by formula (L3-1) and A 4a - and A 41b - When bonding, the connecting bond (*) on the carbon atom side indicated in formula (L3-1) is preferably connected to the A in formula (Ia-4). 41a - and A 41b - bonding.

[0290] <Compound (II)>

[0291] Compound (II) is a compound having an acid-decomposable group formed by protecting a polar group with a leaving group that is released by the action of an acid, two or more of the above-mentioned structural sites X, and one or more of the following structural sites Z, and is a compound that generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural site Z upon irradiation with actinic rays or radiation.

[0292] Structural site Z: a ​​nonionic site capable of neutralizing acid.

[0293] Wherein, compound (II) satisfies the following condition IIB,

[0294] Condition IIB: The compound (II) is connected to two or more anionic sites A1 in the structural site X under the action of an acid. - The structure in which the portion Z of the above-mentioned structural portion is not cut off.

[0295] Furthermore, the meaning and specific form of "the linking site is not decomposed by the action of acid" in condition IIB are as described in condition IB. In compound (II), the anion site A1 - The connecting sites and / or anion sites A1 - The connection position with the structural part Z is a position where the leaving group is released (including decomposition) by the action of an acid and the connection position can be cut, and the structure in which the polar group is protected by the leaving group that is released by the action of an acid is not included. In addition, "the connection position is not decomposed by the action of an acid" means, for example, when compound (II) is a compound represented by formula (IIa) described below, L 51 and L 52 The structure in which the linking group is not cut off by the action of acid.

[0296] In compound (II), the definition of the structural part X and A1 - and M1 + The definition of the structural part X in the above compound (I) and A1 -and M1 + The definitions and meanings of are the same, and the preferred embodiments are also the same.

[0297] In the above compound (II), when H + Substituting the cationic site M1 in the structural site X + Among the compounds PII formed by H + Substituting the cationic site M1 in the structural site X + The preferred range of the acid dissociation constant a1 of the acidic site represented by HA1 is the same as that of the acid dissociation constant a1 in the above-mentioned compound PI.

[0298] In addition, when compound (II) is a compound that produces an acid having two first acidic sites derived from the structural site X and the structural site Z, for example, compound PII corresponds to a "compound having two HA1s." When the acid dissociation constant of compound PII is determined, compound PII becomes a "compound having one A1." - and 1 HA1 compound" and the acid dissociation constant of "compound with 1 A1 - and 1 HA1" becomes "a compound with 2 A1 - The acid dissociation constant for the compound "corresponds to the acid dissociation constant a1.

[0299] The acid dissociation constant a1 is determined by the above-mentioned method for measuring the acid dissociation constant.

[0300] When compound (II) is irradiated with actinic rays or radiation, the above-mentioned compound PII corresponds to the generated acid.

[0301] In addition, the above two or more structural parts X may be the same or may not pass through. - and 2 or more of the above M1 + They can be the same or different.

[0302] The nonionic site capable of neutralizing the acid in the structural site Z is not particularly limited, but is preferably a site containing, for example, a group capable of electrostatically interacting with a proton or a functional group having an electron.

[0303] Examples of functional groups having groups or electrons capable of electrostatically interacting with protons include functional groups having a macrocyclic compound structure such as a cyclic polyether, or functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π conjugation. Examples of nitrogen atoms having an unshared electron pair that does not contribute to π conjugation include nitrogen atoms having a partial structure represented by the following formula:

[0304] [Chemical Formula 15]

[0305] Unshared electron pairs

[0306] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Among these, a primary amine structure, a secondary amine structure, and a tertiary amine structure are preferred.

[0307] Compound (II) has an acid-decomposable group formed by protecting a polar group with a leaving group that is released by the action of an acid. In compound (II), the type, number, and position of the acid-decomposable group are the same as those in compound (I), and the preferred embodiments are also the same.

[0308] The compound (II) is not particularly limited, and examples thereof include compounds represented by the following formula (IIa).

[0309] [Chemical Formula 16]

[0310]

[0311] In the above formula (IIa), A 51a - and A 51b - Respectively with A in the above formula (Ia-1) 11 - The meaning is the same and the preferred method is the same. 51a + and M 51b + Respectively with M in the above formula (Ia-1) 11 + The meaning is the same and the preferred method is also the same.

[0312] In the above formula (IIa), L 51 and L 52 They have the same meanings as L1 in the above formula (Ia-1), and preferred embodiments are also the same.

[0313] In addition, when L in formula (IIa) 51 When the divalent linking group represented by formula (L1) is represented, L in formula (L1) 111 The connecting bond (*) on the side is preferably bonded to the nitrogen atom indicated in formula (IIa). 52 When the divalent linking group represented by formula (L1) is represented, L in formula (L1) 111 The side connecting bond (*) is preferably bonded to the nitrogen atom indicated in formula (IIa).

[0314] In formula (IIa), R 2X Represents a monovalent organic group. 2X The monovalent organic group represented is not particularly limited, and examples thereof include -CH2- which may be substituted by one or more combinations selected from -CO-, -NH-, -O-, -S-, -SO- and -SO2-, alkyl (preferably having 1 to 10 carbon atoms. It may be linear or branched), cycloalkyl (preferably having 3 to 15 carbon atoms) or alkenyl (preferably having 2 to 6 carbon atoms), etc.

[0315] The alkylene group, the cycloalkylene group, and the alkenylene group may be substituted with a substituent. The substituent is not particularly limited, and examples thereof include a monovalent group represented by the formula (1L) or (2L) and a halogen atom (preferably a fluorine atom).

[0316] Furthermore, in the above formula (IIa), when H + Replaced by M 51a + and M 51b + Among the compounds PIIa composed of organic cations represented by 51a The acid dissociation constant a1-7 of the acidic site represented by H and the acid dissociation constant a1-7 derived from A 51b The acid dissociation constant a1-8 of the acidic site represented by H corresponds to the above-mentioned acid dissociation constant a1.

[0317] In addition, in the above compound (IIa), H + Substituting the cationic site M1 in the structural site X + The compound PIIa corresponds to HA 51a -L 51 -N(R 2X )-L 52 -A 51b H. Compound PIIa is the same as the acid generated by the compound represented by formula (IIa) by irradiation with actinic rays or radiation.

[0318] And, M 51a + 、M 51b + 、A 51a - 、A 51b - , L 51 , L 52 and R 2X At least one of them has an acid-decomposable group as a substituent.

[0319] From the viewpoint of achieving a more excellent effect of the present invention, the specific compound contained in the resist composition preferably satisfies the following condition (A) and further satisfies two or more of the following conditions (B1) to (B3) (preferably satisfies the following condition (A) and further satisfies any one of the following conditions (B1) to (B3)).

[0320] (A) The type of the acid-decomposable group of the specific compound is a structure represented by the above formula (1) (ester structure) or a structure represented by the formula (2) (acetal structure).

[0321] (B1) The type of the acid-decomposable group of the specific compound is a structure (ester structure) represented by the above formula (1).

[0322] (B2) In the specific compound, the acid-decomposable group is located at the cationic site.

[0323] (B3) The specific compound corresponds to the above-mentioned compound (I), and the anion site A2 - The structure corresponds to the above formula (BB-1) to formula (BB-3).

[0324] The specific compound may be used alone or in combination of two or more.

[0325] When two or more specific compounds are used, a combination of at least one compound selected from the following compound (IA) and the following compound (II-A) (hereinafter also referred to as compound (XA)) and at least one compound selected from the following compound (IB) and the following compound (II-B) (hereinafter also referred to as compound (XB)) is preferred, and a combination of at least one compound (IA) and at least one compound (IB) is more preferred. This results in further improved defect reduction performance.

[0326] Compound (IA): A compound corresponding to the above compound (I), having two or more structural parts X and only one structural part Y

[0327] Compound (IB): A compound corresponding to the above compound (I), having only one structural site X and only one structural site Y

[0328] Compound (II-A): A compound corresponding to the above compound (II), having three or more structural parts X and only one structural part Z

[0329] Compound (II-B): A compound corresponding to the above compound (II), having only two structural sites X and only one structural site Z

[0330] When the resist composition contains compound (XA) and compound (XB), the mass ratio of the content of compound (XA) to the content of compound (XB) (compound (XA) / compound (XB)) is preferably 0.05 to 19.00, more preferably 0.18 to 5.67, and even more preferably 0.43 to 2.33. When the mass ratio is within this range, defect resistance is further improved.

[0331] When the resist composition contains compound (XA) and compound (XB), it is preferred to use compound (XA) that satisfies the above condition (A) and further satisfies two or more of the above conditions (B1) to (B3), and compound (XB) that satisfies the above condition (A) and further satisfies two or more of the above conditions (B1) to (B3). This results in further improved defect resistance.

[0332] The molecular weight of the specific compound is preferably 300 to 5000, more preferably 500 to 4000, and even more preferably 700 to 3000.

[0333] The content of the specific compound is preferably 0.1 to 80.0% by mass, more preferably 1.0 to 60.0% by mass, and even more preferably 5.00 to 50.0% by mass relative to the total solid content of the composition. Furthermore, the solid content refers to the components that form the resist film and does not include the solvent. Furthermore, any component that forms the resist film, even if it is in a liquid state, is considered a solid component.

[0334] The specific compound may be used alone or in combination of two or more. When two or more are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0335] Specific examples of the specific compound are shown below, but the present invention is not limited thereto.

[0336] [Chemical Formula 17]

[0337]

[0338] [Chemical Formula 18]

[0339]

[0340] [Chemical Formula 19]

[0341]

[0342] [Chemical Formula 20]

[0343]

[0344] [Chemical Formula 21]

[0345]

[0346] [Chemical Formula 22]

[0347]

[0348] [Chemical Formula 23]

[0349]

[0350] [Chemical Formula 24]

[0351]

[0352] [Chemical Formula 25]

[0353]

[0354] [Chemical Formula 26]

[0355]

[0356]

[0357] [Chemical Formula 27]

[0358]

[0359] [Chemical Formula 28]

[0360]

[0361] [Chemical Formula 29]

[0362]

[0363] [Chemical formula 30]

[0364]

[0365] [Chemical Formula 31]

[0366]

[0367] [Chemical Formula 32]

[0368]

[0369] [Chemical Formula 33]

[0370]

[0371] <Photoacid generator (B)>

[0372] The resist composition may contain a photoacid generator (B). The photoacid generator (B) corresponds to a photoacid generator other than the above-mentioned specific compound.

[0373] The photoacid generator (B) may be in the form of a low molecular weight compound or in the form of being embedded in a part of a polymer. Furthermore, the low molecular weight compound form and the form of being embedded in a part of a polymer may be used in combination.

[0374] When the photoacid generator (B) is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

[0375] When the photoacid generator (B) is in a form of being embedded in a part of the polymer, it may be embedded in a part of the resin (A) or in a resin different from the resin (A).

[0376] In the present invention, the photoacid generator (B) is preferably in the form of a low molecular weight compound.

[0377] As the photoacid generator (B), for example, + X - The compound (onium salt) represented by ” is preferably a compound that generates an organic acid upon exposure.

[0378] Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphorsulfonic acid), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids), carbonylsulfonylimide acids, bis(alkylsulfonyl)imidic acids, and tris(alkylsulfonyl)methylated acids.

[0379] In the "M + X - In the compound represented by ", M + represents an organic cation.

[0380] The above-mentioned organic cation is preferably a cation represented by formula (ZaI) (cation (ZaI)) or a cation represented by formula (ZaII) (cation (ZaII)).

[0381] In addition, the cation represented by formula (ZaI) (cation (ZaI)) or the cation represented by formula (ZaII) (cation (ZaII)) is as described above.

[0382] As M + The organic cation represented by also preferably has an acid-decomposable group as one embodiment. Examples of the acid-decomposable group include the acid-decomposable group represented by the above formula (1) and the acid-decomposable group represented by the formula (2).

[0383] In the "M + X- ”, X represents an organic anion.

[0384] The organic anion is not particularly limited, but is preferably a non-nucleophilic anion (an anion having a significantly low ability to induce a nucleophilic reaction).

[0385] Examples of the non-nucleophilic anion include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, aralkyl carboxylic acid anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methylated anions.

[0386] The aliphatic portion in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms.

[0387] The alkyl group may be, for example, a fluoroalkyl group (which may or may not have a substituent other than a fluorine atom, and may be a perfluoroalkyl group).

[0388] The aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include phenyl, tolyl, and naphthyl.

[0389] The alkyl, cycloalkyl, and aryl groups listed above may have a substituent. The substituent is not particularly limited, but specific examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0390] The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms, and examples thereof include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl.

[0391] Examples of the sulfonylimide anion include saccharin anion.

[0392] The alkyl group in the bis(alkylsulfonyl)imide anion and the tri(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, and are preferably fluorine atoms or alkyl groups substituted with fluorine atoms.

[0393] Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion can bond to each other to form a ring structure, thereby increasing the acid strength.

[0394] The non-nucleophilic anion is preferably an aliphatic sulfonic acid anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion in which the alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methide anion in which the alkyl group is substituted with a fluorine atom.

[0395] As the photoacid generator (B), for example, the photoacid generators disclosed in paragraphs

[0135] to

[0171] of International Publication No. 2018 / 193954, paragraphs

[0077] to

[0116] of International Publication No. 2020 / 066824, and paragraphs

[0018] to

[0075] and

[0334] to

[0335] of International Publication No. 2017 / 154345 are also preferably used.

[0396] When the resist composition contains a photoacid generator (B), its content is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, relative to the total solids content of the composition. Furthermore, the content is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0397] The photoacid generator (B) may be used alone or in combination of two or more. When two or more photoacid generators are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0398] [Acid-decomposable resin (resin (A))]

[0399] The resist composition contains a resin that decomposes and increases in polarity by the action of an acid (also referred to as "acid-decomposable resin" or "resin (A)" as described above).

[0400] That is, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0401] The resin (A) generally contains a group that decomposes and increases its polarity by the action of an acid (hereinafter also referred to as an "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group.

[0402] As the repeating unit having an acid-decomposable group, in addition to the repeating unit having an acid-decomposable group described later, the repeating unit having an acid-decomposable group described later is also preferred.

[0403] <Repeating Unit Having an Acid-Decomposable Group>

[0404] An acid-decomposable group refers to a group that decomposes to form a polar group upon the action of an acid. The acid-decomposable group preferably has a structure in which the polar group is protected by a leaving group that is released upon the action of an acid. That is, the resin (A) contains a repeating unit having a group that decomposes to form a polar group upon the action of an acid. The polarity of the resin containing this repeating unit increases upon the action of an acid, thereby increasing its solubility in alkaline developer solutions and decreasing its solubility in organic solvents.

[0405] Below, after the acid-decomposable group is described, the repeating unit having the acid-decomposable group is described. In addition, the acid-decomposable group described below can be used as the acid-decomposable group possessed by the above-mentioned specific compound. Moreover, in the specific compound, in the connecting portion between the anion sites and / or the connecting portion between the anion site and the structural site Z, the position where the leaving group can be separated (including decomposition) by the action of the acid and can cut the connecting portion does not include a structure in which the polar group is protected by a leaving group that is separated by the action of the acid.

[0406] As described above, as the repeating unit having an acid-decomposable group, in addition to the repeating unit having an acid-decomposable group described below, the repeating unit having an acid-decomposable group described below is also preferred.

[0407] (Acid-decomposable group)

[0408] An acid-decomposable group is a group that decomposes to generate a polar group upon the action of an acid. The acid-decomposable group preferably has a structure in which the polar group is protected by a leaving group that is detached upon the action of an acid. The acid-decomposable group can decompose to generate a polar group upon the action of an acid.

[0409] As the polar group, an alkali-soluble group is preferred, and examples thereof include acidic groups such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as an alcoholic hydroxyl group.

[0410] Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

[0411] Examples of the leaving group that leaves by the action of an acid include groups represented by formulae (Y1) to (Y4).

[0412] Formula (Y1): -C(Rx1)(Rx2)(Rx3)

[0413] Formula (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0414] Formula (Y3): -C(R 36 )(R 37 )(OR 38 )

[0415] Formula (Y4): -C(Rn)(H)(Ar)

[0416] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (straight-chain or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (straight-chain or branched), or an aryl group (monocyclic or polycyclic). Furthermore, when all of Rx1 to Rx3 are alkyl groups (straight-chain or branched), it is preferred that at least two of Rx1 to Rx3 are methyl groups.

[0417] Among them, it is preferred that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferred that Rx1 to Rx3 each independently represent a linear alkyl group.

[0418] Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring.

[0419] The alkyl group represented by Rx1 to Rx3 is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

[0420] The cycloalkyl groups for Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0421] The aryl group represented by Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl, and anthracenyl.

[0422] As the alkenyl group of Rx1 to Rx3, a vinyl group is preferable.

[0423] The ring formed by two of Rx1 to Rx3 being bonded together is preferably a cycloalkyl group. The cycloalkyl group formed by two of Rx1 to Rx3 being bonded together is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0424] In a cycloalkyl group formed by bonding two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0425] The group represented by formula (Y1) or formula (Y2) is preferably a mode in which, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0426] When the resist composition is a resist composition for EUV exposure, for example, the alkyl group, cycloalkyl group, alkenyl group, or aryl group represented by Rx1 to Rx3 and the ring formed by bonding two of Rx1 to Rx3 further preferably have a fluorine atom or an iodine atom as a substituent.

[0427] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 With R 38 Examples of the monovalent organic group include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. 36 A hydrogen atom is also preferred.

[0428] Furthermore, the above-mentioned alkyl, cycloalkyl, aryl, and aralkyl groups may also contain groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups. For example, in the above-mentioned alkyl, cycloalkyl, aryl, and aralkyl groups, one or more methylene groups may be substituted with groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups.

[0429] Furthermore, in the repeating unit having an acid-decomposable group described below, R 38 It may bond with another substituent on the main chain of the repeating unit to form a ring. 38The group formed by bonding with another substituent on the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0430] When the resist composition is, for example, a resist composition for EUV exposure, it is also preferable to use R 36 ~R 38 The monovalent organic group represented by R 37 With R 38 The ring formed by bonding to each other further has a fluorine atom or an iodine atom as a substituent.

[0431] As the formula (Y3), a group represented by the following formula (Y3-1) is preferred.

[0432] [Chemical Formula 34]

[0433]

[0434] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these (for example, a group formed by combining an alkyl group and an aryl group).

[0435] M represents a single bond or a divalent linking group.

[0436] Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (for example, a combination of an alkyl group and a cycloalkyl group).

[0437] In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be substituted with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group.

[0438] Furthermore, it is preferred that one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group composed of an alkylene group and an aryl group.

[0439] At least two of Q, M, and L1 may be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0440] From the perspective of pattern miniaturization, L2 is preferably a secondary alkyl group or a tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl, cyclohexyl, or norbornyl, and examples of the tertiary alkyl group include tert-butyl or adamantyl. In these embodiments, the Tg (glass transition temperature) and activation energy of the resin (A) are increased in the repeating unit having an acid-decomposable group described later, thereby ensuring film strength while also suppressing fogging.

[0441] When the resist composition is, for example, a resist composition for EUV exposure, the alkyl group, cycloalkyl group, aryl group, and a group composed of these represented by L1 and L2 preferably further have a fluorine atom or an iodine atom as a substituent. Furthermore, the alkyl group, cycloalkyl group, aryl group, and aralkyl group preferably contain a heteroatom such as an oxygen atom in addition to a fluorine atom and an iodine atom (i.e., one methylene group in the alkyl group, cycloalkyl group, aryl group, and aralkyl group is substituted with a group containing a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group).

[0442] Furthermore, when the resist composition is, for example, a resist composition for EUV exposure, the hetero atom among the alkyl group which may contain a hetero atom represented by Q, the cycloalkyl group which may contain a hetero atom, the aryl group which may contain a hetero atom, the amino group, the ammonium group, the mercapto group, the cyano group, the aldehyde group, and a group formed by combining them, is preferably a hetero atom selected from a fluorine atom, an iodine atom, and an oxygen atom.

[0443] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0444] When the resist composition is, for example, a resist composition for EUV exposure, the aromatic ring group represented by Ar, and the alkyl group, cycloalkyl group, and aryl group represented by Rn preferably have a fluorine atom and an iodine atom as a substituent.

[0445] From the viewpoint of further improving acid decomposability, it is also preferred that when a non-aromatic ring is directly bonded to a polar group (or its residue) in a leaving group protecting a polar group, the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have a halogen atom such as a fluorine atom as a substituent.

[0446] In addition, the leaving group that is released by the action of acid may be a 2-cyclopentenyl group having a substituent (alkyl group, etc.) such as a 3-methyl-2-cyclopentenyl group, or a cyclohexyl group having a substituent (alkyl group, etc.) such as a 1,1,4,4-tetramethylcyclohexyl group.

[0447] (Repeating unit containing an acid-decomposable group)

[0448] Next, the repeating unit having an acid-decomposable group which may be contained in the resin (A) will be described.

[0449] As the repeating unit having an acid-decomposable group, in addition to the repeating unit having the above-mentioned acid-decomposable group, a repeating unit represented by the following formula (A) is preferred.

[0450] [Chemical Formula 35]

[0451]

[0452] L1 represents a divalent linking group that may have a fluorine atom or an iodine atom, R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine atom or an iodine atom, or an aryl group that may have a fluorine atom or an iodine atom, and R2 represents a leaving group that can be released by the action of an acid and may have a fluorine atom or an iodine atom. At least one of L1, R1, and R2 has a fluorine atom or an iodine atom.

[0453] L1 represents a divalent linking group that can have a fluorine atom or an iodine atom. As a divalent linking group that can have a fluorine atom or an iodine atom, -CO-, -O-, -S-, -SO-, -SO2-, a hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.) that can have a fluorine atom or an iodine atom and a linking group formed by connecting a plurality of them etc. can be enumerated. Wherein, as L1, preferably -CO-, arylene group or an alkylene group with -arylene group-fluorine atom or iodine atom-, more preferably -CO- or an alkylene group with -arylene group-fluorine atom or iodine atom-.

[0454] The arylene group is preferably a phenylene group.

[0455] The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

[0456] The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0457] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.

[0458] The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

[0459] The total number of fluorine atoms and iodine atoms contained in the alkyl group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0460] The above-mentioned alkyl group may contain heteroatoms such as oxygen atoms in addition to halogen atoms.

[0461] R2 represents a leaving group that is released by the action of an acid and that may have a fluorine atom or an iodine atom. Examples of the leaving group that may have a fluorine atom or an iodine atom include those represented by the above formulas (Y1) to (Y4) and having a fluorine atom or an iodine atom, and the preferred embodiments are the same.

[0462] Furthermore, as the repeating unit having an acid-decomposable group, a repeating unit represented by formula (AI) is also preferred.

[0463] [Chemical Formula 36]

[0464]

[0465] In formula (AI),

[0466] Xa1 represents a hydrogen atom or an alkyl group which may have a substituent.

[0467] T represents a single bond or a divalent linking group.

[0468] Rx1 to Rx3 each independently represent an alkyl group (straight-chain or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (straight-chain or branched), or an aryl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (straight-chain or branched), preferably at least two of Rx1 to Rx3 are methyl groups.

[0469] Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring (monocyclic or polycyclic cycloalkyl group).

[0470] As the alkyl group which may have a substituent represented by Xa1, for example, there can be mentioned a methyl group or a group represented by -CH2-R 11 The group represented by R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom. An alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0471] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0472] T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0473] The alkyl group represented by Rx1 to Rx3 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

[0474] The cycloalkyl group represented by Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group.

[0475] The aryl group represented by Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl, and anthracenyl.

[0476] As the alkenyl group of Rx1 to Rx3, a vinyl group is preferable.

[0477] The cycloalkyl group formed by bonding two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl. In addition, polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are also preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.

[0478] In a cycloalkyl group formed by bonding two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0479] The repeating unit represented by the formula (AI) is preferably such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0480] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0481] The repeating unit represented by the formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond).

[0482] The content of repeating units having an acid-degradable group is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more relative to all repeating units in the resin (A). Furthermore, the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, particularly preferably 70 mol% or less, and most preferably 60 mol% or less.

[0483] Specific examples of repeating units having an acid-decomposable group are shown below, but the present invention is not limited thereto. In the formula, Xa1 represents any one of H, CH3, CF3, and CH2OH, and Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0484] [Chemical Formula 37]

[0485]

[0486] [Chemical Formula 38]

[0487]

[0488] [Chemical Formula 39]

[0489]

[0490] [Chemical Formula 40]

[0491]

[0492] [Chemical Formula 41]

[0493]

[0494] (Repeating unit having an acid-decomposable group containing an unsaturated bond)

[0495] As one embodiment of the resin (A), it is preferred that the resin (A) contain a repeating unit having an acid-decomposable group containing an unsaturated bond.

[0496] As the repeating unit having an acid-decomposable group including an unsaturated bond, a repeating unit represented by formula (B) is preferred.

[0497] [Chemical Formula 42]

[0498]

[0499] In formula (B),

[0500] Xb represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent.

[0501] L represents a single bond or a divalent linking group which may have a substituent.

[0502] Ry1-Ry3 each independently represents a hydrogen atom, a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. Furthermore, any two of Ry1-Ry3 may be bonded to form a monocyclic or polycyclic ring (e.g., a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0503] At least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group, or any two of Ry1 to Ry3 are bonded to form a monocyclic or polycyclic alicyclic ring (for example, a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group). Furthermore, when two or more of Ry1 to Ry3 are not hydrogen atoms and any one of Ry1 to Ry3 represents a hydrogen atom, the other two of Ry1 to Ry3 are bonded to form a ring having one or more vinylene groups in the ring structure, and at least one of the vinylene groups is adjacent to the carbon atom to which the hydrogen atom represented by any one of Ry1 to Ry3 is bonded.

[0504] The alkyl group represented by Ry1 to Ry3 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

[0505] The cycloalkyl group represented by Ry1 to Ry3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group.

[0506] The aryl group represented by Ry1 to Ry3 is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl, and anthracenyl.

[0507] As the alkenyl group of Ry1 to Ry3, a vinyl group is preferable.

[0508] The alkynyl group represented by Ry1 to Ry3 is preferably an ethynyl group.

[0509] The cycloalkenyl groups represented by Ry1 to Ry3 preferably have a structure containing a double bond in a part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.

[0510] The cycloalkyl group formed by bonding two of Ry1 to Ry3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl. In addition, polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are also preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.

[0511] In cycloalkyl and cycloalkenyl groups formed by bonding two of Ry1 to Ry3, for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom, a carbonyl group, a group having a heteroatom such as an -SO2- group or a -SO3- group, or a vinylene group, or a combination thereof. Furthermore, in these cycloalkyl and cycloalkenyl groups, one or more ethylene groups in the cycloalkane ring and the cycloalkene ring may be substituted with a vinylene group.

[0512] As a preferred embodiment of the combination of Ry1 to Ry3, for example, the following embodiments can be cited: a embodiment in which Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group or an aryl group, and Ry2 and Rx3 are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group; and a embodiment in which Ry1 is a hydrogen atom, Ry2 and Ry3 are bonded to each other to form a ring having one or more vinylene groups in the ring structure, and at least one of the vinylene groups is adjacent to the carbon atom to which the hydrogen atom represented by Ry1 is bonded.

[0513] When Ry1 to Ry3 further have a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0514] As the alkyl group which may have a substituent represented by Xb, for example, a methyl group or a group represented by -CH2-R 11 The group represented by R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom. An alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0515] Examples of the divalent linking group of L include -Rt-, -CO-, -COO-Rt-, -COo-Rt-CO-, -Rt-CO-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, preferably an aromatic ring group.

[0516] L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have a substituent such as a halogen atom, a hydroxyl group, or an alkoxy group. An aromatic group is preferred.

[0517] When the above groups in formula (B) have a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0518] The repeating unit represented by formula (B) is preferably an acid-decomposable tertiary (meth)acrylate repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group, and L represents a -CO- group), an acid-decomposable tertiary hydroxystyrene alkyl ether repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group, and L represents a phenyl group), or an acid-decomposable tertiary styrene carboxylate repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group, and L represents a -Rt-CO- group (Rt is an aromatic group)).

[0519] The content of repeating units having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in the resin (A). The upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less.

[0520] Specific examples of the repeating unit having an acid-decomposable group containing an unsaturated bond are shown below, but the present invention is not limited thereto.

[0521] In addition, in the formula, Xb and L1 have the same meaning as Xb and L in the above formula (B). And, Ar represents an aromatic ring group. R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR"' or -COOR"': R"' is an alkyl group or a fluoroalkyl group having 1 to 20 carbon atoms) or a substituent such as a carboxyl group. R' represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group or a monocyclic or polycyclic aryl group. Q represents a heteroatom such as an oxygen atom, a group having heteroatoms such as a carbonyl group, an -SO2- group and a -SO3- group, a vinylene group or a combination thereof. l, n and m represent integers greater than 0. There is no restriction on the upper limit value, for example, it is 6 or less, and preferably 4 or less.

[0522] [Chemical Formula 43]

[0523]

[0524] [Chemical Formula 44]

[0525]

[0526] [Chemical Formula 45]

[0527]

[0528] [Chemical Formula 46]

[0529]

[0530] The resin (A) may contain repeating units other than the above-mentioned repeating units.

[0531] For example, the resin (A) may contain at least one repeating unit selected from the group consisting of the following Group A and / or at least one repeating unit selected from the group consisting of the following Group B.

[0532] Group A: A group consisting of the following repeating units (20) to (29).

[0533] (20) Repeating unit having an acid group as described later

[0534] (21) The repeating unit having a fluorine atom or an iodine atom described later

[0535] (22) Repeating units having a lactone group, a sultone group or a carbonate group as described later

[0536] (23) Repeating unit having a photoacid generating group described later

[0537] (24) A repeating unit represented by the formula (V-1) or the following formula (V-2)

[0538] (25) The repeating unit represented by formula (A) described below

[0539] (26) The repeating unit represented by formula (B) described later

[0540] (27) The repeating unit represented by the formula (C) described later

[0541] (28) The repeating unit represented by formula (D) described below

[0542] (29) The repeating unit represented by the formula (E) described later

[0543] Group B: A group consisting of the following repeating units (30) to (32).

[0544] (30) The repeating unit described later having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group

[0545] (31) The repeating unit described later having an alicyclic hydrocarbon structure and not exhibiting acid decomposability

[0546] (32) The repeating unit described later having neither a hydroxyl group nor a cyano group and represented by formula (III)

[0547] The resin (A) preferably has an acid group and, as described below, preferably contains a repeating unit having an acid group. The definition of the acid group will be described later together with preferred embodiments of the repeating unit having an acid group.

[0548] When the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above-mentioned Group A.

[0549] Furthermore, when the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When the resin (A) contains both a fluorine atom and an iodine atom, the resin (A) may have a single repeating unit containing both a fluorine atom and an iodine atom, or the resin (A) may contain both a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom.

[0550] Furthermore, when the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably further contains a repeating unit having an aromatic group.

[0551] When the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably has at least one repeating unit selected from the group consisting of the above-mentioned Group B.

[0552] When the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably contains neither a fluorine atom nor a silicon atom.

[0553] Furthermore, when the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably does not have an aromatic group.

[0554] <Repeating Unit Having an Acid Group>

[0555] The resin (A) preferably contains a repeating unit having an acid group.

[0556] The acid group preferably has a pKa of 13 or less. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10, as described above.

[0557] When resin (A) has an acid group with a pKa of 13 or less, the acid group content in resin (A) is not particularly limited, but is generally 0.2 to 6.0 mmol / g. It is preferably 0.8 to 6.0 mmol / g, more preferably 1.2 to 5.0 mmol / g, and even more preferably 1.6 to 4.0 mmol / g. When the acid group content is within this range, development proceeds smoothly, resulting in an excellent pattern shape and resolution.

[0558] Preferred examples of the acid group include a carboxyl group, a hydroxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, and an isopropanol group.

[0559] Furthermore, in the hexafluoroisopropanol group, one or more (preferably one to two) fluorine atoms may be substituted with groups other than fluorine atoms (e.g., alkoxycarbonyl groups). The resulting -C(CF3)(OH)-CF2- is also preferably used as an acid group. Furthermore, one or more fluorine atoms may be substituted with groups other than fluorine atoms to form a ring containing -C(CF3)(OH)-CF2-.

[0560] The repeating unit having an acid group is preferably a repeating unit different from the repeating unit having a structure in which a polar group is protected by a leaving group that is released by the action of the acid and the repeating unit having a lactone group, a sultone group or a carbonate group described later.

[0561] The repeating unit having an acid group may have a fluorine atom or an iodine atom.

[0562] As the repeating unit having an acid group, a repeating unit represented by formula (B) is preferred.

[0563] [Chemical Formula 47]

[0564]

[0565] R3 represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom.

[0566] The monovalent organic group optionally containing a fluorine atom or an iodine atom is preferably a group represented by -L4-R8. L4 represents a single bond or an ester group. R8 can include an alkyl group optionally containing a fluorine atom or an iodine atom, a cycloalkyl group optionally containing a fluorine atom or an iodine atom, an aryl group optionally containing a fluorine atom or an iodine atom, or a group composed of a combination thereof.

[0567] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

[0568] L2 represents a single bond, an ester group, or a divalent group formed by combining -CO-, -O- and an alkylene group (preferably having 1 to 6 carbon atoms. It may be linear or branched. Furthermore, -CH2- may be substituted by a halogen atom).

[0569] L3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. Examples of the alicyclic hydrocarbon ring group include a monocyclic or polycyclic ring group, and examples thereof include a cycloalkyl ring group, a norbornene ring group, and an adamantane ring group.

[0570] R6 represents a hydroxyl group or a fluorinated alcohol group. The fluorinated alcohol group is preferably a monovalent group represented by the following formula (3L).

[0571] *-L 6X -R 6X (3L)

[0572] L 6X The divalent linking group is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO2-, and -NR A -, an alkylene group (preferably having 1 to 6 carbon atoms and may be linear or branched), and a divalent linking group formed by combining a plurality of these. A , can be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In addition, the above alkylene group may have a substituent. As a substituent, for example, a halogen atom (preferably a fluorine atom) and a hydroxyl group can be mentioned. As R 6X , represents a hexafluoroisopropanol group. In addition, when R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon ring group with a valence of (n+m+1).

[0573] R7 represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0574] m represents an integer greater than or equal to 1. m is preferably an integer of 1 to 3, more preferably an integer of 1 to 2.

[0575] n represents an integer greater than or equal to 0 or 1. n is preferably an integer of 1-4.

[0576] In addition, (n+m+1) is preferably an integer of 1-5.

[0577] Examples of the repeating unit having an acid group include the following repeating units.

[0578] [Chemical Formula 48]

[0579]

[0580] As the repeating unit having an acid group, a repeating unit represented by the following formula (I) is also preferred.

[0581] [Chemical Formula 49]

[0582]

[0583] In formula (I),

[0584] R 41 、R 42 and R 43Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 42 It can bond with Ar4 to form a ring. In this case, R 42 represents a single bond or an alkylene group.

[0585] X4 represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group.

[0586] L4 represents a single bond or an alkylene group.

[0587] Ar4 represents an (n+1) valent aromatic ring group, when it is combined with R 42 When they are bonded to form a ring, they represent an (n+2)-valent aromatic ring group.

[0588] n represents an integer of 1 to 5.

[0589] As R in formula (I) 41 、R 42 and R 43 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl, more preferably an alkyl group having 8 or less carbon atoms, and further preferably an alkyl group having 3 or less carbon atoms.

[0590] As R in formula (I) 41 、R 42 and R 43 The cycloalkyl group may be monocyclic or polycyclic. Among them, preferred are monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl.

[0591] As R in formula (I) 41 、R 42 and R 43 The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

[0592] As R in formula (I) 41 、R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group is preferably the same as the above R 41 、R 42 and R 43 The alkyl group in is the same as the alkyl group.

[0593] Preferred substituents in the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, urea groups, carbamate groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, and nitro groups. The substituent preferably has 8 or fewer carbon atoms.

[0594] Ar4 represents an (n+1)-valent aromatic ring group. When n is 1, the divalent aromatic ring group is preferably an arylene group having 6 to 18 carbon atoms such as phenylene, tolylene, naphthylene, and anthrylene, or a divalent aromatic ring group containing a heterocycle such as a 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. In addition, the above aromatic ring group may have a substituent.

[0595] Specific examples of the (n+1)-valent aromatic ring group when n is an integer of 2 or greater include groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group.

[0596] The (n+1)-valent aromatic ring group may further have a substituent.

[0597] Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include R in formula (I): 41 、R 42 and R 43 The alkyl groups mentioned above, alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl; and the like.

[0598] As -CONR represented by X4 64 -(R 64 represents a hydrogen atom or an alkyl group) 64 Examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl, and preferably alkyl groups having 8 or less carbon atoms.

[0599] X4 is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

[0600] The alkylene group in L4 is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group.

[0601] Ar4 is preferably an aromatic ring group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, and a biphenylene ring group.

[0602] The repeating unit represented by formula (I) preferably has a hydroxystyrene structure. That is, Ar4 is preferably a benzene ring group.

[0603] As the repeating unit represented by formula (I), a repeating unit represented by the following formula (1) is preferred.

[0604] [Chemical Formula 50]

[0605]

[0606] In formula (1),

[0607] A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group.

[0608] R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group, or an aryloxycarbonyl group. When there are multiple R groups, they may be the same or different. When there are multiple R groups, they may collectively form an alkyl group. R is preferably a hydrogen atom.

[0609] a represents an integer of 1 to 3.

[0610] b represents an integer from 0 to (5-a).

[0611] The repeating units having an acid group are exemplified below. In the formula, a represents 1 or 2.

[0612] [Chemical Formula 51]

[0613]

[0614] [Chemical Formula 52]

[0615]

[0616] [Chemical Formula 53]

[0617]

[0618] [Chemical Formula 54]

[0619]

[0620] Among the above-mentioned repeating units, the repeating units specifically described below are preferred: wherein R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0621] [Chemical Formula 55]

[0622]

[0623] [Chemical Formula 56]

[0624]

[0625] The content of repeating units having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in the resin (A). The upper limit thereof is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less.

[0626] <Repeating Unit Having Fluorine Atom or Iodine Atom>

[0627] In addition to the <repeating units having an acid-decomposable group> and <repeating units having an acid group> described above, resin (A) may also contain repeating units having a fluorine atom or an iodine atom. Furthermore, the <repeating units having a fluorine atom or an iodine atom> mentioned here are preferably different from other types of repeating units belonging to Group A, such as the <repeating units having a lactone group, a sultone group, or a carbonate group> and the <repeating units having a photoacid-generating group> described below.

[0628] As the repeating unit having a fluorine atom or an iodine atom, a repeating unit represented by formula (C) is preferred.

[0629] [Chemical Formula 57]

[0630]

[0631] L5 represents a single bond or an ester group.

[0632] R9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom.

[0633] R 10 represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group composed of a combination thereof.

[0634] The repeating units having a fluorine atom or an iodine atom are exemplified below.

[0635] [Chemical Formula 58]

[0636]

[0637] The content of repeating units having fluorine atoms or iodine atoms relative to all repeating units in the resin (A) is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. The upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less.

[0638] As described above, since the repeating units having a fluorine atom or an iodine atom do not include the <repeating unit having an acid-decomposable group> and the <repeating unit having an acid group>, the content of the repeating units having a fluorine atom or an iodine atom mentioned above also means the content of the repeating units having a fluorine atom or an iodine atom other than the <repeating unit having an acid-decomposable group> and the <repeating unit having an acid group>.

[0639] The total content of repeating units containing at least one of fluorine atoms and iodine atoms in the repeating units of resin (A) is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and particularly preferably 40 mol% or more, relative to all repeating units of resin (A). The upper limit is not particularly limited, but is, for example, 100 mol% or less.

[0640] In addition, examples of the repeating unit containing at least one of a fluorine atom and an iodine atom include a repeating unit having a fluorine atom or an iodine atom and an acid-decomposable group, a repeating unit having a fluorine atom or an iodine atom and an acid group, and a repeating unit having a fluorine atom or an iodine atom.

[0641] <Repeating Unit Having a Lactone Group, a Sultone Group, or a Carbonate Group>

[0642] The resin (A) may contain a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter also collectively referred to as "a repeating unit having a lactone group, a sultone group, or a carbonate group").

[0643] The repeating unit having a lactone group, a sultone group, or a carbonate group preferably does not have an acid group such as a hydroxyl group or a hexafluoropropanol group.

[0644] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. Among these, a structure in which another ring structure is fused to a 5- to 7-membered ring lactone structure to form a bicyclic structure or a spirocyclic structure, or a structure in which another ring structure is fused to a 5- to 7-membered ring sultone structure to form a bicyclic structure or a spirocyclic structure is more preferred.

[0645] Resin (A) preferably contains a repeating unit having a lactone group or a sultone group, in which one or more hydrogen atoms are extracted from a ring member atom of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3).

[0646] Furthermore, the lactone group or the sultone group may be directly bonded to the main chain. For example, the ring member atoms of the lactone group or the sultone group may constitute the main chain of the resin (A).

[0647] [Chemical Formula 59]

[0648]

[0649] The lactone structure or sultone structure moiety may have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, carboxyl groups, halogen atoms, cyano groups, and acid-decomposable groups. n2 represents an integer from 0 to 4. When n2 is 2 or greater, multiple Rb2s may be different, and multiple Rb2s may be bonded to each other to form a ring.

[0650] Examples of the repeating unit containing a group having a lactone structure represented by any of formulae (LC1-1) to (LC1-21) or a sultone structure represented by any of formulae (SL1-1) to (SL1-3) include repeating units represented by the following formula (AI).

[0651] [Chemical Formula 60]

[0652]

[0653] In formula (AI), Rb0 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

[0654] Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom.

[0655] Examples of the halogen atom of Rb0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group.

[0656] Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group composed of a combination thereof. Among these, a single bond or a linking group represented by -Ab1-CO2- is preferred. Ab1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

[0657] V represents a group formed by extracting one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-21), or a group formed by extracting one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3).

[0658] When optical isomers exist in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. Furthermore, a single optical isomer may be used alone, or a mixture of multiple optical isomers may be used. When a single optical isomer is used primarily, its optical purity (ee) is preferably 90 or greater, more preferably 95 or greater.

[0659] As the carbonate group, a cyclic carbonate group is preferred.

[0660] As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following formula (A-1) is preferred.

[0661] [Chemical Formula 61]

[0662]

[0663] In formula (A-1), R A 1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

[0664] n represents an integer greater than or equal to 0.

[0665] R A 2 When n is 2 or more, there are multiple R A 2 They can be the same or different.

[0666] A represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group composed of a combination thereof.

[0667] Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0668] The repeating units having a lactone group, a sultone group, or a carbonate group are exemplified below.

[0669] [Chemical Formula 62]

[0670]

[0671] [Chemical Formula 63]

[0672]

[0673] [Chemical Formula 64]

[0674]

[0675] The content of repeating units having a lactone group, a sultone group, or a carbonate group is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more relative to all repeating units in the resin (A). Furthermore, the upper limit thereof is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less.

[0676] <Repeating Unit Having a Photoacid Generating Group>

[0677] The resin (A) may contain, as a repeating unit other than the above-mentioned repeating units, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as a "photoacid-generating group").

[0678] In this case, it can be considered that the repeating unit having the photoacid generating group corresponds to the photoacid generator B described above.

[0679] Examples of such a repeating unit include a repeating unit represented by the following formula (4).

[0680] [Chemical Formula 65]

[0681]

[0682] R 41 Represents a hydrogen atom or a methyl group. 41 represents a single bond or a divalent linking group. 42 Represents a divalent linking group. 40 It represents a structural site that is decomposed by irradiation with actinic rays or radiation to generate an acid in the side chain.

[0683] The repeating units having a photoacid-generating group are exemplified below.

[0684] [Chemical Formula 66]

[0685]

[0686] In addition, examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs

[0094] to

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

[0094] of WO-2018 / 193954.

[0687] The content of repeating units having a photoacid generating group is preferably 1 mol% or more, more preferably 5 mol% or more, relative to all repeating units in the resin (A). The upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.

[0688] <Repeating unit represented by formula (V-1) or the following formula (V-2)>

[0689] The resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).

[0690] The repeating units represented by the following formula (V-1) and the following formula (V-2) are preferably repeating units different from the above-mentioned repeating units.

[0691] [Chemical Formula 67]

[0692]

[0693] Where,

[0694] R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. The alkyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms.

[0695] n3 represents an integer from 0 to 6.

[0696] n4 represents an integer from 0 to 4.

[0697] X 4 is a methylene group, an oxygen atom or a sulfur atom.

[0698] The repeating unit represented by formula (V-1) or (V-2) is exemplified below.

[0699] Examples of the repeating unit represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of International Publication No. 2018 / 193954.

[0700] <Repeating Unit for Reducing Main Chain Mobility>

[0701] From the perspective of suppressing excessive diffusion of generated acid and pattern collapse during development, the resin (A) preferably has a high glass transition temperature (Tg). The Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. However, excessively high Tgs can reduce the dissolution rate in the developer, so the Tg is preferably 400°C or less, more preferably 350°C or less.

[0702] In addition, in this specification, the glass transition temperature (Tg) of a polymer such as resin (A) is calculated by the following method. First, the Tg of a homopolymer consisting solely of each repeating unit contained in the polymer is calculated separately by the Bicerano method. The calculated Tg is then referred to as "repeating unit Tg". Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg in each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and their sum is set as the Tg (°C) of the polymer.

[0703] The Bicerano method is described in Prediction of Polymer Properties, Marcel Dekker Inc., New York (1993), etc. Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0704] In order to increase the Tg of the resin (A) (preferably to exceed 90°C), it is preferable to reduce the mobility of the main chain of the resin (A). The following methods (a) to (e) can be used to reduce the mobility of the main chain of the resin (A).

[0705] (a) Introducing bulky substituents into the main chain

[0706] (b) Introducing multiple substituents into the main chain

[0707] (c) Introducing a substituent that triggers interaction between resins (A) near the main chain

[0708] (d) Forming a main chain in a ring structure

[0709] (e) Connecting the ring structure to the main chain

[0710] Furthermore, the resin (A) preferably has a repeating unit showing a Tg of 130° C. or higher as a homopolymer.

[0711] The type of repeating unit showing a homopolymer Tg of 130°C or higher is not particularly limited, as long as the repeating unit has a homopolymer Tg of 130°C or higher as calculated by the Bicerano method. Depending on the type of functional group in the repeating units represented by formulae (A) to (E) described later, the repeating unit corresponding to the homopolymer Tg of 130°C or higher may be used.

[0712] (Repeating unit represented by formula (A))

[0713] As an example of a specific means for realizing the above-mentioned (a), there is mentioned a method of introducing a repeating unit represented by the formula (A) into the resin (A).

[0714] [Chemical Formula 68]

[0715]

[0716] In formula (A), R A Represents a group having a polycyclic structure. x represents a hydrogen atom, a methyl group, or an ethyl group. A group having a polycyclic structure is a group having multiple ring structures, and the multiple ring structures may or may not be fused.

[0717] Specific examples of the repeating unit represented by formula (A) include the repeating units described in paragraphs

[0107] to

[0119] of International Publication No. 2018 / 193954.

[0718] (Repeating unit represented by formula (B))

[0719] As an example of a specific means for realizing the above-mentioned (b), there is mentioned a method of introducing a repeating unit represented by the formula (B) into the resin (A).

[0720] [Chemical Formula 69]

[0721]

[0722] In formula (B), R b1 ~R b4 Each independently represents a hydrogen atom or an organic group, R b1 ~R b4 At least two of them represent organic groups.

[0723] Furthermore, when at least one of the organic groups is a group having a ring structure directly connected to the main chain of the repeating unit, the types of the other organic groups are not particularly limited.

[0724] Furthermore, when any of the organic groups is not a group having a ring structure directly connected to the main chain in the repeating unit, at least two or more of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms.

[0725] Specific examples of the repeating unit represented by formula (B) include the repeating units described in paragraphs

[0113] to

[0115] of International Publication No. 2018 / 193954.

[0726] (Repeating unit represented by formula (C))

[0727] As an example of a specific means for realizing the above-mentioned (c), there is mentioned a method of introducing a repeating unit represented by the formula (C) into the resin (A).

[0728] [Chemical Formula 70]

[0729]

[0730] In formula (C), R c1 ~R c4 Each independently represents a hydrogen atom or an organic group, R c1 ~R c4 At least one of the groups is a group having a hydrogen-bonding hydrogen atom within 3 atoms from the main chain carbon. Of these, it is preferred that the group have a hydrogen-bonding hydrogen atom within 2 atoms (closer to the main chain) in order to cause interaction between the main chains of the resin (A).

[0731] Specific examples of the repeating unit represented by formula (C) include the repeating units described in paragraphs

[0119] to

[0121] of International Publication No. 2018 / 193954.

[0732] (Repeating unit represented by formula (D))

[0733] As an example of a specific means for realizing the above-mentioned (d), there is mentioned a method of introducing a repeating unit represented by the formula (D) into the resin (A).

[0734] [Chemical Formula 71]

[0735]

[0736] In formula (D), "cylic" represents a group whose main chain is formed by a cyclic structure. The number of atoms constituting the ring is not particularly limited.

[0737] Specific examples of the repeating unit represented by formula (D) include the repeating units described in paragraphs

[0126] to

[027] of International Publication No. 2018 / 193954.

[0738] (Repeating unit represented by formula (E))

[0739] As an example of a specific means for realizing the above-mentioned (e), there is mentioned a method of introducing a repeating unit represented by the formula (E) into the resin (A).

[0740] [Chemical Formula 72]

[0741]

[0742] In formula (E), Re each independently represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, which may have a substituent.

[0743] "Cyclic" refers to a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited.

[0744] Specific examples of the repeating unit represented by formula (E) include the repeating units described in paragraphs

[0131] to

[0133] of International Publication No. 2018 / 193954.

[0745] <Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group>

[0746] The resin (A) may include a repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.

[0747] Examples of the repeating units having a lactone group, a sultone group, or a carbonate group in the resin (A) include the repeating units described in the above section "Repeating units having a lactone group, a sultone group, or a carbonate group." The preferred content is also the same as described in the above section "Repeating units having a lactone group, a sultone group, or a carbonate group."

[0748] The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group, thereby improving substrate adhesion and developer affinity.

[0749] The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.

[0750] The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include the repeating units described in paragraphs

[0153] to

[0158] of International Publication No. 2020 / 004306.

[0751] The resin (A) may also contain a repeating unit having an alkali-soluble group.

[0752] Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonimide groups, bissulfonimide groups, and aliphatic alcohols substituted with electron-withdrawing groups at the α-position (e.g., hexafluoroisopropanol groups), with carboxyl groups being preferred. By including repeating units having alkali-soluble groups in resin (A), the resolution in contact hole applications is improved. Examples of repeating units having alkali-soluble groups include those described in paragraphs

[0085] and

[0086] of JP-A-2014-98921.

[0753] <Repeating Unit Having an Alicyclic Hydrocarbon Structure and Not Exhibiting Acid Decomposability>

[0754] Resin (A) may also contain repeating units having an alicyclic hydrocarbon structure and being non-acid decomposable. This can reduce the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0755] <Repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group>

[0756] The resin (A) may include a repeating unit represented by the formula (III) which does not have either a hydroxyl group or a cyano group.

[0757] [Chemical Formula 73]

[0758]

[0759] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.

[0760] Ra represents a hydrogen atom, an alkyl group or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group or an acyl group.

[0761] The cyclic structure of R5 includes monocyclic hydrocarbon groups and polycyclic hydrocarbon groups. Examples of the monocyclic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) and cycloalkenyl groups having 3 to 12 carbon atoms.

[0762] Specific examples of detailed definitions of the groups and repeating units in formula (III) include those described in paragraphs

[0169] to

[0173] of International Publication No. 2020 / 004306.

[0763] <Other repeating units>

[0764] The resin (A) may contain repeating units other than the above-mentioned repeating units.

[0765] For example, the resin (A) may include a repeating unit selected from the group consisting of a repeating unit having a thioxane ring group, a repeating unit having an oxazorone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group.

[0766] Such repeating units are exemplified below.

[0767] [Chemical Formula 74]

[0768]

[0769] In addition to the above-mentioned repeating structural units, the resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, compatibility with standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc.

[0770] It is also preferred that all repeating units of the resin (A) consist of (meth)acrylate repeating units (especially when the composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF). In this case, any of the following repeating units can be used: a repeating unit in which all repeating units are methacrylate repeating units, a repeating unit in which all repeating units are acrylate repeating units, or a repeating unit in which all repeating units are composed of methacrylate repeating units and acrylate repeating units. Preferably, the acrylate repeating units account for 50 mol% or less of all repeating units.

[0771] The resin (A) can be synthesized according to a conventional method (eg, radical polymerization).

[0772] The weight-average molecular weight of resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000, as measured by GPC. By setting the weight-average molecular weight of resin (A) to 1,000 to 200,000, deterioration in heat resistance and dry etching resistance can be further suppressed. Furthermore, deterioration in film-forming properties due to poor developability and increased viscosity can be further suppressed.

[0773] The dispersity (molecular weight distribution) of the resin (A) is generally 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and the smoother the sidewalls of the resist pattern and the better the roughness.

[0774] In the resist composition, the content of the resin (A) is preferably 50.0 to 99.9% by mass, more preferably 60.0 to 99.0% by mass, based on the total solid content of the composition.

[0775] Furthermore, the resin (A) may be used alone or in combination of two or more.

[0776] [Acid diffusion controller (C)]

[0777] The resist composition may contain an acid diffusion controller (C).

[0778] The acid diffusion controller captures the acid generated from the photoacid generator during exposure, acting as a quencher. This quencher suppresses the reaction of the acid-decomposable resin in the unexposed area caused by the excess acid. Examples of acid diffusion controllers include basic compounds (CA), basic compounds (CB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation, low molecular weight compounds (CD) containing nitrogen atoms and groups that are dissociated by the action of an acid, and onium salt compounds (CE) containing nitrogen atoms in the cation portion.

[0779] Furthermore, as the acid diffusion controller, an onium salt that is a relatively weak acid relative to the photoacid generating component can also be used.

[0780] When a photoacid generator (specific photoacid generators and other photoacid generators are also collectively referred to as photoacid-generating components) and an onium salt that generates an acid relatively weak relative to the acid generated by the photoacid-generating component are used in coexistence, if the acid generated by the photoacid-generating component collides with the onium salt having unreacted weak acid anions upon irradiation with actinic rays or radiation, the weak acid is released through salt exchange, and an onium salt having a strong acid anion is generated. In this process, the strong acid is exchanged for a weaker acid with lower catalytic activity, thereby apparently deactivating the acid and controlling its diffusion.

[0781] As the onium salt that becomes a relatively weak acid with respect to the photoacid generating component, compounds represented by the following formulae (d1-1) to (d1-3) are preferred.

[0782] [Chemical Formula 75]

[0783]

[0784] Where R 51 is an organic group and preferably has 1 to 30 carbon atoms.

[0785] Z 2c The organic group preferably has 1 to 30 carbon atoms. 2c In the organic group represented by 3- When adjacent, the carbon atom (α carbon atom) does not have a fluorine atom and / or a perfluoroalkyl group as a substituent. The above-mentioned α carbon atom is a ring member atom of a cyclic structure, preferably a methylene group. 2c In comparison with SO3 - When the atom at the β-position of is a carbon atom (β-carbon atom), the β-carbon atom also does not have a fluorine atom and / or a perfluoroalkyl group as a substituent.

[0786] R 52 is an organic group (alkyl group, etc.), Y 3is -SO2-, a linear, branched or cyclic alkylene or arylene group, Y 4 is -CO- or -SO2-, and Rf is a hydrocarbon group having a fluorine atom (such as a fluoroalkyl group).

[0787] M + Each independently represents an ammonium cation, a sulfonium cation or an iodonium cation. + , the organic cations mentioned in the description of the specific compound (for example, M in the above formula (Ia-1)) can also be used. 11 + (represented by an organic cation).

[0788] As one embodiment, it is also preferred that these cations have an acid-decomposable group. Examples of the acid-decomposable group include the acid-decomposable group represented by the above formula (1) and the acid-decomposable group represented by the formula (2).

[0789] As the acid diffusion controller, a zwitterion can be used. The zwitterion preferably has a carboxylate anion, and more preferably has a sulfonium cation or an iodonium cation.

[0790] In the resist composition of the present invention, a known acid diffusion controller can be appropriately used. For example, known compounds disclosed in paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

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

[0791] Furthermore, for example, as specific examples of basic compounds (CA), the compounds described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824 can be cited, as specific examples of basic compounds (CB) whose basicity is reduced or disappears by irradiation with actinic rays or radiation, the compounds described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824 can be cited, as specific examples of low molecular weight compounds (CD) having a nitrogen atom and a group that is detached by the action of an acid, the compounds described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824 can be cited, and as specific examples of onium salt compounds (CE) having a nitrogen atom in the cation part, the compounds described in paragraph

[0164] of International Publication No. 2020 / 066824 can be cited.

[0792] When the resist composition contains an acid diffusion controller, the content of the acid diffusion controller (the total amount when multiple types are present) is preferably 0.1 to 11.0 mass %, more preferably 0.1 to 10.0 mass %, further preferably 0.1 to 8.0 mass %, and particularly preferably 0.1 to 4.0 mass % relative to the total solid content of the composition.

[0793] In the resist composition, the acid diffusion controller may be used alone or in combination of two or more.

[0794] Hydrophobic resin (D)

[0795] The resist composition may contain a hydrophobic resin different from the resin (A) in addition to the above-mentioned resin (A).

[0796] The hydrophobic resin is preferably designed to be localized on the surface of the resist film, but unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule and does not need to contribute to uniform mixing of polar and nonpolar substances.

[0797] Examples of the effects of adding a hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with respect to water and suppression of outgassing.

[0798] From the perspective of localization to the film surface, the hydrophobic resin preferably contains at least one of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain of the resin, and more preferably contains at least two of these. Furthermore, the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the resin main chain or substituted by a side chain.

[0799] Examples of the hydrophobic resin include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306.

[0800] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, further preferably 0.1 to 10 mass %, and particularly preferably 0.1 to 5.0 mass % relative to the total solid content of the resist composition.

[0801] [Surfactant (E)]

[0802] The resist composition may contain a surfactant. If the surfactant is contained, a pattern with better adhesion and fewer development defects can be formed.

[0803] The surfactant is preferably a fluorine-based and / or silicon-based surfactant.

[0804] As the fluorine-based and / or silicon-based surfactant, for example, the surfactants disclosed in paragraphs

[0218] and

[0219] of International Publication No. 2018 / 19395 can be used.

[0805] These surfactants may be used alone or in combination of two or more.

[0806] When the resist composition contains a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass %, more preferably 0.0005 to 1 mass %, based on the total solid content of the composition.

[0807] [Solvent (F)]

[0808] The resist composition may contain a solvent.

[0809] The solvent preferably contains at least one of (M1) propylene glycol monoalkyl ether carboxylate and (M2), wherein (M2) is at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, linear ketone, cyclic ketone, lactone, and alkylene carbonate. Furthermore, the solvent may contain components other than components (M1) and (M2).

[0810] The present inventors have discovered that using such solvents in combination with the above-mentioned resins improves the coating properties of the composition and enables the formation of patterns with fewer development defects. While the reason for this is not yet clear, the present inventors believe that this is because these solvents have a good balance of solubility, boiling point, and viscosity in the above-mentioned resins, thereby suppressing uneven film thickness of the composition film and the generation of precipitates during the spin coating process.

[0811] The details of component (M1) and component (M2) are described in paragraphs

[0218] to

[0226] of International Publication No. 2020 / 004306.

[0812] When the solvent further contains components other than components (M1) and (M2), the content of the components other than components (M1) and (M2) is preferably 5 to 30% by mass based on the total amount of the solvent.

[0813] The content of the solvent in the resist composition is preferably set to a solid content concentration of 0.5 to 30% by mass, more preferably 1 to 20% by mass. This can further improve the coating properties of the resist composition.

[0814] In addition, the solid content means all components except the solvent.

[0815] [Other additives]

[0816] The resist composition may further contain a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (eg, a phenol compound having a molecular weight of 1000 or less or an alicyclic or aliphatic compound containing a carboxylic acid group).

[0817] The resist composition may further contain a dissolution-inhibiting compound. Here, the "dissolution-inhibiting compound" is a compound having a molecular weight of 3,000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0818] The resist composition of the present invention is suitable as a photosensitive composition for EUV light.

[0819] EUV light has a wavelength of 13.5nm, which is shorter than ArF light (193nm). Therefore, the number of incident photons is low when exposure is performed at the same sensitivity. Consequently, the random variation in the number of photons significantly impacts "photon shot noise," which can lead to LER degradation and bridging defects. To reduce photon shot noise, increasing the number of incident photons by increasing the exposure dose is a method, but this trades off against the need for higher sensitivity.

[0820] When the A value obtained by the following formula (1) is high, the absorption efficiency of EUV light and electron beams by the resist film formed from the resist composition becomes high, which is effective in reducing photon shot noise. The A value represents the absorption efficiency of EUV light and electron beams in the mass ratio of the resist film.

[0821] Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[0]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127)

[0822] The A value is preferably 0.120 or greater. There is no particular upper limit, but if the A value is too large, the transmittance of the resist film to EUV light and electron beams decreases, the optical image profile in the resist film deteriorates, and as a result, it becomes difficult to obtain a good pattern shape. Therefore, the A value is preferably 0.240 or less, and more preferably 0.220 or less.

[0823] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solid content relative to all atoms in the total solid content of the actinic ray or radiation-sensitive resin composition, [C] represents the molar ratio of carbon atoms derived from the total solid content relative to all atoms in the total solid content of the actinic ray or radiation-sensitive resin composition, [N] represents the molar ratio of nitrogen atoms derived from the total solid content relative to all atoms in the total solid content of the actinic ray or radiation-sensitive resin composition, [O] represents the molar ratio of oxygen atoms derived from the total solid content relative to all atoms in the total solid content of the actinic ray or radiation-sensitive resin composition, [F] represents the molar ratio of fluorine atoms derived from the total solid content relative to all atoms in the total solid content of the actinic ray or radiation-sensitive resin composition, [S] represents the molar ratio of sulfur atoms derived from the total solid content relative to all atoms in the total solid content of the actinic ray or radiation-sensitive resin composition, and [I] represents the molar ratio of iodine atoms derived from the total solid content relative to all atoms in the total solid content of the actinic ray or radiation-sensitive resin composition.

[0824] For example, when the resist composition contains a resin whose polarity increases with the action of an acid (acid-decomposable resin), a photoacid generator, an acid diffusion controller, and a solvent, the resin, the photoacid generator, and the acid diffusion controller correspond to the solid component. That is, all atoms in the total solid component correspond to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion controller. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid component to all atoms in the total solid component. Based on the above example, [H] represents the molar ratio of the sum of hydrogen atoms derived from the resin, hydrogen atoms derived from the photoacid generator, and hydrogen atoms derived from the acid diffusion controller to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion controller.

[0825] The A value can be calculated by calculating the structure of the constituent components of the total solid content in the resist composition and the atomic ratio when the content is known. Furthermore, even when the constituent components are unknown, the atomic ratio of the constituent components can be calculated using analytical methods such as elemental analysis for a resist film obtained by evaporating the solvent component of the resist composition.

[0826] [Resist film and pattern forming method]

[0827] The steps of the pattern forming method using the resist composition are not particularly limited, but preferably include the following steps.

[0828] Step 1: A step of forming a resist film on a substrate using a resist composition.

[0829] Step 2: Exposure of the resist film

[0830] Step 3: Developing the exposed resist film using a developer

[0831] Hereinafter, the steps of each of the above processes will be described in detail.

[0832] <Step 1: Resist Film Formation Step>

[0833] Step 1 is a step of forming a resist film on a substrate using a resist composition.

[0834] The resist composition is as defined above.

[0835] As a method of forming a resist film on a substrate using a resist composition, a method of applying the resist composition on the substrate is mentioned, for example.

[0836] In addition, the resist composition is preferably filtered before application, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0837] The resist composition can be applied to substrates (e.g., silicon or silicon dioxide coatings) used in the manufacture of integrated circuit devices, for example, by an appropriate coating method such as a spin coater or a coating machine. Spin coating using a spin coater is preferred. The rotation speed during spin coating using a spin coater is preferably 1000 to 3000 rpm.

[0838] After applying the resist composition, the substrate may be dried to form a resist film. In addition, various base films (inorganic films, organic films, anti-reflective films) may be formed under the resist film as needed.

[0839] Examples of drying methods include drying by heating. Heating can be performed using a device typically included in an exposure machine and / or a developer, or using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0840] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the perspective of enabling formation of finer patterns with higher precision. In the case of EUV exposure, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. Furthermore, in the case of ArF immersion exposure, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0841] Alternatively, a top coat layer may be formed on the resist film using a top coat composition.

[0842] The topcoat composition is preferably capable of being uniformly applied to the upper layer of the resist film without mixing with the resist film. The topcoat layer is not particularly limited and can be formed by a conventionally known method. For example, the topcoat layer can be formed based on the contents described in paragraphs

[0072] to

[0082] of Japanese Patent Application Laid-Open No. 2014-059543.

[0843] For example, it is preferable to form a top coat layer containing a basic compound as described in Japanese Patent Application Laid-Open No. 2013-61648 on the resist film. Specific examples of the basic compound that can be contained in the top coat layer include basic compounds that can be contained in the resist composition.

[0844] Furthermore, the topcoat layer preferably further includes a compound including at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0845] <Process 2: Exposure Process>

[0846] Step 2 is a step of exposing the resist film to light.

[0847] As an exposure method, a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask can be mentioned.

[0848] Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Preferably, the wavelength is 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light of 1 to 200 nm. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams.

[0849] After exposure, it is preferable to perform baking (heating) before development. Baking promotes the reaction of the exposed portion, thereby further improving the sensitivity and pattern shape.

[0850] The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.

[0851] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.

[0852] Heating can be performed using a device included in a general exposure machine and / or developing machine, or using a hot plate or the like.

[0853] This process is also called post-exposure bake.

[0854] <Step 3: Development Step>

[0855] Step 3 is a step of developing the exposed resist film using a developer to form a pattern.

[0856] The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0857] Examples of the developing method include: a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method); a method of developing by causing the developer to bulge on the surface of the substrate due to surface tension and allowing the developer to stand for a certain period of time (puddle method); a method of spraying the developer onto the surface of the substrate (spray method); and a method of continuously spraying the developer while scanning a developer spray nozzle at a certain speed on a substrate rotating at a certain speed (dynamic dispense method).

[0858] Furthermore, after the development step, a step of stopping the development while replacing the solvent with another solvent may be performed.

[0859] The development time is not particularly limited as long as it is a time for the resin in the unexposed portion to fully dissolve, but is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.

[0860] The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0861] The alkaline developer preferably uses an alkaline aqueous solution containing an alkali. The type of the alkaline aqueous solution is not particularly limited, and examples thereof include alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic bases, primary amines, secondary amines, tertiary amines, alcoholamines, or cyclic amines. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohol, surfactant, etc. can be added to the alkaline developer. The alkali concentration of the alkaline developer is generally 0.1 to 20% by mass. Furthermore, the pH of the alkaline developer is generally 10.0 to 15.0.

[0862] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0863] The developer may contain a plurality of solvents or other solvents or water. The developer may contain water in an amount of less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially no water.

[0864] The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, relative to the total amount of the developer.

[0865] <Other Processes>

[0866] The pattern forming method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0867] As a rinse liquid used in the rinse step after the development step using an alkaline developer, pure water can be mentioned, for example. In addition, an appropriate amount of a surfactant can be added to the pure water.

[0868] An appropriate amount of surfactant may be added to the flushing solution.

[0869] The rinsing liquid used in the rinsing step following the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern. A solution containing a common organic solvent can be used. The rinsing liquid preferably contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0870] The method of the rinsing process is not particularly limited. For example, there can be a method of continuously spraying a rinsing liquid on a substrate rotating at a certain speed (spin coating method), a method of immersing the substrate in a tank filled with rinsing liquid for a certain period of time (immersion method), and a method of spraying the rinsing liquid onto the surface of the substrate (spray coating method).

[0871] Furthermore, the pattern forming method of the present invention may include a heating step (post-bake) after the rinsing step. This step can remove the developer and rinse solution remaining between and within the pattern due to baking. Furthermore, this step also has the effect of smoothing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is typically performed at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0872] Furthermore, the formed pattern can be used as a mask to perform etching of the substrate. That is, the pattern formed in step 3 can be used as a mask to form a pattern on the substrate by processing the substrate (or the underlying film and the substrate).

[0873] The processing method of the substrate (or the underlying film and the substrate) is not particularly limited, but is preferably a method of forming a pattern on the substrate by dry etching the substrate (or the underlying film and the substrate) using the pattern formed in step 3 as a mask. The dry etching is preferably oxygen plasma etching.

[0874] The various materials used in the resist composition and the pattern forming method of the present invention (for example, solvent, developer, rinse solution, anti-reflective film forming composition, top coat forming composition, etc.) preferably do not contain impurities such as metal. The content of the impurities included in these materials is preferably less than 1 mass ppm, more preferably less than 10 mass ppb, further preferably less than 100 mass ppt, especially preferably less than 10 mass ppt, most preferably less than 1 mass ppt. Here, as metallic impurities, for example, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W and Zn etc. can be enumerated.

[0875] As a method for removing impurities such as metals from various materials, for example, filtration using a filter can be cited. The details of filtration using a filter are described in paragraph

[0321] of International Publication No. 2020 / 004306.

[0876] In addition, as methods for reducing impurities such as metals contained in various materials, for example, there are a method of selecting raw materials with a low metal content as raw materials constituting various materials, a method of filtering the raw materials constituting various materials, and a method of performing distillation under conditions that minimize contamination by lining the inside of an apparatus with Teflon (registered trademark).

[0877] In addition to filtering, impurities can be removed by an adsorbent, or a combination of filtering and adsorbent can be used. As the adsorbent, known adsorbents can be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce the impurities such as metals contained in the above-mentioned various materials, it is necessary to prevent the mixing of metal impurities in the manufacturing process. Whether the metal impurities are fully removed from the manufacturing device can be confirmed by measuring the content of the metal components contained in the cleaning solution used when cleaning the manufacturing device. The content of the metal components contained in the cleaning solution after use is preferably less than 100 mass ppt (parts per trillion), more preferably less than 10 mass ppt, and further preferably less than 1 mass ppt.

[0878] To prevent static electricity charging and the resulting electrostatic discharge that can cause malfunctions in the chemical piping and various components (such as filters, O-rings, and hoses), a conductive compound can be added to organic processing fluids such as rinse solutions. The conductive compound is not particularly limited; an example of such a compound is methanol. The amount added is not particularly limited; however, to maintain optimal developing and rinsing properties, it is preferably 10% by mass or less, and more preferably 5% by mass or less.

[0879] For example, SUS (stainless steel) or various types of piping coated with antistatic polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin) can be used as liquid medicine piping. Similarly, antistatic polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin) can be used for filters and O-rings.

[0880] [Method for manufacturing electronic device]

[0881] Furthermore, the present invention relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method, and an electronic device manufactured by the manufacturing method.

[0882] The electronic device of the present invention is an electronic device that is suitably mounted on electrical and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment).

[0883] Example

[0884] Below, the present invention is further described in detail according to the embodiments. As long as it does not depart from the purpose of the present invention, the materials, usage amounts, ratios, processing contents and processing steps shown in the following examples can be appropriately changed. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0885] [Various components of the actinic ray or radiation-sensitive resin composition]

[0886] [Acid-decomposable resin (resin (A))]

[0887] The resins A (resins A-1 to A-55) shown in Tables 3 and 6 are shown below.

[0888] Resins A-1 to A-55 were synthesized according to a known method. Table 1 shows the composition ratio (molar ratio; corresponding from left to right), weight average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit described below.

[0889] The weight average molecular weight (Mw) and the dispersity (Mw / Mn) (in terms of polystyrene) of resins A-1 to A-55 were measured by GPC (carrier: tetrahydrofuran (THF)). 13 The composition ratio (molar ratio) of the resin was measured by C-NMR (nuclear magnetic resonance).

[0890] [Table 1]

[0891]

[0892] [Table 2]

[0893]

[0894] The structural formulas of resins A-1 to A-55 shown in Table 1 are shown below.

[0895] [Chemical Formula 76]

[0896]

[0897] [Chemical Formula 77]

[0898]

[0899] [Chemical Formula 78]

[0900]

[0901] [Chemical Formula 79]

[0902]

[0903] [Chemical formula 80]

[0904]

[0905]

[0906] [Chemical Formula 81]

[0907]

[0908] [Chemical Formula 82]

[0909]

[0910] [Chemical Formula 83]

[0911]

[0912] 〔Photoacid generator〕

[0913] <Compounds (I) and (II) (Specific Compounds) and Comparative Compounds>

[0914] The structures of compounds (I) and (II) (compounds X-1 to X-44) and comparative compounds (compounds Z-1 and Z-2) shown in Tables 3 and 6 are shown below.

[0915] Compounds X-1 to X-44 and compounds Z-1 and Z-2 were synthesized according to the synthesis method of compound X-1 described later.

[0916] Comparative compound Z-1 below corresponds to a structure having an acetal structure decomposable by acid in the linking site connecting anionic sites, and comparative compound Z-2 below corresponds to a structure having no acid-decomposable group.

[0917] [Chemical Formula 84]

[0918]

[0919] [Chemical Formula 85]

[0920]

[0921] [Chemical Formula 86]

[0922]

[0923] [Chemical Formula 87]

[0924]

[0925] [Chemical Formula 88]

[0926]

[0927] [Chemical Formula 89]

[0928]

[0929]

[0930] [Chemical formula 90]

[0931]

[0932] [Chemical Formula 91]

[0933]

[0934] [Chemical Formula 92]

[0935]

[0936] [Chemical Formula 93]

[0937]

[0938] [Chemical Formula 94]

[0939]

[0940] [Chemical Formula 95]

[0941]

[0942] [Chemical Formula 96]

[0943]

[0944] [Chemical Formula 97]

[0945]

[0946] [Chemical Formula 98]

[0947]

[0948] [Chemical Formula 99]

[0949]

[0950] In addition, the numerical values ​​added to each of the above-mentioned compounds (I) (compounds X-1 to X-44) and comparative compounds (compounds Z-1 and Z-2) (for example, in the case of compound X-1, the numerical values ​​corresponding to -3.41 and -0.24, respectively, from the left) represent the acid dissociation constant pKa of the acid generated by each compound by exposure (hereinafter also referred to as "generated acid"). For example, when two cations are decomposed by exposure, compound X-1 generates an acid with the following structure. The acid generated by compound X-1 has two acidic sites (proton donor sites) of *-SO3H and *-SO2-NH-CO-*, respectively, from the left, and the acid dissociation constant pKa derived from each acidic site is -3.41 and -0.24. That is, the numerical values ​​added to each of the above-mentioned compounds represent the acid dissociation constant pKa derived from each acidic site (proton donor site) of the acid generated by each compound by exposure.

[0951] [Chemical Formula 100]

[0952]

[0953] When measuring the acid dissociation constant pKa of the acid generated by compound (I) (compounds X-1 to X-44) and comparative compounds (compounds Z-1 and Z-2), specifically, H + The compounds formed by replacing each cationic site in each compound (for example, in the case of compound X-7, H + For the compound (a compound formed by substituting two triphenylsulfonium cations), as described above, the values ​​of the substituent constant based on Hammett and the database of known literature values ​​were calculated using ACD / Labs' software package 1. In addition, when the pKa could not be calculated using the above method, the value obtained by DFT (density functional theory) and Gaussian16 was used.

[0954] In each of compounds X-1 to X-18 and X-21 to X-44, the highest value among the values ​​added to each compound corresponds to the acid dissociation constant a2 derived from structural site Y. Furthermore, all values ​​other than the highest value among the values ​​added to each compound correspond to the acid dissociation constant a1 derived from structural site X.

[0955] In each of Compounds X-19 and X-20, the numerical value added to each compound corresponds to the acid dissociation constant a1 derived from the structural site X.

[0956] (Synthesis Example 1: Synthesis of Compound X-1)

[0957] [Chemical Formula 101]

[0958]

[0959] Magnesium (18.0 g) was added to tetrahydrofuran (500 mL) to obtain a mixture. 4-bromotrifluorotoluene (151.5 g) was added dropwise to the obtained mixture. Then, the above mixture was stirred for 1 hour to prepare Grignard reagent A. Thionyl chloride (37.7 g) was added to tetrahydrofuran (500 mL) to obtain a mixed solution. The obtained mixed solution was cooled to 0°C, and the previously prepared Grignard reagent A was added dropwise to the above mixed solution. After the above mixed solution was stirred for 1 hour, 1N hydrochloric acid (600 mL) was added to the above mixed solution while maintaining the temperature of the above mixed solution at 0°C. The reaction product generated in the above mixed solution was extracted with ethyl acetate (600 mL). The obtained organic phase was washed with saturated sodium bicarbonate aqueous solution (500 mL) and water (500 mL), and then the solvent was distilled off from the above organic phase. The obtained concentrate was washed with hexane (300 mL) and filtered to obtain Intermediate A (60 g) as a filtrate (yield 56%).

[0960] [Chemical Formula 102]

[0961]

[0962] Intermediate A (30.0 g) was added to a mixture of phosphorus pentoxide (6.8 g) and methanesulfonic acid (90.8 g). The resulting mixture was cooled to 10°C, 2,6-dimethylphenol (11.9 g) was added, and the mixture was stirred at 20°C for 30 minutes. The resulting mixture was heated to 50°C, stirred for 3 hours, and then water (300 mL) was added dropwise below 20°C. Extraction was performed with dichloromethane (300 mL), the organic layer was washed with water (300 mL), and the solvent was distilled off. The concentrate was crystallized with ethyl acetate (300 mL), and intermediate B (35 g) was obtained by filtration (yield 73%).

[0963] [Chemical Formula 103]

[0964]

[0965] To intermediate B (20.0 g) were added tert-butyl-2-bromoacetate (7.9 g), cesium carbonate (18.2 g) and dimethylacetamide (174 g), and stirred at 40°C for 2 hours. The resulting mixture was cooled to room temperature and filtered, followed by addition of dichloromethane (150 g) and washing twice with 1N hydrochloric acid (100 mL). Furthermore, the organic layer was washed twice with water (100 mL), and the solvent was distilled off. The concentrate was crystallized with diisopropyl ether (200 mL) and filtered to obtain intermediate C (19 g) (yield 78%).

[0966] [Chemical Formula 104]

[0967]

[0968] Dichloromethane (100 mL) and water (100 mL) were mixed, and the sodium salt (5.0 g) and Intermediate C (13.7 g) were added. After stirring for 1 hour, the aqueous layer was removed, and the organic layer was washed with 0.1N hydrochloric acid (100 mL) and water (100 mL). The solvent was removed by filtration to obtain the product (13.8 g) (yield 90%).

[0969] <Photoacid Generator B>

[0970] The structures of the photoacid generators B (compounds B-1 to B-16) shown in Tables 3 and 6 are shown below.

[0971] [Chemical Formula 105]

[0972]

[0973] [Chemical Formula 106]

[0974]

[0975]

[0976] 〔Acid diffusion controller〕

[0977] The structures of the acid diffusion controllers C (compounds C-1 to C-8) shown in Tables 3 and 6 are shown below.

[0978] [Chemical Formula 107]

[0979]

[0980] [Chemical Formula 108]

[0981]

[0982] Hydrophobic resin and topcoat resin

[0983] The hydrophobic resins (D-1 to D-6) shown in Tables 3 and 6, and the top coat layer resins (PT-1 to PT-3) shown in Table 7 were synthesized resins.

[0984] Table 2 shows the molar ratio, weight average molecular weight (Mw), and dispersion degree (Mw / Mn) of the repeating units in the hydrophobic resins (D-1 to D-6) shown in Tables 3 and 6, and the top coat resins (PT-1 to PT-3) shown in Table 7.

[0985] The weight average molecular weight (Mw) and the dispersity (Mw / Mn) (in terms of polystyrene) of the hydrophobic resins D-1 to D-6 and the top coat resins PT-1 to PT-3 were measured by GPC (carrier: tetrahydrofuran (THF)). 13 The composition ratio (molar ratio) of the resin was measured by C-NMR (nuclear magnetic resonance).

[0986] [Table 3]

[0987]

[0988] The monomer structures used in the synthesis of the hydrophobic resins D-1 to D-6 shown in Table 2 and the top coat resins PT-1 to PT-3 shown in Table 7 are shown below.

[0989] [Chemical Formula 109]

[0990]

[0991] 〔Surfactant〕

[0992] The surfactants shown in Tables 3 and 6 are shown below.

[0993] E-1: Megaface F176 (manufactured by DIC CORPORATION, fluorine-based surfactant)

[0994] E-2: Megaface R08 (manufactured by DIC CORPORATION, fluorine and silicone surfactants)

[0995] E-3: PF656 (manufactured by OMNOVA Solutions Inc., fluorine-based surfactant)

[0996] Solvent

[0997] The solvents shown in Tables 3 and 6 are shown below.

[0998] F-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0999] F-2: Propylene glycol monomethyl ether (PGME)

[1000] F-3: Propylene glycol monoethyl ether (PGEE)

[1001] F-4: Cyclohexanone

[1002] F-5: Cyclopentanone

[1003] F-6: 2-Heptanone

[1004] F-7: Ethyl lactate

[1005] F-8: γ-butyrolactone

[1006] F-9: Propylene carbonate

[1007] [Preparation and Patterning of Actinic Ray-Sensitive or Radiation-Sensitive Resin Compositions: EUV Exposure]

[1008] [Preparation of actinic ray-sensitive or radiation-sensitive resin composition (1)]

[1009] The components shown in Table 3 were mixed so that the solid content concentration became 2% by mass. Then, the resulting mixed solution was filtered by first filtering through a polyethylene filter with a pore size of 50 nm, then filtering through a nylon filter with a pore size of 10 nm, and finally filtering through a polyethylene filter with a pore size of 5 nm to prepare an actinic ray or radiation-sensitive resin composition (hereinafter also referred to as a resist composition). In addition, in the resist composition, the solid content represents all components except the solvent. The obtained resist composition was used in the Examples and Comparative Examples.

[1010] [Table 4]

[1011] (Table 3-1)

[1012]

[1013] [Table 5]

[1014] (Table 3-Part 2)

[1015]

[1016] [Table 6]

[1017] (Table 3-Part 3)

[1018]

[1019] [Table 7]

[1020] (Table 3-4)

[1021]

[1022] [Table 8]

[1023] (Table 3-5)

[1024]

[1025] [Table 9]

[1026] (Table 3-6)

[1027]

[1028] [Pattern formation and evaluation]

[1029] Using the resist composition prepared above, the LWR of the pattern developed under the following conditions was evaluated.

[1030] In all tests, the resist composition (actinic ray-sensitive or radiation-sensitive resin composition) used for pattern formation was one that had been left to stand at 4° C. for 3 months after production.

[1031] <Pattern formation (1): EUV exposure, alkaline aqueous solution development>

[1032] An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 20 nm thick base film. The resist composition shown in Table 4 was applied thereto and baked at 100°C for 60 seconds to form a 30 nm thick resist film.

[1033] The silicon wafer having the obtained resist film was subjected to pattern irradiation using an EUV exposure apparatus (manufactured by Exitech Corporation, Micro Exposure Tool, NAO.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask having a line size of 20 nm and a line:space ratio of 1:1 was used as a reticle.

[1034] The exposed resist film was baked at 90° C. for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, rinsed with pure water for 30 seconds, and then spin-dried to obtain a positive pattern.

[1035] Evaluation of LWR: EUV Exposure and Alkaline Aqueous Solution Development

[1036] For a 20nm (1:1) line and space pattern analyzed using the optimal exposure when analyzing a line pattern with an average line width of 20nm, the line width was observed at any point when observed from the top of the pattern using a length-measuring scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), and the measurement deviation was evaluated using 3σ. The smaller the value, the better the performance. LWR (nm) is preferably 4.5nm or less, more preferably 3.9nm or less, and further preferably 3.6nm or less. The obtained LWR (nm) values ​​were classified and evaluated according to the following evaluation criteria. The results are shown in Table 4.

[1037] "A" LWR value is less than 3.6nm

[1038] "B" LWR value exceeds 3.6nm and is less than 3.9nm

[1039] "C" LWR value exceeds 3.9nm and is less than 4.1nm

[1040] "C-" LWR value exceeds 4.1nm and is less than 4.5nm

[1041] The value of “D” LWR exceeds 4.5nm

[1042] Table 4 is shown below.

[1043] In Tables 4 and 5, in the "Characteristics of Specific Compounds" column, "Type of Acid-Decomposable Group" indicates which of the structures of Formula (1) (ester structure) and Formula (2) (acetal structure) the acid-decomposable group in the specific compound corresponds to. Furthermore, when the structure of the acid-decomposable group does not correspond to either of the structures of Formula (1) or Formula (2), "-" is indicated.

[1044] Furthermore, in the "Characteristics of Specific Compound" column, "Position of Acid-Decomposable Group" indicates at which position the acid-decomposable group is located in the anion site or the cation site, when the acid-decomposable group in the specific compound corresponds to either of the structures of Formula (1) (ester structure) and Formula (2) (acetal structure). The case where the acid-decomposable group is located in the cation site is indicated as "A," and the case where it is located in the anion site is indicated as "B." Furthermore, when the acid-decomposable group does not correspond to any of the structures of Formula (1) and Formula (2), it is indicated as "-."

[1045] Furthermore, in the column “Characteristics of a specific compound”, “Structure of a specific compound” indicates that the specific compound corresponds to the structure of either of the above-mentioned compounds (I) and (II).

[1046] Furthermore, in the "Characteristics of Specific Compounds" column, "Anion Site A2- "Type" indicates that the specific compound corresponds to the above-mentioned compound (I), and indicates the anion site A2 - Does the structure of correspond to the above formula (BB-1) to formula (BB-3)? 2 The case where the structure corresponds to the above formula (BB-1) to formula (BB-3) is represented as "A", and the case where it does not correspond can be represented as "B". In addition, when the structure of a specific compound does not correspond to the above compound (I), it is represented as "-".

[1047] [Table 10]

[1048]

[1049] [Table 11]

[1050]

[1051] [Table 12]

[1052]

[1053] [Table 13]

[1054]

[1055] [Table 14]

[1056]

[1057] [Table 15]

[1058]

[1059] As shown in the table, it was confirmed that the resist compositions of Examples were capable of forming patterns excellent in LWR performance even when used after long-term storage after production.

[1060] Furthermore, it was confirmed that when the specific compound contained in the resist composition of the example satisfies the following condition (A) and satisfies two or more of the following conditions (B1) to (B3) (preferably when all of the following conditions (B1) to (B3) are satisfied), the LWR performance of the pattern formed when used after long-term storage after production is further improved.

[1061] (A) The type of the acid-decomposable group of the specific compound is a structure represented by the above formula (1) (ester structure) or a structure represented by the formula (2) (acetal structure).

[1062] (B1) The type of the acid-decomposable group of the specific compound is a structure (ester structure) represented by the above formula (1).

[1063] (B2) In the specific compound, the acid-decomposable group is located at the cationic site.

[1064] (B3) The specific compound corresponds to the above-mentioned compound (I), and the anion site A2 - The structure corresponds to the above formula (BB-1) to formula (BB-3).

[1065] The resist composition of the comparative example did not exhibit the expected effect.

[1066] <Pattern formation (2): EUV exposure, organic solvent development>

[1067] An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 20 nm thick base film. The resist composition shown in Table 5 was applied thereto and baked at 100°C for 60 seconds to form a 30 nm thick resist film.

[1068] The silicon wafer having the obtained resist film was subjected to pattern irradiation using an EUV exposure apparatus (manufactured by Exitech Corporation, Micro Exposure Tool, NAO.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A mask having a line size of 20 nm and a line:space ratio of 1:1 was used as a reticle.

[1069] The exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.

[1070] Evaluation of LWR: EUV Exposure, Organic Solvent Development

[1071] The LWR (nm) of the formed pattern was measured using the same method as described in "LWR Evaluation: EUV Exposure, Alkaline Aqueous Solution Development." The LWR (nm) is preferably 4.5 nm or less, more preferably 3.9 nm or less, and even more preferably 3.6 nm or less. The obtained LWR (nm) values ​​were classified and evaluated according to the following evaluation criteria. The results are shown in Table 5.

[1072] "A" LWR value is less than 3.6nm

[1073] "B" LWR value exceeds 3.6nm and is less than 3.9nm

[1074] "C" LWR value exceeds 3.9nm and is less than 4.1nm

[1075] "C-" LWR value exceeds 4.1nm and is less than 4.5nm

[1076] The value of “D” LWR exceeds 4.5nm

[1077] [Table 16]

[1078]

[1079] [Table 17]

[1080]

[1081] [Table 18]

[1082]

[1083] [Table 19]

[1084]

[1085] [Table 20]

[1086]

[1087] [Table 21]

[1088]

[1089] As shown in the table, it was confirmed that the resist compositions of Examples were capable of forming patterns excellent in LWR performance even when used after long-term storage after production.

[1090] Furthermore, it was confirmed that when the specific compound contained in the resist composition of the example satisfies the following condition (A) and satisfies two or more of the following conditions (B1) to (B3) (preferably when all of the following conditions (B1) to (B3) are satisfied), the LWR performance of the pattern formed when used after long-term storage after production is further improved.

[1091] (A) The type of the acid-decomposable group of the specific compound is a structure represented by the above formula (1) (ester structure) or a structure represented by the formula (2) (acetal structure).

[1092] (B1) The type of the acid-decomposable group of the specific compound is a structure (ester structure) represented by the above formula (1).

[1093] (B2) In the specific compound, the acid-decomposable group is located at the cationic site.

[1094] (B3) The specific compound corresponds to the above-mentioned compound (I), and the anion site A2 - The structure corresponds to the above formula (BB-1) to formula (BB-3).

[1095] The resist composition of the comparative example did not exhibit the expected effect.

[1096] [Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition and Pattern Formation: ArF Immersion Exposure]

[1097] [Preparation of actinic ray-sensitive or radiation-sensitive resin composition (2)]

[1098] The components shown in Table 6 were mixed so that the solid content concentration became 4% by mass. Then, the resulting mixed solution was filtered by first filtering through a polyethylene filter with a pore size of 50 nm, then filtering through a nylon filter with a pore size of 10 nm, and finally filtering through a polyethylene filter with a pore size of 5 nm to prepare an actinic ray or radiation-sensitive resin composition (hereinafter also referred to as a resist composition). In addition, in the resist composition, the solid content represents all components except the solvent. The obtained resist composition was used in the Examples and Comparative Examples.

[1099] [Table 22]

[1100] Table 6

[1101]

[1102] [Preparation of top coating composition]

[1103] The various components contained in the top coating composition shown in Table 7 are shown below.

[1104] <Resin>

[1105] As the resins shown in Table 7, resins PT-1 to PT-3 shown in Table 2 were used.

[1106] <Additives>

[1107] The structures of the additives shown in Table 7 are shown below.

[1108] [Chemical Formula 110]

[1109]

[1110] <Surfactant>

[1111] The surfactants shown in Table 7 are shown below.

[1112] E-3: PF656 (manufactured by OMNOVA Solutions Inc., fluorine-based surfactant)

[1113] <Solvent>

[1114] The solvents shown in Table 7 are shown below.

[1115] FT-1: 4-Methyl-2-pentanol (MIBC)

[1116] FT-2: n-decane

[1117] FT-3: diisoamyl ether

[1118] <Preparation of Top Coat Composition>

[1119] The components listed in Table 7 were mixed to a solids concentration of 3% by mass. The resulting mixture was then filtered, first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm, to prepare a topcoat composition. The solids content referred to herein refers to all components excluding the solvent. The resulting topcoat composition was used in the Examples.

[1120] [Table 23]

[1121]

[1122] [Pattern formation and evaluation]

[1123] Using the resist composition prepared above, the LWR of the pattern developed under the following conditions was evaluated.

[1124] In all tests, the resist composition (actinic ray-sensitive or radiation-sensitive resin composition) used for pattern formation was one that had been left to stand at 4° C. for 3 months after production.

[1125] <Pattern formation (3): ArF immersion exposure, alkaline aqueous solution development>

[1126] An organic antireflective film-forming composition, ARC29SR (manufactured by Brewer Science), was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 98 nm thick antireflective film. The resist composition shown in Table 8 was applied thereto and baked at 100°C for 60 seconds to form a 90 nm thick resist film. For Examples 3-20 to 3-22, a topcoat film (the type of topcoat composition used is shown in Table 8) was formed on top of the resist film. The topcoat film thickness was 100 nm in each case.

[1127] The resist film was exposed using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, dipole, outer sigma 0.950, inner sigma 0.890, Y deflection) through a 6% halftone mask with a 1:1 line-to-space pattern and a line width of 45 nm. Ultrapure water was used as the immersion liquid.

[1128] The exposed resist film was baked at 90° C. for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, rinsed with pure water for 30 seconds, and then spin-dried to obtain a positive pattern.

[1129] Evaluation of LWR: ArF immersion exposure and alkaline aqueous solution development

[1130] For a 45nm (1:1) line and space pattern analyzed using the optimal exposure when analyzing a line pattern with an average line width of 45nm, the line width was observed at any point when observed from the top of the pattern using a length-measuring scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), and the measurement deviation was evaluated using 3σ. The smaller the value, the better the performance. LWR (nm) is preferably less than 3.5nm, more preferably less than 2.9nm, and further preferably less than 2.5nm. The obtained LWR (nm) values ​​were classified and evaluated according to the following evaluation criteria. The results are shown in Table 8.

[1131] "A" LWR value is less than 2.5nm

[1132] "B" LWR value exceeds 2.5nm and is less than 2.9nm

[1133] "C" LWR value exceeds 2.9nm and is less than 3.2nm

[1134] "C-" LWR value exceeds 3.2nm and is less than 3.5nm

[1135] The value of “D” LWR exceeds 3.5nm

[1136] Table 8 is shown below.

[1137] In Tables 8 and 9, in the "Characteristics of Specific Compounds" column, "Type of Acid-Decomposable Group" indicates whether the acid-decomposable group in the specific compound corresponds to any of the structures of Formula (1) (ester structure) and Formula (2) (acetal structure). Furthermore, when the structure of the acid-decomposable group does not correspond to either of the structures of Formula (1) or Formula (2), "-" is indicated.

[1138] Furthermore, in the "Characteristics of Specific Compound" column, "Position of Acid-Decomposable Group" indicates at which position the acid-decomposable group is located in the anion site or the cation site, when the acid-decomposable group in the specific compound corresponds to either of the structures of Formula (1) (ester structure) and Formula (2) (acetal structure). The case where the acid-decomposable group is located in the cation site is indicated as "A," and the case where it is located in the anion site is indicated as "B." Furthermore, when the acid-decomposable group does not correspond to any of the structures of Formula (1) and Formula (2), it is indicated as "-."

[1139] Furthermore, in the column “Characteristics of a specific compound”, “Structure of a specific compound” indicates that the specific compound corresponds to the structure of either of the above-mentioned compounds (I) and (II).

[1140] Furthermore, in the column “Type and characteristic part of specific compound”, “Anion site A2 - "Type" indicates that the specific compound corresponds to the above-mentioned compound (I), and indicates the anion site A2 - Does the structure of correspond to the above formula (BB-1) to formula (BB-3)? - The case where the structure corresponds to the above formula (BB-1) to formula (BB-3) is represented as "A", and the case where it does not correspond can be represented as "B". In addition, when the structure of a specific compound does not correspond to the above compound (I), it is represented as "-".

[1141] [Table 24]

[1142]

[1143] As shown in the table, it was confirmed that the resist compositions of Examples were capable of forming patterns excellent in LWR performance even when used after long-term storage after production.

[1144] Furthermore, it was confirmed that when the specific compound contained in the resist composition of the example satisfies the following condition (A) and satisfies two or more of the following conditions (B1) to (B3) (preferably when all of the following conditions (B1) to (B3) are satisfied), the LWR performance of the pattern formed when used after long-term storage after production is further improved.

[1145] (A) The type of the acid-decomposable group of the specific compound is a structure represented by the above formula (1) (ester structure) or a structure represented by the formula (2) (acetal structure).

[1146] (B1) The type of the acid-decomposable group of the specific compound is a structure (ester structure) represented by the above formula (1).

[1147] (B2) In the specific compound, the acid-decomposable group is located at the cationic site.

[1148] The specific compound (B3) corresponds to the above-mentioned compound (I), and the structure of the anion site A2 corresponds to the above-mentioned formula (BB-1) to formula (BB-3).

[1149] The resist composition of the comparative example did not exhibit the expected effect.

[1150] <Pattern formation (4): ArF immersion exposure, organic solvent development>

[1151] An organic antireflective film-forming composition, ARC29SR (manufactured by Brewer Science), was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 98 nm thick antireflective film. The resist composition shown in Table 9 was applied thereto and baked at 100°C for 60 seconds to form a 90 nm thick resist film (actinic ray or radiation-sensitive film). For Examples 4-20 to 4-22, a topcoat film (the type of topcoat composition used is shown in Table 9) was formed on top of the resist film. The topcoat film thickness was 100 nm in each case.

[1152] The resist film was exposed using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, dipole, outer sigma 0.950, inner sigma 0.850, Y deflection) through a 6% halftone mask with a 1:1 line-to-space pattern and a line width of 45 nm. Ultrapure water was used as the immersion liquid.

[1153] The exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then rinsed with 4-methyl-2-pentanol for 30 seconds. Thereafter, the film was spin-dried to obtain a negative pattern.

[1154] Evaluation of LWR: ArF immersion exposure and organic solvent development

[1155] The LWR (nm) of the formed pattern was measured using the same method as in "LWR Evaluation: ArF Exposure, Alkaline Aqueous Solution Development." The LWR (nm) is preferably 3.5 nm or less, more preferably 2.9 nm or less, and even more preferably 2.5 nm or less. The obtained LWR (nm) values ​​were classified and evaluated according to the following evaluation criteria. The results are shown in Table 9.

[1156] "A" LWR value is less than 2.5nm

[1157] "B" LWR value exceeds 2.5nm and is less than 2.9nm

[1158] "C" LWR value exceeds 2.9nm and is less than 3.2nm

[1159] "C-" LWR value exceeds 3.2nm and is less than 3.5nm

[1160] The value of “D” LWR exceeds 3.5nm

[1161] Table 9 is shown below.

[1162] [Table 25]

[1163]

[1164] As shown in the table, it was confirmed that the resist compositions of Examples were capable of forming patterns excellent in LWR performance even when used after long-term storage after production.

[1165] Furthermore, it was confirmed that when the specific compound contained in the resist composition of the example satisfies the following condition (A) and satisfies two or more of the following conditions (B1) to (B3) (preferably when all of the following conditions (B1) to (B3) are satisfied), the LWR performance of the pattern formed when used after long-term storage after production is further improved.

[1166] (A) The type of the acid-decomposable group of the specific compound is a structure represented by the above formula (1) (ester structure) or a structure represented by the formula (2) (acetal structure).

[1167] (B1) The type of the acid-decomposable group of the specific compound is a structure (ester structure) represented by the above formula (1).

[1168] (B2) In the specific compound, the acid-decomposable group is located at the cationic site.

[1169] (B3) The specific compound corresponds to the above-mentioned compound (I), and the anion site A2 - The structure corresponds to the above formula (BB-1) to formula (BB-3).

[1170] The resist composition of the comparative example did not exhibit the expected effect.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin which decomposes and increases in polarity by the action of an acid and a compound which generates an acid by irradiation with actinic rays or radiation, The compound that generates an acid upon irradiation with actinic rays or radiation includes at least one of the following compounds (I) and (II). Compound (I): having one or more of the following structural sites X and one or more of the following structural sites Y, and an acid-decomposable group formed by protecting a polar group with a leaving group that is released by the action of an acid, and generating an acid containing the following first acidic site derived from the following structural site X and the following second acidic site derived from the following structural site Y upon irradiation with actinic rays or radiation, Structural site X: Anionic site A1 - and cationic site M1 + and the first acidic site represented by HA1 is formed by irradiation with actinic rays or radiation. Structural site Y: Anionic site A2 - and cationic site M2 + and a second acidic site represented by HA2 is formed by irradiation with actinic rays or radiation. in, Compound (I) satisfies the following conditions IA and IB, Condition IA: In the compound (I), H + Substituting the cationic site M1 in the structural site X + and the cationic site M2 in the structural site Y + The compound PI has the following acid dissociation constant: a1, which comes from the acid dissociation constant a1. + Substituting the cationic site M1 in the structural site X + and an acidic site represented by HA1; and an acid dissociation constant a2 derived from the reaction with H + Substituting the cationic site M2 in the structural site Y + and an acidic site represented by HA2, and the acid dissociation constant a2 is greater than the acid dissociation constant a1, Condition IB: The compound (I) is connected to one or more anionic sites A1 in the structural site X under the action of an acid. - With one or more anionic sites A2 in the structural site Y - The structure where the part is not cut off, Compound (II): having two or more of the structural sites X and one or more of the following structural sites Z, and an acid-decomposable group formed by protecting a polar group with a leaving group that is released by the action of an acid, and generating an acid containing two or more of the first acidic sites derived from the structural site X and the structural site Z upon irradiation with actinic rays or radiation, Structural site Z: a ​​nonionic site capable of neutralizing acid. Wherein, compound (II) satisfies the following condition IIB, Condition IIB: The compound (II) is connected to two or more anionic sites A1 in the structural site X under the action of an acid. - The structure in which the portion Z of the structural portion is not cut off, The acid-decomposable group is a group represented by the following formula (1) or (2), In formula (1), R 11 ~R 13 Each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R 11 ~R 13 Two of them are optionally bonded to each other to form a ring, represents the bonding position, In formula (2), R2 represents an alkyl group or a cycloalkyl group, and R3 represents a hydrogen atom, an alkyl group or a cycloalkyl group. In addition, R2 and R3 may be bonded to each other to form a ring. Indicates the bonding position.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein The acid-decomposable group refers to a group represented by the above formula (1).

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein In the compound (I), the cationic site M1 + and the cationic site M2 + At least one of the compounds has the acid-decomposable group, and in the compound (II), the cationic site M1 + At least one of them has the acid-decomposable group.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The anion site A2 - represents a structure represented by any of formulae (BB-1) to (BB-3), 。 5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The anion site A1 - represents a structure represented by any of formulae (AA-1) and (AA-3), 。 6 . A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 .

7. A pattern forming method comprising the following steps: A step of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5; a step of exposing the resist film to light; and A step of developing the exposed resist film using a developer.

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

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