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

Abstract

The present application provides a kind of photosensitive or radiation-sensitive resin composition, and using above-mentioned photosensitive or radiation-sensitive resin composition, resist film, pattern forming method, and the manufacturing method of electronic device capable of forming CDU excellent pattern by the manufacturing method of electronic device, the photosensitive or radiation-sensitive resin composition contains acid-decomposable resin A and acid-decomposable resin B, wherein, regarding the resin A and the resin B, the absolute value of the difference of the mole basis content of the repeating unit with acid-decomposable group is 5-20 mole %, the structure of acid-decomposable group is same, the ratio of the mass basis content is 10 / 90-90 / 10, the absolute value of the difference of weight average molecular weight is 100-5000, and the absolute value of the difference of molecular weight distribution is 0.05 or more.

Description

Technical Field

[0001] This invention relates to a photosensitive radioactive or radiosensitive linear resin composition, a resist film, a patterning method, and a method for manufacturing electronic devices. Background Technology

[0002] In the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), micro-processing is performed by using photolithography with photosensitive or linear resin compositions.

[0003] As a photolithography method, one example is a method in which a resist film is formed from a photosensitive radioactive or radiosensitive linear resin composition, the obtained resist film is exposed, and then developed to form a resist pattern.

[0004] As a photosensitive or radiosensitive linear resin composition, compositions containing a resin (acid-degradable resin) comprising repeating units having acid-degradable groups are known.

[0005] In recent years, photosensitive radioactive or radiosensitive linear resin compositions suitable for patterning using thick-film resist films have also been proposed (for example, see Patent Document 1). Patent Document 1 describes a resist composition using two resins comprising repeating units having acid-degrading groups.

[0006] Previous technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2017 / 078031 Summary of the Invention

[0009] The technical problem to be solved by the invention

[0010] Although Patent Document 1 discloses a photosensitive radioactive or radiosensitive linear resin composition capable of forming patterns with good sensitivity and excellent cross-sectional shape, it is known from the research of the inventors that there is room for further improvement in the CDU (Critical Dimension Uniformity) for displaying the uniformity of pattern size within the wafer surface.

[0011] The objective of this invention is to provide a photosensitive radioactive or radioactive linear resin composition capable of forming excellent patterns on a CDU, a resist film using the above-mentioned photosensitive radioactive or radioactive linear resin composition, a pattern forming method, and a method for manufacturing an electronic device.

[0012] means for solving technical problems

[0013] The inventors have discovered that the above-mentioned problems can be solved by the following structure.

[0014] <1>

[0015] A photosensitive or radiosensitive linear resin composition comprising resin (A) and resin (B), wherein resin (A) comprises repeating units having acid-degrading groups, and resin (B) comprises repeating units having acid-degrading groups.

[0016] The molar percentage G of the repeating units having acid-degradable groups in the above resin (A) A The molar content G of the repeating units having acid-degradable groups in the above-mentioned resin (B) B The absolute value of the difference is |G A -G B | is 5 mol% or more and 20 mol% or less

[0017] The acid-degrading groups in resin (A) have the same structure as the acid-degrading groups in resin (B).

[0018] The content S of the above resin (A) based on mass, relative to the total solids content in the above photosensitive or radiosensitive linear resin composition, is... A The content S of the above resin (B) based on its mass B The ratio of S A / S B It is 10 / 90 to 90 / 10.

[0019] The weight-average molecular weight Mw of the above resin (A) A The weight-average molecular weight Mw of the above resin (B) B The absolute value of the difference is |Mw A -Mw B | is between 100 and 5000

[0020] The above Mw A Divide by the number-average molecular weight Mn of the above resin (A) A The obtained value is the molecular weight distribution Mw of the aforementioned resin (A). A / Mn A With the above Mw B Divide by the number-average molecular weight Mn of the above resin (B) B The obtained value is the molecular weight distribution Mw of the aforementioned resin (B). B / Mn B The absolute value of the difference is |Mw A / MnA -Mw B / Mn B | is above 0.05.

[0021] <2>

[0022] according to <1> The photosensitive radioactive or radiosensitive linear resin composition, wherein,

[0023] The repeating units containing acid-degradable groups in the above-mentioned resin (A) and resin (B) are represented by the following general formula (Aa2).

[0024] [Chemical Formula 1]

[0025]

[0026] In the general formula (Aa2), R 101 R represents a hydrogen atom, fluorine atom, iodine atom, alkyl group, or aryl group. 102 This indicates a group that is released through the action of an acid.

[0027] <3>

[0028] according to <1> or <2> The photosensitive radioactive or radiosensitive linear resin composition, wherein,

[0029] The above S A / S B It ranges from 40 / 60 to 60 / 40.

[0030] <4>

[0031] according to <1> to <3> The photosensitive or radiosensitive linear resin composition described in any one of the above examples has a viscosity of 10 to 100 mPa·s at 25°C.

[0032] <5>

[0033] according to <1> to <4> The photosensitive radioactive or radiosensitive linear resin composition described in any one of the following statements, wherein,

[0034] The above | G A -G B | is 10 mol% or more and 20 mol% or less.

[0035] <6>

[0036] according to <1> to <5> The photosensitive radioactive or radiosensitive linear resin composition described in any one of the following statements, wherein,

[0037] The above G A Less than 30 mol%.

[0038] <7>

[0039] according to <1> to <6> The photosensitive radioactive or radiosensitive linear resin composition described in any one of the following statements, wherein,

[0040] The above | Mw A / Mn A -Mw B / Mn B | is above 0.10.

[0041] <8>

[0042] according to <1> to <7> The photosensitive radioactive or radiosensitive linear resin composition described in any one of the following statements, wherein,

[0043] The above | Mw A -Mw B | is between 1000 and 5000.

[0044] <9>

[0045] according to <1> to <8> The photosensitive radioactive or radiosensitive linear resin composition described in any one of the following statements, wherein,

[0046] The Z-average molecular weight Mz of the above resin (A) A The Z-average molecular weight Mz of the above resin (B) B The absolute value of the difference is |Mz A -Mz B | is above 100.

[0047] <10>

[0048] according to <9> The photosensitive radioactive or radiosensitive linear resin composition, wherein,

[0049] The above | Mz A -Mz B | is above 1000.

[0050] <11>

[0051] A resist film, which is used <1> to <10> It is formed from any one of the photosensitive radioactive or radiosensitive linear resin compositions.

[0052] <12>

[0053] A pattern forming method comprising the following steps:

[0054] use <1> to <10> The process of forming a resist film on a substrate using any one of the photosensitive or radiosensitive linear resin compositions;

[0055] The process of exposing the above-mentioned resist film to obtain an exposed resist film;

[0056] The process of developing the exposed resist film with a developer to form a pattern.

[0057] <13>

[0058] according to <12> The pattern forming method, wherein,

[0059] The light source used for the above exposure was KrF.

[0060] <14>

[0061] according to <12> or <13> The pattern forming method, wherein,

[0062] The thickness of the resist film formed on the substrate is 500 nm or more.

[0063] <15>

[0064] A method for manufacturing an electronic device, comprising: <12> to <14> The pattern forming method described in any one of the following statements.

[0065] Invention Effects

[0066] According to the present invention, a photosensitive radioactive or radioactive linear resin composition capable of forming excellent patterns of CDUs can be provided, as well as a resist film using the above-mentioned photosensitive or radioactive linear resin composition, a pattern forming method, and a method for manufacturing electronic devices. Detailed Implementation

[0067] Hereinafter, an example of a method for implementing the present invention will be described.

[0068] In this specification, the numerical range indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits.

[0069] In this specification, the designations of groups (atomic groups) that do not specify whether they are substituted or unsubstituted include both substituted and unsubstituted groups. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, "organic group" in this specification refers to a group containing at least one carbon atom.

[0070] Furthermore, in this specification, the type, position, and number of substituents when "substituents may be present" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic groups other than hydrogen atoms, and can be selected from the following substituents T.

[0071] (Substituent T)

[0072] Examples of substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxyacetyl; alkylthioalkyl groups such as methylthioalkyl and tert-butylthioalkyl; arylthioalkyl groups such as phenylthioalkyl and p-tolylthioalkyl; alkyl; cycloalkyl; aryl; heteroaryl; hydroxyl; carboxyl; formyl; sulfonyl; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonamide; silyl; amino; monoalkylamino; dialkylamino; arylamino; nitro; formyl; and combinations thereof.

[0073] Unless otherwise stated, the bonding orientation of the divalent groups marked in this specification is not limited. For example, in a compound represented by the general formula "LMN", when M is -OCO-C(CN)=CH-, if the position bonded to the L side is set as *1 and the position bonded to the N side is set as *2, M can be either *1-OCO-C(CN)=CH-*2 or *1-CH=C(CN)-COO-*2.

[0074] In this specification, "(meth)acrylic acid" is a general term encompassing acrylic acid and methacrylic acid, and specifically refers to "at least one of acrylic acid and methacrylic acid". Similarly, "(meth)acrylic acid" is a general term encompassing acrylic acid and methacrylic acid, and specifically refers to "at least one of acrylic acid and methacrylic acid".

[0075] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), Z-average molecular weight (Mz), and molecular weight distribution (also referred to as dispersion) (Mw / Mn) of the resin are defined as polystyrene equivalents determined by GPC using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 °C, flow rate: 1.0 mL / min, detector: refractive index detector).

[0076] In this manual, "photochemical rays" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet radiation represented by an excimer laser, extreme ultraviolet (EUV), X-rays, and electron beams (EB). In this manual, "light" refers to photochemical rays or radiation.

[0077] Unless otherwise stated, “exposure” in this specification includes not only exposures using bright-line spectra of mercury lamps, far-ultraviolet radiation (represented by excimer lasers), extreme ultraviolet radiation, X-rays, and EUV, but also depictions using particle beams such as electron beams and ion beams.

[0078] [Photosensitive or radiosensitive linear resin composition]

[0079] The photosensitive radioactive or radiosensitive linear resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains resin (A) and resin (B), wherein resin (A) comprises repeating units having acid-degrading groups, and resin (B) comprises repeating units having acid-degrading groups. In the photosensitive radioactive or radiosensitive linear resin composition,

[0080] The molar percentage G of repeating units having the acid-decomposing groups in the above resin (A) A The molar percentage G of the repeating units having the acid-degrading groups in the resin (B) described above. B The absolute value of the difference is |G A -G B | is 5 mol% or more and 20 mol% or less

[0081] The acid-degrading groups in resin (A) have the same structure as the acid-degrading groups in resin (B).

[0082] The content S of the above resin (A) based on mass, relative to the total solids content in the above photosensitive or radiosensitive linear resin composition, is... A The content S of the above resin (B) based on its mass B The ratio of S A / S B It is 10 / 90 to 90 / 10.

[0083] The weight-average molecular weight Mw of the above resin (A) A The weight-average molecular weight Mw of the above resin (B) B The absolute value of the difference is |Mw A -Mw B | is between 100 and 5000

[0084] The above Mw A Divide by the number-average molecular weight Mn of the above resin (A) A The obtained value is the molecular weight distribution Mw of the aforementioned resin (A). A / Mn A With the above Mw B Divide by the number-average molecular weight Mn of the above resin (B) B The obtained value is the molecular weight distribution Mw of the aforementioned resin (B). B / Mn B The absolute value of the difference is |Mw A / Mn A -Mw B / Mn B | is above 0.05.

[0085] The reason why the composition of the present invention can form excellent CDU patterns is not yet fully understood, but the inventors speculate as follows: Since the same type of acid-degradable resin tends to aggregate, regions with high and low densities of acid-degradable resin are generated within the surface of the film formed using a photosensitive radioactive or radiosensitive linear resin composition containing only one type of acid-degradable resin. Therefore, the CDU of the pattern obtained by exposing and developing the aforementioned film sometimes decreases. Furthermore, even when using two or more acid-degradable resins, if the difference in properties between the resins is too small, aggregation cannot be suppressed overall, and excellent CDU cannot be obtained. Conversely, if the difference in properties between the resins is too large, the individual resins will aggregate, and excellent CDU cannot be obtained.

[0086] Therefore, the inventors conducted in-depth research and discovered that a photosensitive or radiosensitive linear resin composition containing at least two acid-degradable resins with differences in their properties and content within a specific range can suppress the above-mentioned aggregation and form a pattern with excellent CDU.

[0087] Typically, the photosensitive radioactive or radiosensitive linear resin composition of the present invention is a photoresist composition (preferably a chemically amplified photoresist composition), which can be a positive photoresist composition or a negative photoresist composition. Furthermore, the photosensitive radioactive or radiosensitive linear resin composition of the present invention can be a photoresist composition for alkaline development or a photoresist composition for organic solvent development.

[0088] <Resin (A) containing repeating units with acid-degrading groups>

[0089] The resin (A) (also simply referred to as "resin (A)") comprising repeating units having acid-degrading groups contained in the composition of the present invention will be described.

[0090] Resin (A) contains repeating units with acid-degradable groups.

[0091] An acid-degradable group refers to a group that decomposes to produce a polar group through the action of an acid. Preferably, the acid-degradable group has a structure protected by a group (a dissociated group) in which the polar group is removed by the action of an acid. That is, resin (A) preferably contains repeating units containing groups that decompose to produce polar groups through the action of an acid. Resin (A) is preferably a resin whose polarity increases through the action of an acid, its solubility in alkaline developing solutions increases, and its solubility in organic solvents decreases.

[0092] As a polar group, an alkali-soluble group is preferred. Examples include carboxyl, phenolic hydroxyl, fluorinated alcohol, sulfonic acid, sulfonamide, sulfonylimide, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene, and acid groups such as hydroxyl groups and alcohols.

[0093] As a polar group, it is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) or a sulfonic acid group.

[0094] As a group that is released by the action of an acid (release group), for example, groups represented by formulas (Y1) to (Y4) can be cited.

[0095] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0096] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0097] Equation (Y3): -C(R) 38 (R) 37 (OR) 38 )

[0098] Equation (Y4): -C(Rn)(H)(Ar)

[0099] In formulas (Y1) and (Y2), Rx1 to Rx3 independently represent alkyl (straight-chain or branched) or cycloalkyl (monocyclic or polycyclic). Furthermore, when all of Rx1 to Rx3 are alkyl (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl.

[0100] Preferably, Rx1 to Rx3 represent straight-chain or branched alkyl groups, and more preferably, Rx1 to Rx3 represent straight-chain alkyl groups.

[0101] Two of Rx1 to Rx3 can also be bonded to form a single ring or multiple rings.

[0102] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0103] As for the cycloalkyl groups Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, as well as polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are preferred.

[0104] The cycloalkyl group formed by the bonding of two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0105] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0106] The group represented by formula (Y1) or formula (Y2) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0107] In formula (Y3), R 36 ~R 38 Each can be used independently to represent a hydrogen atom or a monovalent substituent. R 37 With R 38 They can bond with each other to form a ring. As a monovalent substituent, there are no particular limitations; examples include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R 36 Hydrogen atoms are preferred.

[0108] As formula (Y3), it is preferably a group represented by the following formula (Y3-1).

[0109] [Chemical Formula 2]

[0110]

[0111] Here, L1 and L2 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, or groups formed by combining them (e.g., groups formed by combining alkyl and aryl).

[0112] M represents a single bond or a divalent linker.

[0113] Q represents an alkyl group that may have heteroatoms, a cycloalkyl group that may have heteroatoms, an aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group that may have heteroatoms, or a group composed of combinations thereof (e.g., a group composed of alkyl and cycloalkyl groups).

[0114] In alkyl and cycloalkyl groups, for example, one of the methylene groups can be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0115] In addition, it is preferred that one of L1 and L2 is a hydrogen atom and the other is an alkyl, cycloalkyl, aryl, or a group composed of alkylene and aryl groups.

[0116] At least two of Q, M and L1 can be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0117] From the viewpoint of miniaturizing the pattern, L2 is preferably a secondary alkyl or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl, while examples of tertiary alkyl groups include tertiary butyl or adamantanecycloyl. In these cases, the increased Tg (glass transition temperature) and activation energy ensure film strength and suppress blurring.

[0118] In formula (Y4), Ar represents an aromatic cycloalgyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0119] As a repeating unit having an acid-decomposable group, it is preferred to be at least one of the repeating units represented by the following general formula (Aa1) and the repeating units represented by the following general formula (Aa2).

[0120] [Chemical Formula 3]

[0121]

[0122] In the general formula (Aa1), L1 represents a divalent linking group, R1 represents a hydrogen atom, fluorine atom, iodine atom, alkyl or aryl group, and R2 represents a group that is removed by the action of an acid.

[0123] L1 represents a divalent linking group. Examples of divalent linking groups include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups (e.g., alkylene, cycloalkylene, alkenyl, aryl, etc.) and linking groups formed by multiple of them. The aforementioned hydrocarbon groups may have substituents.

[0124] L1 is preferably -CO-, alkylene, or arylene.

[0125] As an arylene, it is preferably an arylene with 6 to 20 carbon atoms, more preferably an arylene with 6 to 10 carbon atoms, and even more preferably a phenylene.

[0126] The alkylene group can 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. The alkylene group preferably contains fluorine or iodine atoms. The total number of fluorine and iodine atoms in the alkylene group is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0127] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group, or an aryl group.

[0128] Alkyl groups can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in an alkyl group, but it is preferably 1 to 10, more preferably 1 to 3.

[0129] When the alkyl group has fluorine or iodine atoms, there is no particular limitation on the total number of fluorine and iodine atoms contained in the alkyl group, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0130] The aforementioned alkyl groups may also have heteroatoms such as oxygen atoms in addition to halogen atoms.

[0131] R2 represents a group that is released by the action of an acid (a released radical).

[0132] As a detaching radical, examples can be the groups represented by the aforementioned formulas (Y1) to (Y4), and the preferred range is the same as the aforementioned range.

[0133] [Chemical Formula 4]

[0134]

[0135] In the general formula (Aa2), R 101 R represents a hydrogen atom, fluorine atom, iodine atom, alkyl group, or aryl group. 102 This indicates a group that is released through the action of an acid.

[0136] R 101 It represents a hydrogen atom, fluorine atom, iodine atom, alkyl group, or aryl group.

[0137] Alkyl groups can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in an alkyl group, but it is preferably 1 to 10, more preferably 1 to 3.

[0138] When the alkyl group has fluorine or iodine atoms, there is no particular limitation on the total number of fluorine and iodine atoms contained in the alkyl group, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0139] The aforementioned alkyl groups may also have heteroatoms such as oxygen atoms in addition to halogen atoms.

[0140] R 102 This refers to a group that is released by the action of an acid (a free radical).

[0141] As a detaching radical, examples can be the groups represented by the aforementioned formulas (Y1) to (Y4), and the preferred range is the same as the aforementioned range.

[0142] Considering the large difference in solubility before and after deprotection, the repeating unit containing acid-degradable groups in resin (A) is preferably a repeating unit represented by the above general formula (Aa2), and more preferably a repeating unit represented by the following general formula (AI).

[0143] [Chemical Formula 5]

[0144]

[0145] In the general formula (AI),

[0146] Xa1 represents a hydrogen atom or an alkyl group.

[0147] T represents a single bond or a divalent linker.

[0148] Rx1 to Rx3 each independently represent an alkyl group (straight-chain or branched) or a cycloalkyl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups.

[0149] Two of Rx1 to Rx3 can also be bonded together to form cycloalkyl groups (monocyclic or polycyclic).

[0150] Alkyl groups represented by Xa1 can have substituents. Examples of alkyl groups represented by Xa1 include methyl groups or those with -CH2-R groups. 11 The group indicated by R. 11 The substituent represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent substituent. Examples include alkyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, acyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, and alkoxy groups with 5 or fewer carbon atoms that can be substituted by a halogen atom. Preferably, it is an alkyl group with 3 or fewer carbon atoms, and more preferably, it is a methyl group. As Xa1, it is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0151] The divalent linking group represented by T can have substituents.

[0152] Examples of divalent linking groups represented by T include alkylene groups, aromatic cycloalkanes, -COO-Rt- groups, and -O-Rt- groups. In these formulas, Rt represents an alkylene group or a cycloalkylene group.

[0153] T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0154] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0155] As for the cycloalkyl groups Rx1 to Rx3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl.

[0156] The cycloalkyl group formed by the bonding of two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. In addition, polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are also preferred. Among them, monocyclic cycloalkyl groups with 5 to 6 carbon atoms are preferred.

[0157] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0158] The repeating unit represented by the general formula (AI) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0159] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituents is preferably 8 or less.

[0160] As the repeating unit represented by the general formula (AI), the acid-degradable (meth)acrylate tertiary alkyl ester repeating unit is preferred (Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond repeating unit).

[0161] The resin (A) preferably contains at least one repeating unit selected from repeating units represented by the following general formulas (A-VIII) to (A-XII) as repeating units having acid-decomposable groups.

[0162] [Chemical Formula 6]

[0163]

[0164] In general formula (A-VIII), R5 represents tert-butyl, 1,1'-dimethylpropyl, or -CO-O-(tert-butyl) group.

[0165] In the general formula (A-IX), R6 and R7 independently represent monovalent substituents. Examples of monovalent substituents include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups.

[0166] In the general formula (AX), p represents 1 or 2.

[0167] In the general formulas (AX) to (A-XII), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R9 represents an alkyl group having 1 to 3 carbon atoms.

[0168] In general formula (A-XII), R 10 It refers to alkyl or adamantyl groups having 1 to 3 carbon atoms.

[0169] Resin (A) may have only one repeating unit with an acid-decomposable group, or it may have two or more repeating units.

[0170] The molar percentage of repeating units with acid-degradable groups in resin (A) relative to all repeating units in resin (A) (total percentage if there are two or more repeating units with acid-degradable groups) G A Preferably, it is 70 mol% or less, more preferably 50 mol% or less, further preferably 30 mol% or less, particularly preferably 10 mol% or more and 30 mol% or less, and most preferably 20 mol% or more and 30 mol% or less. G A The larger the value, the greater the dissolution contrast during development, which results in better CDU performance. However, if the value is too large... A If the size is too large, the hydrophobicity of the acid-decomposing groups can easily lead to development defects. Therefore, G... A The preferred range is the one described above.

[0171] In addition to repeating units with acid-decomposable groups, resin (A) may also have other repeating units.

[0172] When resin (A) has other repeating units besides repeating units with acid-degradable groups, the molar percentage of the other repeating units in resin (A) (total percentage when there are two or more other repeating units) is preferably 30 mol% or more and 90 mol% or less, more preferably 50 mol% or more and 90 mol% or less, and especially preferably 70 mol% or more and 80 mol% or less, relative to all repeating units in resin (A).

[0173] The following section explains other repeating units.

[0174] (Repeating units with acid groups)

[0175] Resin (A) may also contain repeating units with acid groups.

[0176] As a repeating unit having an acid group, it is preferably a repeating unit represented by the following general formula (B).

[0177] [Chemical Formula 7]

[0178]

[0179] R3 represents a hydrogen atom or a monovalent substituent. The monovalent substituent can have a fluorine atom or an iodine atom. Preferably, the monovalent substituent is -L. 40 -R8 indicates a group. L 40 Represents a single bond or ester group. R8 can be an alkyl group that can have fluorine or iodine atoms, a cycloalkyl group that can have fluorine or iodine atoms, an aryl group that can have fluorine or iodine atoms, or a combination thereof.

[0180] R4 and R5 represent hydrogen, fluorine, iodine, or alkyl groups that may have fluorine or iodine atoms, respectively.

[0181] L2 represents a single bond or an ester group.

[0182] L3 represents an aromatic hydrocarbon cyclic group with a valence of (n+m+1) or an alicyclic hydrocarbon cyclic group with a valence of (n+m+1). Examples of aromatic hydrocarbon cyclic groups include benzene and naphthyl groups. Examples of alicyclic hydrocarbon cyclic groups include monocyclic and polycyclic groups, such as cycloalkyl groups.

[0183] R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Additionally, when R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon cyclic group with a (n+m+1) valence.

[0184] R7 represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0185] m represents an integer greater than or equal to 1. m is preferably an integer from 1 to 3, and more preferably an integer from 1 to 2.

[0186] n represents an integer of 0 or 1 or higher. n is preferably an integer between 1 and 4.

[0187] In addition, (n+m+1) is preferably an integer from 1 to 5.

[0188] As a repeating unit having an acid group, it is also preferred to be a repeating unit represented by the following general formula (I).

[0189] [Chemical Formula 8]

[0190]

[0191] In general formula (I),

[0192] R 41 R 42 and R 43 Each of these groups independently represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group, or alkoxycarbonyl group. Wherein, R... 42 It can bond with Ar4 to form a ring, at which point R 42 Indicates a single bond or an alkylene group.

[0193] X4 indicates a single bond, -COO-, or -CONR. 64 -, R 64 It represents a hydrogen atom or an alkyl group.

[0194] L4 indicates a single bond or alkylene group.

[0195] Ar4 represents an aromatic ring group with an (n+1) valence, when it is combined with R 42 When bonded to form a ring, it represents an aromatic ring group with an (n+2) valence.

[0196] n represents an integer from 1 to 5.

[0197] R in general formula (I) 41 R 42 and R 43 The alkyl group is preferably an alkyl group with 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, more preferably an alkyl group with 8 or fewer carbon atoms, and even more preferably an alkyl group with 3 or fewer carbon atoms.

[0198] R in general formula (I) 41 R 42 and R 43 The cycloalkyl group can be monocyclic or polycyclic. Preferably, it is a monocyclic cycloalkyl group with 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, or cyclohexyl.

[0199] R in general formula (I) 41 R 42 and R 43 The halogen atom can be fluorine, chlorine, bromine, or iodine, with fluorine being the preferred atom.

[0200] R in general formula (I) 41 R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group is preferably a derivative of the above-mentioned R. 41 R 42 and R 43 The alkyl group in the text is the same as the alkyl group in the text.

[0201] Ar4 represents an aromatic cyclic group with an (n+1) valence. When n is 1, the divalent aromatic cyclic group can have substituents, such as arylene groups with 6 to 18 carbon atoms, such as phenylene, tolylene group, naphthylene, and anthracene, or aromatic cyclic groups containing heterocycles, such as thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring.

[0202] Specific examples of (n+1) valence aromatic cyclic groups when n is an integer greater than or equal to 2 can be exemplified by groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-described examples of divalent aromatic cyclic groups. (n+1) valence aromatic cyclic groups may also have substituents.

[0203] Substituents that can be present as the above-mentioned alkyl, cycloalkyl, alkoxycarbonyl, alkylene, and (n+1) valence aromatic cyclic groups include, for example, R in general formula (I). 41 R 42 and R 43 The examples listed include alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy alkoxy groups; aryl groups such as phenyl groups; etc.

[0204] As represented by X4 -CONR 64 -(R 64 R in (representing hydrogen atom or alkyl group) 64 Alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, are alkyl groups with 20 or fewer carbon atoms, and preferably alkyl groups with 8 or fewer carbon atoms.

[0205] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0206] The alkylene group in L4 is preferably an alkylene group with 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene.

[0207] Ar4 is preferably an aromatic cyclic group with 6 to 18 carbon atoms, and more preferably a benzene cyclic group, a naphthyl cyclic group, or a biphenylene cyclic group.

[0208] The following are specific examples of repeating units represented by general formula (I), but the present invention is not limited thereto. In the formula, a represents 1, 2, or 3.

[0209] [Chemical Formula 9]

[0210]

[0211] [Chemical Formula 10]

[0212]

[0213] (Having at least one repeating unit selected from lactone, sulcinolone, carbonate, and hydroxyadamantane structures (A-2))

[0214] The resin (A) may contain repeating units (A-2) having at least one selected from lactone, carbonate, sulcinolone and hydroxyadamantane structures.

[0215] There are no particular limitations on the lactone or sulfonolactone structure in the repeating unit having a lactone or sulfonolactone structure. Preferably, it is a 5- to 7-membered ring lactone or 5- to 7-membered ring sulfonolactone structure. More preferably, it is formed by forming a bicyclic or spirocyclic structure in the 5- to 7-membered ring lactone structure, or by forming a bicyclic or spirocyclic structure in the 5- to 7-membered ring sulfonolactone structure, to form other ring structures.

[0216] As repeating units having a lactone structure or a sulcinolone structure, examples can be found in paragraphs 0094 to 0107 of WO2016 / 136354.

[0217] Resin (A) may contain repeating units having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.

[0218] As a repeating unit having a carbonate structure, the repeating unit described in paragraphs 0106 to 0108 of WO2019 / 054311 can be cited as an example.

[0219] Resin (A) may contain repeating units having a hydroxyadamantane structure. Examples of repeating units having a hydroxyadamantane structure include repeating units represented by the following general formula (AIIa).

[0220] [Chemical Formula 11]

[0221]

[0222] In the general formula (AIIa), R1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R2c to R4c each independently represent a hydrogen atom or a hydroxyl group. At least one of R2c to R4c represents a hydroxyl group. Preferably, one or two of R2c to R4c are hydroxyl groups and the remainder are hydrogen atoms.

[0223] (Repeating units containing fluorine or iodine atoms)

[0224] Resin (A) may contain repeating units with fluorine or iodine atoms.

[0225] As a repeating unit having fluorine or iodine atoms, the repeating unit described in paragraphs 0076 to 0081 of Japanese Patent Application Publication No. 2019-045864 can be cited as an example.

[0226] (Repeating unit with photoacid-generating group)

[0227] Resin (A) may also contain repeating units having photoacid-generating groups (groups that generate acid by irradiation with photochemical rays or radiation) as repeating units other than those mentioned above.

[0228] As a repeating unit having a photoacid-generating group, the repeating unit described in paragraphs 0092 to 0096 of Japanese Patent Application Publication No. 2019-045864 can be cited as an example.

[0229] (Repeating unit with alkali-soluble group)

[0230] Resin (A) may also contain repeating units with alkali-soluble groups.

[0231] Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide 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 the resin (A), the resolution in contact hole applications is improved.

[0232] Examples of repeating units with alkali-soluble groups include repeating units formed from acrylic acid and methacrylic acid, where the alkali-soluble groups are directly bonded to the resin backbone, or repeating units where the alkali-soluble groups are bonded to the resin backbone via linking groups. Furthermore, the linking groups can have monocyclic or polycyclic cyclic hydrocarbon structures.

[0233] As a repeating unit having an alkali-soluble group, it is preferably a repeating unit formed of acrylic acid or methacrylic acid.

[0234] (None of them contain repeating units with acid-decomposing groups or polar groups)

[0235] Resin (A) may also have repeating units that do not have acid-decomposable groups or polar groups. The repeating units that do not have acid-decomposable groups or polar groups preferably have an alicyclic hydrocarbon structure.

[0236] As repeating units that do not have acid-decomposable groups or polar groups, examples include the repeating units described in paragraphs 0236-0237 of U.S. Patent Application Publication No. 2016 / 0026083 and the repeating units described in paragraph 0433 of U.S. Patent Application Publication No. 2016 / 0070167.

[0237] In addition to the repeating structural units mentioned above, resin (A) may also have various repeating structural units for the purpose of adjusting dry etching resistance, standard developer compatibility, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc.

[0238] Resin (A) can be synthesized using conventional methods (e.g., free radical polymerization).

[0239] The weight-average molecular weight (Mw) of resin (A) A The preferred value is 1,000 to 200,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 30,000. By using Mw A Within the aforementioned range, it is possible to prevent the deterioration of heat resistance and dry etching resistance, thereby preventing the deterioration of developability and the deterioration of film-forming properties due to increased viscosity. Furthermore, if Mw A If the value is 1000 or higher, the glass transition temperature of the film formed using the composition of the present invention can be increased, thus suppressing acid diffusion and improving CDU. If Mw A If the value is below 200,000, the volume of each molecule of resin (A) will not become too large, pattern wobbling will be suppressed, and CDU will be well maintained. Additionally, Mw A This is the converted value of polystyrene determined by the aforementioned GPC method.

[0240] Mw A Divide by the number-average molecular weight Mn of resin (A) A The obtained value is the molecular weight distribution (Mw) of resin (A). A / Mn A The molecular weight distribution is typically 1.00–5.00, preferably 1.00–3.00, and more preferably 1.10–2.00. A smaller molecular weight distribution results in superior resolution and resist shape, smoother sidewalls of the pattern, and better surface roughness. Furthermore, a smaller molecular weight distribution leads to more uniform polymer distribution, which in turn helps suppress pattern swaying, thus improving CDU (Chemical Deposition and Resist) performance.

[0241] Z-average molecular weight (Mz) of resin (A) A The preferred value is 1,000 to 200,000, more preferably 3,000 to 100,000, and even more preferably 5,000 to 50,000. Additionally, Mz A This is the converted value of polystyrene determined by the aforementioned GPC method. When the molecular weight at each dissolution position of the molecular weight distribution curve is set as Mi, and the number of molecules is set as Ni, the Z-average molecular weight Mz is calculated by the following formula.

[0242] Mz=∑(Ni·Mi 3 ) / ∑(Ni·Mi 2 )

[0243] The content (S) of resin (A) relative to the total solids content in the composition of the present invention, based on the mass of the resin (A). A Preferably, it is 40-90% by mass, more preferably 50-80% by mass.

[0244] Furthermore, in this specification, solid components refer to components other than solvents. Even if the aforementioned components are in a liquid state, they can still be considered solid components. Total solid components refer to the total solid components obtained by summing up all solid components.

[0245] <Resin containing repeating units with acid-degrading groups (B)>

[0246] In addition to the resin (A) described above, the composition of the present invention further contains a resin (B) comprising repeating units having acid-degrading groups (also simply referred to as "resin (B)").

[0247] Resin (A) and resin (B) satisfy all of the following conditions 1 to 5.

[0248] Condition 1: The molar percentage (G) of repeating units with acid-degradable groups in resin (A) A The molar content G of repeating units with acid-degradable groups in resin (B) B The absolute value of the difference is |G A -G B | is 5 mol% or more and 20 mol% or less.

[0249] Condition 2: The acid-decomposing groups in resin (A) have the same structure as the acid-decomposing groups in resin (B).

[0250] Condition 3: The mass basis content S of resin (A) relative to the total solids content in the photosensitive or radiosensitive linear resin composition. A Content S relative to the mass of resin (B) B The ratio of S A / S B It ranges from 10 / 90 to 90 / 10.

[0251] Condition 4: The weight-average molecular weight Mw of resin (A) A The weight-average molecular weight Mw of resin (B) B The absolute value of the difference is |Mw A -Mw B | is between 100 and 5000.

[0252] Condition 5: Mw A Divide by the number-average molecular weight Mn of resin (A) A The obtained value is the molecular weight distribution Mw of resin (A). A / Mn A With Mw B Divide by the number-average molecular weight Mn of resin (B) B The obtained value is the molecular weight distribution Mw of resin (B). B / Mn B The absolute value of the difference is |Mw A / Mn A -Mw B / Mn B | is above 0.05.

[0253] The repeating units containing acid-degradable groups in resin (B) are the same as those in resin (A). Furthermore, other repeating units that resin (B) may have are also the same as those in resin (A).

[0254] Furthermore, as described in condition 2 above, the acid-degradable groups in resin (B) are the same as those in resin (A). By satisfying condition 2, the aggregation of resin (A) and resin (B) can be suppressed, resulting in excellent CDU.

[0255] The molar percentage of repeating units with acid-degradable groups in resin (B) relative to all repeating units in resin (B) (total percentage if there are two or more repeating units with acid-degradable groups) G B Preferably, it is 70 mol% or less, more preferably 50 mol% or less, even more preferably 30 mol% or less, particularly preferably 10 mol% or more and 30 mol% or less, and most preferably 20 mol% or more and 30 mol% or less.

[0256] Among them, as described in condition 1 above, the molar content G of repeating units with acid-degradable groups in resin (A) is... A The molar content G of repeating units with acid-degradable groups in resin (B) B The absolute value of the difference is |G A -G B The concentration is 5 mol% or more and 20 mol% or less. By satisfying condition 1, the aggregation of resin (A) and resin (B) or the aggregation of resin (A) with each other and the aggregation of resin (B) with each other can be suppressed, and excellent CDU can be obtained.

[0257] |G A -G B | Preferably, it is 10 mol% or more and 20 mol% or less, more preferably 10 mol% or more and 18 mol% or less, and even more preferably 10 mol% or more and 15 mol% or less.

[0258] The weight-average molecular weight (Mw) of resin (B)B Preferably, it is 1,000 to 200,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 30,000. By using Mw B Within the aforementioned range, it is possible to prevent the deterioration of heat resistance and dry etching resistance, thereby preventing the deterioration of developability and the deterioration of film-forming properties due to increased viscosity. Furthermore, if Mw B If the value is 1000 or higher, the glass transition temperature of the film formed using the composition of the present invention can be increased, thus suppressing acid diffusion and improving CDU. If Mw B If the value is below 200,000, the volume of each molecule of resin (B) will not become too large, pattern wobbling will be suppressed, and CDU will be well maintained. Additionally, Mw B This is the converted value of polystyrene determined by the aforementioned GPC method.

[0259] Among them, as described in condition 4 above, the weight-average molecular weight Mw of resin (A) A The weight-average molecular weight Mw of resin (B) B The absolute value of the difference is |Mw A -Mw B | is 100 or higher and 5000 or lower. By satisfying condition 4, the aggregation of resin (A) and resin (B) or the aggregation of resin (A) with each other and the aggregation of resin (B) with each other can be suppressed, and excellent CDU can be obtained.

[0260] |Mw A -Mw B | Preferably, the number is 200 or more and 5000 or less, more preferably 500 or more and 5000 or less, and even more preferably 1000 or more and 5000 or less.

[0261] Mw B Divide by the number-average molecular weight Mn of resin (B) B The obtained value is the molecular weight distribution (Mw) of resin (B). B / Mn B The molecular weight distribution is typically 1.00–5.00, preferably 1.00–3.00, and more preferably 1.10–2.00. A smaller molecular weight distribution results in superior resolution and resist shape, smoother sidewalls of the pattern, and better surface roughness. Furthermore, a smaller molecular weight distribution leads to more uniform polymer distribution, which in turn helps suppress pattern swaying, thus improving CDU (Chemical Deposition and Resist) performance.

[0262] Among them, as described in condition 5 above, |Mw A / Mn A -Mw B / Mn B| is above 0.05. By satisfying condition 5, the aggregation of resin (A) and resin (B) can be suppressed, and excellent CDU can be obtained.

[0263] |Mw A / Mn A -Mw B / Mn B | Preferably 0.10 or more, more preferably 0.10 or more and 0.30 or less, even more preferably 0.10 or more and 0.20 or less, and especially preferably 0.10 or more and 0.15 or less.

[0264] Z-average molecular weight (Mz) of resin (B) B The preferred value is 1,000 to 200,000, more preferably 3,000 to 100,000, and even more preferably 5,000 to 50,000. Additionally, Mz B This is the converted value of polystyrene determined by the aforementioned GPC method.

[0265] Z-average molecular weight Mz of resin (A) A The Z-average molecular weight Mz of resin (B) B The absolute value of the difference is |Mz A -Mz B | Preferably 100 or more, more preferably 1000 or more, even more preferably 1000 or more and 10000 or less, and especially preferably 1000 or more and 5000 or less.

[0266] The content (S) of resin (B) relative to the total solids content in the composition of the present invention, based on the mass of the resin (B). B Preferably, it is 40-90% by mass, more preferably 50-80% by mass.

[0267] Wherein, as described in condition 3 above, the content S of resin (A) relative to the mass basis of the total solids content in the composition of the present invention is... A The content S of resin (B) relative to the total solids content in the composition of the present invention is based on the mass of the resin (B). B The ratio is S A / S B The ratio is 10 / 90 to 90 / 10. By satisfying condition 5, the aggregation of resin (A) and resin (B) can be suppressed, and excellent CDU can be obtained.

[0268] S A / S B Preferably, it is 40 / 60 to 60 / 40, and more preferably 45 / 55 to 55 / 45.

[0269] The compositions of the present invention contain at least two acid-degradable resins. When the compositions of the present invention contain two acid-degradable resins, one is designated as resin (A) and the other as resin (B). When the compositions of the present invention contain three or more acid-degradable resins equivalent to resin (A) or resin (B), for convenience, the resin with the highest molar content of repeating units having acid-degradable groups can be designated as resin (A), and the other resins can be designated as resin (B). The content S of resin (B) relative to the total solids content in the compositions of the present invention is then defined as follows: B The molar percentage (G) of repeating units with acid-degradable groups in resin (B). B The weight-average molecular weight Mw of resin (B) B The number-average molecular weight Mn of resin (B) B The Z-average molecular weight Mz of resin (B) B It can be determined as follows. That is, when there are n types of resin equivalent to resin (B), S B G can be obtained using the following equation (1). B Mw can be obtained using the following equation (2). B Mn can be obtained using the following equation (3). B Mz can be obtained using the following equation (4). B It can be obtained using the following formula (5). Where n represents an integer greater than 2, i represents an integer from 1 to n, and S... Bi G represents the percentage of each resin (B) relative to the total solids content in the composition of the present invention, based on a mass ratio. Bi Mw represents the molar percentage of repeating units with acid-degradable groups in each resin corresponding to resin (B). Bi Mn represents the weight-average molecular weight of each resin equivalent to resin (B). Bi Mz represents the number-average molecular weight of each resin equivalent to resin (B). Bi X represents the Z-average molecular weight of each resin equivalent to resin (B). Bi This indicates the percentage of each resin (B) relative to the total mass of resin (B).

[0270] [Formula 1]

[0271]

[0272] [Formula 2]

[0273]

[0274] [Formula 3]

[0275]

[0276] [Formula 4]

[0277]

[0278] [Formula 5]

[0279]

[0280] <Compounds that produce acid through exposure to photochemical rays or radiation (photoacid generators)>

[0281] The compositions of the present invention preferably contain compounds that produce acids upon irradiation by photochemical rays or radiation (also referred to as "photoacid generator (C)").

[0282] Photoacid generators (C) are not particularly limited to any compound that produces acid by irradiation with photochemical rays or radiation.

[0283] The photoacid generator (C) can be in the form of a low-molecular-weight compound or in the form of being embedded in a part of the polymer. Furthermore, it can be in both the form of a low-molecular-weight compound and the form of being embedded in a part of the polymer.

[0284] When the photoacid generator (C) is in the form of a low molecular weight compound, the weight-average molecular weight (Mw) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.

[0285] The photoacid generator (C) can be incorporated into a part of resin (A) or resin (B), or into a resin different from resin (A) or resin (B).

[0286] The photoacid generator (C) is preferably in the form of a low molecular weight compound.

[0287] The photoacid generator (C) is preferably an ionic compound containing both cations and anions.

[0288] The photoacid-producing agent (C) is preferably a compound that generates organic acids by irradiation with photochemical rays or radiation, and more preferably a compound that generates organic acids by irradiation with photochemical rays or radiation and has fluorine or iodine atoms in its molecule. Examples of such organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acid, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonyl sulfonyl imine acids, bis(alkyl sulfonyl) imine acids, and tri(alkyl sulfonyl) methyl acids.

[0289] Preferred agents for photoacid production (C) include, for example, compounds represented by the following general formula (ZI), compounds represented by the following general formula (ZII), and compounds represented by the following general formula (ZIII).

[0290] [Chemical Formula 12]

[0291]

[0292] In the above general formula (ZI),

[0293] R 201 R 202 and R 203 Each organic group can be represented independently.

[0294] As R 201 R 202 and R 203 The number of carbon atoms in the organic group is preferably 1 to 30, more preferably 1 to 20.

[0295] Furthermore, R 201 ~R 203 The two atoms in the ring can bond together to form a ring structure, or the ring can contain oxygen atoms, sulfur atoms, ester bonds, amide bonds, or carbonyl groups. As R... 201 ~R 203 Examples of groups formed by the bonding of two molecules include alkylene groups (e.g., butylene, pentylene, etc.) and -CH2-CH2-O-CH2-CH2-.

[0296] Z - It represents anion.

[0297] (Cations in compounds represented by the general formula (ZI))

[0298] As preferred embodiments of the cation in the general formula (ZI), examples include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3), and (ZI-4) described later.

[0299] Furthermore, the photoacid-generating agent (C) can be a compound having multiple structures represented by the general formula (ZI). For example, it can be R, which is a compound having the general formula (ZI). 201 ~R 203 At least one of them has an R with another compound represented by the general formula (ZI). 201 ~R 203 A compound having a structure in which at least one of the following is bonded by a single bond or a linking group.

[0300] (Compound (ZI-1))

[0301] First, the compound (ZI-1) will be described.

[0302] Compound (ZI-1) is R of the above general formula (ZI). 201 ~R 203 At least one of them is an arylsulfonium compound, that is, a compound with arylsulfonium as a cation.

[0303] In arylsulfonium compounds, it can be R 201 ~R 203 All are aryl, or can be R 201 ~R 203 One part of it is aryl, and the rest is alkyl or cycloalkyl.

[0304] Examples of arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0305] The aryl group in the arylsulfonium compound is preferably phenyl or naphthyl, more preferably phenyl. The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom, nitrogen atom, or sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups can be the same or different.

[0306] The alkyl or cycloalkyl group in the arylsulfonium compound is preferably a straight-chain alkyl group with 1 to 15 carbon atoms, a branched alkyl group with 3 to 15 carbon atoms, or a cycloalkyl group with 3 to 15 carbon atoms. Examples include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

[0307] R 201 ~R 203 The aryl, alkyl, and cycloalkyl groups may each independently have alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 14 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), halogen atom, hydroxyl or phenylthio group as substituents.

[0308] (Compound (ZI-2))

[0309] Next, the compound (ZI-2) will be described.

[0310] Compound (ZI-2) is represented by R in the general formula (ZI). 201 ~R 203 Each of these refers independently to a compound that does not have an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.

[0311] As R201 ~R 203 Organic groups that do not have aromatic rings typically have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0312] R 201 ~R 203 Each of the following is preferably alkyl, cycloalkyl, allyl, or vinyl, more preferably linear or branched 2-oxoalkyl, 2-oxocycloalkyl, or alkoxycarbonylmethyl, and even more preferably linear or branched 2-oxoalkyl.

[0313] As R 201 ~R 203 Alkyl and cycloalkyl groups, preferably straight-chain alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0314] R 201 ~R 203 It can be further substituted by halogen atoms, alkoxy groups (e.g., carbon atoms of 1 to 5), hydroxyl groups, cyano groups, or nitro groups.

[0315] (Compound (ZI-3))

[0316] Next, compound (ZI-3) will be described.

[0317] Compound (ZI-3) is a compound represented by the following general formula (ZI-3) and having a benzoylmethylsulfonium salt structure.

[0318] [Chemical Formula 13]

[0319]

[0320] In general formula (ZI-3),

[0321] R 1c ~R 5c Each of these can be independently represented as a hydrogen atom, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio, or arylthio.

[0322] R 6c and R 7c Each can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group, or aryl group.

[0323] R x and R y Each can be independently represented as alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl, or vinyl.

[0324] R 1c ~R 5c Any two or more of them, R 5c With R 6c R 6c With R 7c R 5c With R x and R x With R y They can be bonded separately to form ring structures, and the above ring structures can each independently contain oxygen atoms, sulfur atoms, ketone groups, ester bonds or amide bonds.

[0325] Zc - It represents anion.

[0326] R 1c ~R 5c Any two or more of them, R 5c With R 6c R 6c With R 7c R 5c With R x and R x With R y They can be bonded separately to form a ring structure, which can independently contain oxygen atoms, sulfur atoms, ketone groups, ester bonds or amide bonds.

[0327] Examples of the aforementioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of ring structures include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0328] As R 1c ~R 5c Any two or more of them, R 6c With R 7c and R x With R y Examples of groups formed by bonding include butylene and pentylene.

[0329] As R 5c With R 6c and R 5c With R x The bonded group is preferably a single bond or an alkylene group. Examples of alkylene groups include methylene and ethylene.

[0330] As R 6c and R 7cThe alkyl group is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms.

[0331] Alkyl groups can have substituents.

[0332] As R 6c and R 7c The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0333] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0334] Cycloalkyl groups can have substituents.

[0335] As R 6c and R 7c The aryl group is not particularly limited and can be monocyclic or polycyclic. It is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms.

[0336] Aryl groups can have substituents.

[0337] R 6c and R 7c Each of the components is preferably a hydrogen atom, an alkyl group, or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group.

[0338] As R X and R y The alkyl group is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms.

[0339] Alkyl groups can have substituents.

[0340] As R X and R y The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0341] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0342] Cycloalkyl groups can have substituents.

[0343] As RX and R y The 2-oxoalkyl group is not particularly limited, but is preferably a 2-oxoalkyl group with 1 to 20 carbon atoms, more preferably a 2-oxoalkyl group with 1 to 15 carbon atoms, and even more preferably a 2-oxoalkyl group with 1 to 10 carbon atoms.

[0344] 2-Oxoalkyl groups can have substituents.

[0345] As R X and R y The 2-oxocycloalkyl group is not particularly limited, but is preferably a 2-oxocycloalkyl group with 3 to 20 carbon atoms, more preferably a 2-oxocycloalkyl group with 3 to 15 carbon atoms, and even more preferably a 2-oxocycloalkyl group with 3 to 10 carbon atoms.

[0346] 2-Oxocycloalkyl groups can have substituents.

[0347] As R X and R y The alkoxycarbonyl alkyl group is not particularly limited, but is preferably an alkoxycarbonyl alkyl group with 3 to 22 carbon atoms, more preferably an alkoxycarbonyl alkyl group with 3 to 17 carbon atoms, and even more preferably an alkoxycarbonyl alkyl group with 3 to 12 carbon atoms.

[0348] Alkoxycarbonyl alkyl groups can have substituents.

[0349] R X With R y They can connect with each other to form a ring, and the ring structure can contain oxygen atoms, nitrogen atoms, sulfur atoms, ketone groups, ether bonds, ester bonds, and amide bonds.

[0350] The above-mentioned ring structure preferably contains oxygen atoms.

[0351] Examples of the aforementioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of ring structures include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0352] (Compound (ZI-4))

[0353] Next, compound (ZI-4) will be described.

[0354] The compound (ZI-4) is represented by the following general formula (ZI-4).

[0355] [Chemical Formula 14]

[0356]

[0357] In general formula (ZI-4),

[0358] l represents an integer from 0 to 2.

[0359] r represents an integer from 0 to 8.

[0360] R 13 It represents a hydrogen atom, fluorine atom, hydroxyl group, alkyl group, cycloalkyl group, alkoxy group, or alkoxycarbonyl group.

[0361] R 14 This indicates hydroxyl, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, or cycloalkylsulfonyl. R 14 When multiple instances exist, they can be the same or different.

[0362] R 15 Each can be independently represented by an alkyl, cycloalkyl, or naphthyl group. Two Rs 15 They can bond together to form a ring. When two Rs 15 When they bond together to form a ring, they can contain heteroatoms such as oxygen or nitrogen atoms within the ring framework.

[0363] Z - It represents anion.

[0364] In the general formula (ZI-4), R 13 R 14 and R 15 The alkyl group is straight-chain or branched, preferably an alkyl group with 1 to 10 carbon atoms, and more preferably methyl, ethyl, n-butyl or tert-butyl, etc.

[0365] As R 13 The alkyl group is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms. Specifically, it is preferably methyl, ethyl, n-butyl or tert-butyl.

[0366] Alkyl groups can have substituents.

[0367] As R 13 The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0368] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0369] Cycloalkyl groups can have substituents.

[0370] As R 13The alkoxy group is not particularly limited, but is preferably an alkoxy group with 1 to 20 carbon atoms, more preferably an alkoxy group with 1 to 15 carbon atoms, and even more preferably an alkoxy group with 1 to 10 carbon atoms.

[0371] Alkoxy groups can have substituents.

[0372] As R 13 The alkoxycarbonyl group is not particularly limited, but is preferably an alkoxycarbonyl group with 2 to 21 carbon atoms, more preferably an alkoxycarbonyl group with 2 to 16 carbon atoms, and even more preferably an alkoxycarbonyl group with 2 to 11 carbon atoms.

[0373] Alkoxycarbonyl groups can have substituents.

[0374] As R 14 The alkyl group is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms. Specifically, it is preferably methyl, ethyl, n-butyl or tert-butyl.

[0375] Alkyl groups can have substituents.

[0376] As R 14 The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0377] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0378] Cycloalkyl groups can have substituents.

[0379] As R 14 The alkoxy group is not particularly limited, but is preferably an alkoxy group with 1 to 20 carbon atoms, more preferably an alkoxy group with 1 to 15 carbon atoms, and even more preferably an alkoxy group with 1 to 10 carbon atoms.

[0380] Alkoxy groups can have substituents.

[0381] As R 14 The alkoxycarbonyl group is not particularly limited, but is preferably an alkoxycarbonyl group with 2 to 21 carbon atoms, more preferably an alkoxycarbonyl group with 2 to 16 carbon atoms, and even more preferably an alkoxycarbonyl group with 2 to 11 carbon atoms.

[0382] Alkoxycarbonyl groups can have substituents.

[0383] As R 14The alkyl carbonyl group is not particularly limited, but is preferably an alkyl carbonyl group with 2 to 21 carbon atoms, more preferably an alkyl carbonyl group with 2 to 16 carbon atoms, and even more preferably an alkyl carbonyl group with 2 to 11 carbon atoms.

[0384] Alkyl carbonyl groups can have substituents.

[0385] As R 14 The alkyl sulfonyl group is not particularly limited, but is preferably an alkyl sulfonyl group with 1 to 20 carbon atoms, more preferably an alkyl sulfonyl group with 1 to 15 carbon atoms, and even more preferably an alkyl sulfonyl group with 1 to 10 carbon atoms.

[0386] Alkyl sulfonyl groups can have substituents.

[0387] As R 14 The cycloalkylsulfonyl group is not particularly limited, but is preferably a cycloalkylsulfonyl group with 3 to 20 carbon atoms, more preferably a cycloalkylsulfonyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkylsulfonyl group with 3 to 10 carbon atoms.

[0388] Cycloalkylsulfonyl groups can have substituents.

[0389] When there are multiple R 14 At that time, multiple R 14 They can be the same as or different from each other.

[0390] As R 15 The alkyl group is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms. Specifically, it is preferably methyl, ethyl, n-butyl or tert-butyl.

[0391] Alkyl groups can have substituents.

[0392] As R 15 The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0393] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0394] Cycloalkyl groups can have substituents.

[0395] As R 15 The naphthyl group can have substituents.

[0396] 2 Rs 15 They can bond together to form a ring. When two Rs 15When they bond together to form a ring, the ring structure can contain oxygen atoms, nitrogen atoms, sulfur atoms, ketone groups, ether bonds, ester bonds, and amide bonds.

[0397] The above-mentioned ring structure preferably contains oxygen atoms.

[0398] Examples of the aforementioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of ring structures include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0399] In one preferred embodiment, two Rs are preferred. 15 They are alkyl groups and bonded together to form a ring structure.

[0400] (Cations in compounds represented by general formula (ZII) or general formula Z(III))

[0401] Next, general formulas (ZII) and (ZIII) will be explained.

[0402] In general formulas (ZII) and (ZIII), R 204 ~R 207 Each can be represented independently as aryl, alkyl, or cycloalkyl.

[0403] As R 204 ~R 207 The aryl group is preferably phenyl or naphthyl, more preferably phenyl. 204 ~R 207 The aryl group can be an aryl group containing a heterocyclic structure having oxygen, nitrogen, or sulfur atoms. Examples of aryl groups with heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0404] As R 204 ~R 207 Alkyl and cycloalkyl groups, preferably straight-chain alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0405] R 204 ~R 207 The aryl, alkyl, and cycloalkyl groups can each independently have substituents. As R 204 ~R 207The aryl, alkyl, and cycloalkyl groups may have substituents, for example, alkyl (e.g., having 1 to 15 carbon atoms), cycloalkyl (e.g., having 3 to 15 carbon atoms), aryl (e.g., having 6 to 15 carbon atoms), alkoxy (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.

[0406] Z - It represents anion.

[0407] (Anions in compounds represented by general formula (ZI), general formula (ZII), general formula (ZI-3) or general formula (ZI-4))

[0408] Z in the general formula (ZI) - Z in general formula (ZII) - Zc in general formula (ZI-3) - and Z in the general formula (ZI-4) - Preferably, the anion is represented by the following general formula (3).

[0409] [Chemical Formula 15]

[0410]

[0411] In general formula (3),

[0412] Xf represent either a fluorine atom or an alkyl group substituted with at least one fluorine atom.

[0413] R4 and R5 represent hydrogen atoms, fluorine atoms, alkyl groups, or alkyl groups substituted with at least one fluorine atom, respectively. When multiple R4 and R5 are present, they can be the same or different.

[0414] L represents a divalent linker group. When multiple L groups exist, they can be the same or different.

[0415] W represents an organic group.

[0416] o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0417] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Multiple Xf groups may be identical or different.

[0418] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is more preferably a fluorine atom or CF3. Particularly preferred is that all Xf consists of fluorine atoms.

[0419] R4 and R5 independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R4 and R5 are present, they can be the same or different.

[0420] The alkyl groups used as R4 and R5 may have substituents, and the number of carbon atoms is preferably 1 to 4. R4 and R5 are preferably hydrogen atoms.

[0421] Specific examples and preferred embodiments of alkyl groups substituted with at least one fluorine atom are the same as those of Xf in general formula (3).

[0422] L represents a divalent linker group. When multiple L groups exist, they can be the same or different.

[0423] Examples of divalent linking groups include -COO- (-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene (preferably with 1 to 6 carbon atoms), cycloalkylene (preferably with 3 to 15 carbon atoms), alkenylene (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, or -NHCO-alkylene- are preferred, and -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene-, or -OCO-alkylene- are more preferred.

[0424] W represents an organic group.

[0425] There is no particular limitation on the number of carbon atoms in the organic group, which is usually 1 to 30, and preferably 1 to 20.

[0426] There are no particular limitations on the organic group, such as representing alkyl, alkoxy, etc.

[0427] The alkyl group is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably an alkyl group with 1 to 4 carbon atoms.

[0428] Alkyl and alkoxy groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above is preferred, and a fluorine atom is preferred.

[0429] w preferably represents an organic group containing a cyclic structure. Preferably, it is a cyclic organic group.

[0430] Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups.

[0431] Alicyclic groups can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. Among these, alicyclic groups with a large volumetric structure, such as norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl, are preferred.

[0432] Aryl groups can be monocyclic or polycyclic. Examples of such aryl groups include phenyl, naphthyl, phenanthryl, and anthracene.

[0433] The heterocyclic group can be monocyclic or polycyclic. Polycyclic heterocyclic groups can better suppress acid diffusion. Furthermore, the heterocyclic group can be aromatic or non-aromatic. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocycles include tetrahydropyran rings, lactone rings, sulfonyl lactone rings, and decahydroisoquinoline rings. Examples of lactone and sulfonyl lactone rings include the lactone and sulfonyl lactone structures illustrated in the aforementioned resins. Furan rings, thiophene rings, pyridine rings, or decahydroisoquinoline rings are particularly preferred as heterocycles in the heterocyclic group.

[0434] The aforementioned cyclic organic groups may have substituents. Examples of such substituents include alkyl groups (which may be straight-chain or branched, preferably with 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably with 3 to 20 carbon atoms), aryl groups (preferably with 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, carbamate groups, urea groups, thioether groups, sulfonamide groups, and sulfonate groups. Furthermore, the carbon atoms constituting the cyclic organic groups (the carbon atoms that contribute to ring formation) may be carbonyl carbons.

[0435] Z in the general formula (ZI) - Z in general formula (ZII) - Zc in general formula (ZI-3) - and Z in the general formula (ZI-4) - It is also preferred to use anions represented by the following general formula (An-2) or (An-3).

[0436] [Chemical Formula 16]

[0437]

[0438] In general formulas (An-2) and (An-3), Rfa independently represents a monovalent organic group with a fluorine atom, and multiple Rfa can bond together to form a ring.

[0439] Rfa is preferably an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0440] Preferred examples of sulfonium cations in general formula (ZI) and sulfonium cations or iodonium cations in general formula (ZII) are shown below.

[0441] [Chemical Formula 17]

[0442]

[0443] The following shows the anion Z in general formulas (ZI) and (ZII). - Zc in general formula (ZI-3) - Z in general formula (ZI-4) - A preferred example.

[0444] [Chemical Formula 18]

[0445]

[0446] The mass percentage of the photoacid generator (C) in the composition of the present invention is preferably 0.1 to 20% by mass relative to the total solids content of the above composition, more preferably 0.5 to 15% by mass, and even more preferably 0.5 to 10% by mass.

[0447] Photoacid generator (C) can be used alone or in combination with two or more. When two or more photoacid generators (C) are used in combination, it is preferable that their total dosage is within the above-mentioned range.

[0448] <Acid Diffusion Control Agent (D)>

[0449] The compositions of the present invention preferably contain an acid diffusion control agent (also referred to as "acid diffusion control agent (D)").

[0450] The acid diffusion control agent (D) functions as a quencher, which captures the acid generated by the photoacid generator (C) and the like during exposure, and inhibits the reaction of the resin (A) and resin (B) (acid-decomposing resin) in the unexposed part caused by excess generated acid.

[0451] Examples of acid diffusion control agents (D) include basic compounds (DA), basic compounds (DB) whose basicity is reduced or eliminated by irradiation with photochemical rays or radiation, onium salts (DC) that are relatively weak acids relative to photoacid generators (C), low molecular weight compounds (DD) that have nitrogen atoms and groups that are removed by the action of acid, and onium salt compounds (DE) that have nitrogen atoms in the cation portion.

[0452] As the acid diffusion control agent (D), known acid diffusion control agents can be appropriately used. For example, compounds disclosed in paragraphs

[0627] to

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

[0095] to

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

[0403] to

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

[0259] to

[0328] of U.S. Patent Application Publication No. 2016 / 0274458 can be used as acid diffusion control agents (D).

[0453] As basic compounds (DA), examples include the compounds described in paragraphs 0188 to 0208 of Japanese Patent Application Publication No. 2019-045864.

[0454] In this invention, an onium salt (DC) that is a relatively weak acid relative to the photoacid generator (C) can also be used as an acid diffusion control agent (D).

[0455] When a photoacid generator (C) is mixed with an onium salt that produces an acid that is relatively weaker than the acid produced by the photoacid generator (C), if the acid produced by the photoacid generator through photochemical radiation or irradiation collides with the unreacted onium salt containing a weak acid anion, the weak acid is released and an onium salt containing a strong acid anion is produced through salt exchange. In this process, the strong acid is exchanged for a weaker acid with lower catalytic performance; therefore, it is believed that acid deactivation can be achieved by controlling acid diffusion.

[0456] As an onium salt that is a relatively weak acid relative to the photoacid generator (C), the onium salt described in paragraphs 0224 to 0233 of Japanese Patent Application Publication No. 2019-070676 can be cited as an example.

[0457] As a basic compound (DA), compounds having a structure represented by the following formulas (A) to (E) are preferred.

[0458] [Chemical Formula 19]

[0459]

[0460] In general formulas (A) and (E),

[0461] R 200 R 201 and R 202 These can be the same or different, and can independently represent hydrogen atoms, alkyl (preferably 1 to 20 carbon atoms), cycloalkyl (preferably 3 to 20 carbon atoms), aryl (preferably 6 to 20 carbon atoms), alkylcarbonyl (preferably 2 to 21 carbon atoms), cycloalkylcarbonyl (preferably 4 to 21 carbon atoms), arylcarbonyl (preferably 7 to 21 carbon atoms), alkylsulfonyl (preferably 1 to 20 carbon atoms), cycloalkylsulfonyl (preferably 3 to 20 carbon atoms), or arylsulfonyl (preferably 6 to 20 carbon atoms). R 200 R 201 and R 202 At least two of them can bond together to form a ring, and the ring may contain at least one of oxygen atom, sulfur atom, ester bond, amide bond, carbonyl group and sulfonyl group.

[0462] R 203 R 204 R 205 and R 206 They can be the same or different, and each can independently represent an alkyl group with 1 to 20 carbon atoms.

[0463] Regarding the aforementioned alkyl group, as an alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms are preferred.

[0464] The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

[0465] As a basic compound (DA), it is preferably a guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine or piperidine, etc., and more preferably a compound having an imidazole structure, a diazabicyclic structure, a ium hydroxide structure, a ium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or an aniline derivative having a hydroxyl group and / or an ether bond, etc.

[0466] A basic compound (DB) whose basicity is reduced or eliminated by exposure to photochemical rays or radiation (hereinafter also referred to as "compound (DB)") is a compound that has a proton acceptor functional group and decomposes upon exposure to photochemical rays or radiation, thereby reducing, eliminating, or changing from proton acceptor to acidic.

[0467] A proton acceptor functional group is a functional group that has a group or electrons capable of electrostatic interaction with a proton. For example, it represents a functional group having a macrocyclic compound structure, such as cyclic polyethers, or a functional group having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. A nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure as shown in the following formula.

[0468] [Chemical Formula 20]

[0469] Unshared electron pairs

[0470] Preferred partial structures for proton acceptor functional groups include, for example, crown ethers, azacrown ethers, primary amines, secondary amines, tertiary amines, pyridines, imidazoles, and pyrazines.

[0471] Compound (DB) can decompose upon exposure to photochemical rays or radiation, resulting in a decrease or loss of proton acceptor properties, or a change from proton acceptor properties to acidic properties. Here, the decrease or loss of proton acceptor properties, or the change from proton acceptor properties to acidic properties, is a change in proton acceptor properties caused by the addition of a proton to a proton acceptor functional group. Specifically, it means that when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in this chemical equilibrium decreases.

[0472] Proton acceptor properties can be confirmed by performing pH measurements.

[0473] The acid dissociation constant pKa of the compound produced by the decomposition of compound (DB) by irradiation with photochemical rays or radiation preferably satisfies pKa < -1, more preferably -13 < pKa < -1, and even more preferably -13 < pKa < -3.

[0474] The acid dissociation constant pKa represents the acid dissociation constant in aqueous solution, and is defined, for example, as in the Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, MARUZEN Co., Ltd.). A lower pKa value indicates a stronger acid. Specifically, the acid dissociation constant pKa in aqueous solution can be practically determined by measuring the acid dissociation constant at 25°C using an infinitely diluted aqueous solution. Alternatively, the Hammett substituent constant and values ​​based on a database of known literature values ​​can be calculated using the software package described below. All pKa values ​​described in this specification are values ​​calculated using this software package.

[0475] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0476] In the compositions of the present invention, onium salts (DCs) that are relatively weak acids relative to the acid-producing agent can be used as acid diffusion control agents.

[0477] When an acid-producing agent is used in combination with an onium salt that generates an acid relatively weaker than the acid produced by the acid-producing agent, if the acid produced from the acid-producing agent collides with the onium salt containing unreacted weak acid anions through photochemical radiation or irradiation, the weak acid is released through salt exchange, and an onium salt containing strong acid anions is generated. In this process, the strong acid is exchanged for a weaker acid with lower catalytic activity, thus superficially deactivating the acid and enabling control of acid diffusion.

[0478] As a onium salt that is a relatively weak acid relative to the acid-producing agent, it is preferred to be a compound represented by the following general formulas (d1-1) to (d1-3).

[0479] [Chemical Formula 21]

[0480]

[0481] In the formula, R 51 Z is a hydrocarbon group that can have substituents. 2c R is a hydrocarbon group with 1 to 30 carbon atoms that can have substituents (where the fluorine atom in the carbon adjacent to S is assumed to be unsubstituted). 52 Y is an organic group. 3 It is a straight-chain, branched-chain, or cyclic alkylene or arylene group, where Rf is a fluorine-containing hydrocarbon group, and M... + They are independently ammonium cations, sulfonium cations, or iodonium cations.

[0482] As with M + Preferred examples of sulfonium cations or iodonium cations can be exemplified by sulfonium cations represented by general formula (ZI) and iodonium cations represented by general formula (ZII).

[0483] Onium salts (DCs) that are relatively weak acids relative to acid-producing agents can be compounds that have both cation and anion sites within the same molecule and are connected by covalent bonds (hereinafter also referred to as "compounds (DCA)").

[0484] The preferred compound (DCA) is one represented by any one of the following general formulas (C-1) to (C-3).

[0485] [Chemical Formula 22]

[0486]

[0487] In general formulas (C-1) to (C-3),

[0488] R1, R2, and R3 each independently represent a substituent with one or more carbon atoms.

[0489] L1 represents a divalent linker or single bond connecting the cation and anion sites.

[0490] -X - Indicates selection from -COO - -SO3 - -SO2 - and -N - -R4 represents the anionic site. R4 indicates a monovalent substituent having at least one of the following groups at the junction with the adjacent N atom: carbonyl (-C(=O)-), sulfonyl (-S(=O)2-), and thionyl (-S(=O)-).

[0491] R1, R2, R3, R4, and L1 can bond with each other to form a ring structure. Furthermore, in the general formula (C-3), two of R1 to R3 together represent a divalent substituent, which can bond with the N atom through a double bond.

[0492] Examples of substituents that are 1 or more carbon atoms in R1 to R3 include alkyl, cycloalkyl, aryl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, and arylaminocarbonyl. Alkyl, cycloalkyl, or aryl are preferred.

[0493] Examples of L1 as a divalent linking group include straight-chain or branched alkylene groups, cycloalkylene groups, aryl groups, carbonyl groups, ether bonds, ester bonds, amide bonds, carbamate bonds, urea bonds, and groups formed by combining two or more of these. L1 is preferably an alkylene group, aryl group, ether bond, ester bond, or a group formed by combining two or more of these.

[0494] A low molecular weight compound (DD) having a nitrogen atom and a group that can be removed by the action of an acid (hereinafter also referred to as "compound (DD)") is preferably an amine derivative having a group that can be removed by the action of an acid on the nitrogen atom.

[0495] The group that is removed by the action of acid is preferably an acetal group, carbonate group, carbamate group, tertiary ester group, tertiary hydroxyl group or hemiacetal ether group, more preferably a carbamate group or hemiacetal ether group.

[0496] The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.

[0497] Compound (DD) may also have a urethane group with a protecting group on the nitrogen atom. The protecting group constituting the urethane group can be represented by the following general formula (d-1).

[0498] [Chemical Formula 23]

[0499]

[0500] In general formula (d-1),

[0501] Rb can independently represent a hydrogen atom, an alkyl group (preferably with 1 to 10 carbon atoms), a cycloalkyl group (preferably with 3 to 30 carbon atoms), an aryl group (preferably with 3 to 30 carbon atoms), an aralkyl group (preferably with 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably with 1 to 10 carbon atoms). Rb can be linked together to form a ring.

[0502] The alkyl, cycloalkyl, aryl, and aralkyl groups represented by Rb can be independently substituted by functional groups such as hydroxyl, cyano, amino, pyrrolidyl, piperidinyl, morpholino, oxo, alkoxy, or halogen atoms. The same applies to alkoxyalkyl groups represented by Rb.

[0503] As Rb, it is preferably a straight-chain or branched alkyl, cycloalkyl, or aryl group, more preferably a straight-chain or branched alkyl or cycloalkyl group.

[0504] Examples of rings formed by two interconnected Rb groups include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and their derivatives.

[0505] As a specific structure of a group represented by the general formula (d-1), examples can be found in paragraph

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

[0506] The compound (DD) is preferably a compound having a structure represented by the following general formula (6).

[0507] [Chemical Formula 24]

[0508]

[0509] In general formula (6),

[0510] l represents an integer from 0 to 2, m represents an integer from 1 to 3, and l + m = 3.

[0511] Ra represents a hydrogen atom, alkyl, cycloalkyl, aryl, or aralkyl group. When l is 2, the two Ra atoms can be the same or different, and the two Ra atoms can also be connected to each other to form a heterocycle together with the nitrogen atom in the formula. The heterocycle may also contain heteroatoms other than the nitrogen atom in the formula.

[0512] The meaning of Rb is the same as that of Rb in the above general formula (d-1), and the preferred examples are also the same.

[0513] In general formula (6), the alkyl, cycloalkyl, aryl and aralkyl groups that are Ra can be substituted by the same groups that are alkyl, cycloalkyl, aryl and aralkyl groups that are Rb that can be substituted.

[0514] As specific examples of the alkyl, cycloalkyl, aryl, and aralkyl groups of Ra (these groups can be substituted by the above groups), the same groups as those in the specific examples for Rb can be cited.

[0515] As a particularly preferred compound (DD) in this invention, examples of compounds disclosed in paragraph

[0475] of U.S. Patent Application Publication No. 2012 / 0135348A1 can be cited, but are not limited thereto.

[0516] Onium salt compounds (DE) having a nitrogen atom in the cation portion (hereinafter also referred to as "compound (DE)") are preferably compounds having a basic site containing a nitrogen atom in the cation portion. The basic site is preferably an amino group, more preferably an aliphatic amino group. It is further preferred that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferable that electron-withdrawing functional groups (carbonyl groups, sulfonyl groups, cyano groups, and halogen atoms, etc.) are not directly connected to the nitrogen atom.

[0517] As a preferred specific structure of compound (DE), examples can be found in the compound disclosed in paragraph

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

[0518] The content of acid diffusion control agent (D) in the composition of the present invention (total of the contents where multiple agents are present) is preferably 0.01 to 10.0% by mass relative to the total solid content of the composition of the present invention, more preferably 0.01 to 5.0% by mass.

[0519] In this invention, the acid diffusion control agent (D) can be used alone or in combination with two or more.

[0520] Solvent

[0521] The compositions of the present invention preferably contain a solvent (also referred to as "solvent (S)").

[0522] The solvent (S) preferably contains at least one of (M1) propylene glycol monoalkyl ether carboxylic acid ester and (M2), wherein (M2) is selected from at least one of propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone and alkylene carbonate. The solvent may also contain components other than (M1) and (M2).

[0523] If a solvent containing component (M1) or (M2) is used in combination with the aforementioned resin (A) and resin (B), the coatability of the photosensitive or radiosensitive linear resin composition is improved, and a pattern with fewer development defects can be formed, which is therefore preferred.

[0524] Furthermore, examples of organic solvents (S) include alkylene glycol monoalkyl ether carboxylic esters, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionate esters, cyclic lactones (preferably with 4 to 10 carbon atoms), monoketone compounds that may contain rings (preferably with 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetic acid esters, and alkyl pyruvate esters.

[0525] The solvent (S) content in the composition of the present invention is preferably adjusted to a solid component concentration of 0.5 to 40% by mass, more preferably to a solid component concentration of 3 to 30% by mass. In particular, from the viewpoint of superior effect of the present invention, the solid component concentration of the composition of the present invention is preferably 10% by mass or more, and particularly preferably 10 to 30% by mass. In addition, the solid component concentration refers to the mass percentage of the mass of other components (components that may constitute a photosensitive or radiosensitive linear resin composition) other than the solvent relative to the total mass of the photosensitive or radiosensitive linear resin composition.

[0526] <surfactants>

[0527] The compositions of the present invention can contain surfactants (also referred to as "surfactant (E)"). By containing surfactants, the compositions of the present invention can form patterns with better adhesion and fewer development defects.

[0528] The surfactant (E) is preferably a fluorinated and / or silicone surfactant.

[0529] As fluorinated and / or silicone surfactants, examples include those described in paragraph 0276 of U.S. Patent Application Publication No. 2008 / 0248425. Furthermore, Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431, or 4430 (manufactured by Sumitomo 3M Limited); Megaface F171, F173, F176, F189, F113, F110, F177, F120, or R08 (manufactured by DIC CORPORATION); Surflon S-382, SC101, 102, 103, 104, 105, or 106 (manufactured by ASAHI GLASS CO.,LTD.); TroySol S-366 (manufactured by Troy Chemical Industries Inc.); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.); and Surflon S-393 (manufactured by SEIMI CHEMICAL) can be used. (manufactured by Gemco Co., Ltd.); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions Inc.); KH-20 (manufactured by Asahi Kasei Corporation); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Corporation). Additionally, as a silicone surfactant, the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used.

[0530] Furthermore, in addition to the known surfactants described above, the surfactant (E) can also be synthesized using fluorinated aliphatic compounds manufactured by telomerization (also known as telomerization) or oligomerization (also known as oligomerization). Specifically, a polymer having fluorinated aliphatic groups derived from the fluorinated aliphatic compound can be used as the surfactant. This fluorinated aliphatic compound can be synthesized by, for example, the method described in Japanese Patent Application Publication No. 2002-90991.

[0531] As a polymer having fluorinated aliphatic groups, copolymers of monomers having fluorinated aliphatic groups with (poly(oxyalkylene)) acrylates and / or (poly(oxyalkylene)) methacrylates are preferred. These copolymers can be irregularly distributed or block copolymers. Furthermore, examples of poly(oxyalkylene) groups include poly(oxyethylene) groups, poly(oxypropylene) groups, and poly(oxybutene) groups. They can also be alkylene units with different chain lengths within the same chain length, such as poly(oxyethylene, oxypropylene, and oxyethylene block copolymers) or poly(oxyethylene and oxypropylene block copolymers). In addition, copolymers of monomers having fluorinated aliphatic groups with (poly(oxyalkylene)) acrylates (or methacrylates) are not only binary copolymers but can also be ternary or higher copolymers formed by simultaneously copolymerizing monomers having two or more different fluorinated aliphatic groups with two or more different (poly(oxyalkylene)) acrylates (or methacrylates).

[0532] For example, commercially available surfactants include Megaface F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC CORPORATION), which contain C6F. 13 A copolymer of acrylate (or methacrylate) with (poly(oxyethylene)) acrylate (or methacrylate), acrylate (or methacrylate) having C3F7 group, and a copolymer of (poly(oxyethylene)) acrylate (or methacrylate) with (poly(oxypropylene)) acrylate (or methacrylate).

[0533] Furthermore, surfactants other than those of fluorine and / or silicon as described in paragraph

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

[0534] Surfactant (E) can be used alone or in combination of two or more.

[0535] The compositions of the present invention may or may not contain a surfactant (E). When the compositions of the present invention contain a surfactant (E), the content of surfactant (E) relative to the total solid content of the compositions of the present invention is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass.

[0536] <Hydrophobic resin>

[0537] The compositions of the present invention can contain a hydrophobic resin (also referred to as "hydrophobic resin (F)").

[0538] The hydrophobic resin (F) is a different hydrophobic resin from the aforementioned resins (A) and (B).

[0539] Hydrophobic resins (F) are preferably designed to be biased toward the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups in the molecule, and may not contribute to the uniform mixing of polar and nonpolar substances.

[0540] As an example of the effects of adding hydrophobic resin (F), the control of the static and dynamic contact angle of the resist film surface with respect to water and the suppression of outgassing can be cited.

[0541] From the viewpoint of favoring the surface layer of the membrane, the hydrophobic resin (F) preferably has one or more of the following: "fluorine atom", "silicon atom", and "CH3 moiety contained in the side chain portion of the resin", more preferably two or more. Furthermore, the hydrophobic resin (F) preferably has a hydrocarbon group with 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted by the side chain.

[0542] When the hydrophobic resin (F) contains fluorine atoms and / or silicon atoms, the aforementioned fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chain.

[0543] When the hydrophobic resin (F) has fluorine atoms, the preferred partial structure having fluorine atoms is an alkyl group having fluorine atoms, a cycloalkyl group having fluorine atoms, or an aryl group having fluorine atoms.

[0544] The alkyl group having fluorine atoms (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a straight-chain or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and may also have substituents other than fluorine atoms.

[0545] A cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and may also have substituents other than a fluorine atom.

[0546] As an aryl group having a fluorine atom, examples include aryl groups such as phenyl and naphthyl in which at least one hydrogen atom is replaced by a fluorine atom, and it can also have substituents other than a fluorine atom.

[0547] As an example of a repeating unit having fluorine or silicon atoms, the repeating unit illustrated in paragraph 0519 of US2012 / 0251948 can be cited.

[0548] Furthermore, as described above, the hydrophobic resin (F) preferably has a CH3 moiety in the side chain portion.

[0549] Here, the CH3 moiety structure of the side chain portion in the hydrophobic resin includes CH3 moiety structures containing ethyl and propyl groups, etc.

[0550] On the other hand, the methyl groups (e.g., α-methyl groups having repeating units of methacrylic acid structure) directly bonded to the main chain of the hydrophobic resin (F) contribute little to the surface bias of the hydrophobic resin (F) due to the influence of the main chain, and are therefore not included in the CH3 part structure in this invention.

[0551] Regarding hydrophobic resin (F), please refer to paragraphs 0348 to 0415 of Japanese Patent Application Publication No. 2014-010245, which are incorporated into this specification.

[0552] In addition, the resins described in Japanese Patent Application Publication No. 2011-248019, Japanese Patent Application Publication No. 2010-175859 and Japanese Patent Application Publication No. 2012-032544 may preferably be used as the hydrophobic resin (F).

[0553] The compositions of the present invention may contain or not contain hydrophobic resin (F). When the compositions of the present invention contain hydrophobic resin (F), the content of hydrophobic resin (F) relative to the total solid content of the compositions of the present invention is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass.

[0554] <Other Ingredients>

[0555] The compositions of the present invention may contain other components besides those described above. Examples of other components include crosslinking agents, alkali-soluble resins, dissolution-inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in the developer.

[0556] Viscosity

[0557] The viscosity of the composition of the present invention is not particularly limited, but is preferably 10 to 100 mPa·s at 25°C, more preferably 15 to 90 mPa·s, and even more preferably 30 to 70 mPa·s. The viscosity of the photosensitive or radiosensitive linear resin composition is determined using an E-type viscometer (RE-85L type, manufactured by Toki Sangyo Co., Ltd.) at 25°C.

[0558] <Preparation Method>

[0559] The composition of the present invention can be prepared by dissolving the aforementioned resin (A) and resin (B), and as needed, each of the aforementioned components in a solvent (preferably the aforementioned solvent), and filtering the solvent through a filter.

[0560] The pore size of the filter used for filtration is not particularly limited, but is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. Furthermore, depending on the circumstances, it is also preferable to set the pore size of the filter to 0.1 μm or less, preferably 0.05 μm or less, and preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, as disclosed in, for example, Japanese Patent Application Publication No. 2002-62667, circulating filtration can be performed, and multiple filters can be connected in series or parallel for filtration. Furthermore, the composition can be filtered multiple times. In addition, the composition can be degassed before and after filtration.

[0561] <Application>

[0562] The compositions of the present invention undergo a change in properties upon irradiation with photochemical rays or radiation. The compositions of the present invention can be used in semiconductor manufacturing processes such as ICs (Integrated Circuits), in the manufacture of circuit boards such as liquid crystal displays or thermal sensors, in the fabrication of die-casting structures, in other photosensitive etching processes, or in the manufacture of lithographic printing plates or acid-curing compositions. Patterns using the compositions of the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring processes, and MEMS (Micro Electromechanical Systems).

[0563] [Pattern formation method, resist film]

[0564] The pattern forming method of the present invention includes:

[0565] The process of forming a resist film on a substrate using the aforementioned photosensitive radioactive or radiosensitive linear resin composition of the present invention;

[0566] The process of exposing the above-mentioned resist film to obtain an exposed resist film;

[0567] The process of developing the exposed resist film with a developer to form a pattern.

[0568] The following is a detailed description of each process.

[0569] (Process a: Resist film formation process)

[0570] Step a is the process of forming a resist film on a substrate using the composition of the present invention.

[0571] As a method for forming a resist film on a substrate using the composition of the present invention, one example is a method of coating the composition of the present invention onto a substrate.

[0572] The compositions of the present invention can be applied to substrates (e.g., silicon, silicon dioxide coatings) used in the manufacture of integrated circuit components by suitable coating methods such as spin coaters or coating machines. As a coating method, spin coating with a spin coater is preferred.

[0573] After coating the composition of the present invention, the substrate can be dried to form a resist film. In addition, various substrate films (inorganic films, organic films, or anti-reflective films) can be formed under the resist film as needed.

[0574] As a drying method, heating methods (pre-baking: PB) can be cited. Heating can be performed using devices available in general exposure machines and / or developing machines, or by using hot plates or the like.

[0575] The heating temperature is preferably 80-150℃, more preferably 80-140℃.

[0576] The heating time is preferably 30 to 1000 seconds, more preferably 40 to 800 seconds.

[0577] There are no particular limitations on the thickness of the resist film.

[0578] When the resist film is a KrF exposure resist film, the film thickness is preferably 500 nm or more, more preferably 800 nm or more and 12 μm or less, and even more preferably 1 μm or more and 6 μm or less.

[0579] When the resist film is an ArF exposure resist film or an EUV exposure resist film, the film thickness is preferably 10 to 700 nm, more preferably 20 to 400 nm.

[0580] The present invention also relates to a resist film formed using the composition of the present invention. When the thickness of the resist film is 500 nm or more, the effects of the present invention, which enables the formation of excellent CDU patterns, can be significantly achieved.

[0581] A topcoat composition can be used to form a topcoat layer on top of the resist film.

[0582] The topcoat composition is preferably not mixed with the resist film so that it can be further and uniformly coated on the top layer of the resist film.

[0583] The thickness of the top coating is preferably 10–200 nm, more preferably 20–100 nm.

[0584] There are no particular limitations on the top coating. A conventionally known top coating can be formed by conventionally known methods. For example, the top coating can be formed based on the content described in paragraphs 0072 to 0082 of Japanese Patent Application Publication No. 2014-059543.

[0585] (Process b: Exposure process)

[0586] Step b is a process of exposing the resist film to obtain an exposed resist film.

[0587] As an example of exposure methods, one can exemplify methods such as placing a mask between the light source and the resist film, or directly irradiating photochemical rays or radiation without placing a mask.

[0588] Examples of photochemical rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams (EB), with preferred types being KrF excimer lasers (248nm), ArF excimer lasers (193nm), F2 excimer lasers (157nm), EUV (13nm), X-rays, and EB.

[0589] The light source for exposure in step b is preferably KrF.

[0590] It is preferable to bake after exposure and before development (post-exposure baking: PEB).

[0591] The heating temperature is preferably 80-150℃, more preferably 80-140℃.

[0592] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds.

[0593] Heating can be achieved using devices found in general exposure machines and / or developing machines, or by using hot plates or the like.

[0594] This process is also described as baking after exposure.

[0595] (Process c: Development process)

[0596] Step c is the process of developing the exposed resist film with a developer to form a pattern.

[0597] Examples of development methods include: immersing the substrate in a tank filled with developer for a certain time (dip method); using surface tension to accumulate developer on the substrate surface and allowing it to stand for a certain time for development (puddle method); spraying developer onto the substrate surface (spray method); and continuously spraying developer onto a substrate rotating at a constant speed while scanning the developer nozzle at a constant speed (dynamic dispense method).

[0598] Furthermore, after the developing process, a process can be implemented where the developing process is stopped while replacing the solvent with another solvent.

[0599] There are no particular limitations as long as the development time is the time it takes for the resin in the unexposed area to fully dissolve; preferably, it is 10 to 300 seconds, and more preferably 20 to 120 seconds.

[0600] The temperature of the developer is preferably 0–50°C, and more preferably 15–35°C.

[0601] Examples of developing solutions include alkaline developing solutions and organic solvent developing solutions.

[0602] As an alkaline developer, an aqueous alkaline solution containing alkali is preferred. The alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is typically 0.1–20% by mass. Furthermore, the pH of the alkaline developer is typically 10.0–15.0.

[0603] Organic solvent developer refers to a developer that contains organic solvents.

[0604] Organic solvents used in organic solvent developers include well-known organic solvents, such as ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0605] (Other processes)

[0606] The pattern forming method of the present invention can include a step of cleaning with a rinsing solution after the above-described step c.

[0607] As a rinsing solution used in the rinsing process after the development process using an alkaline developer, pure water can be cited as an example. Alternatively, an appropriate amount of surfactant can be added to the rinsing solution.

[0608] In the rinsing process following the developing step using an organic developer, there are no particular restrictions on the rinsing solution used, as long as it does not dissolve the resist pattern; solutions containing common organic solvents can be used. Preferably, the rinsing solution contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Additionally, an appropriate amount of surfactant may be added to the rinsing solution.

[0609] Furthermore, the formed pattern can be used as a mask to perform etching on the substrate. That is, the pattern formed in step c can also be used as a mask to form a pattern on the substrate by processing the substrate (or the lower film and substrate).

[0610] There are no particular limitations on the processing method of the substrate (or the lower film and the substrate), but a preferred method is to form a pattern on the substrate by using the pattern formed in step c as a mask and performing dry etching on the substrate (or the lower film and the substrate).

[0611] Dry etching can be a single-stage etching process or an etching process consisting of multiple stages. When etching consists of multiple stages, the etching processes in each stage can be the same or different.

[0612] Etching can be performed using any known method, with various conditions appropriately determined based on the type and application of the substrate. For example, etching can be performed according to the minutes of the International Society for Optical Engineering (SPIE), Proc. 6924, 692420 (2008), and Japanese Patent Application Publication No. 2009-267112. Furthermore, the method described in Chapter 4, Etching, of the "Semiconductor Process Textbook, 4th Edition, 2007, Publisher: SEMI Japan" can also be used.

[0613] As a dry etching process, oxygen plasma etching is preferred.

[0614] The various materials used in this invention (e.g., solvents, developers, rinsing solutions, compositions for forming antireflective films, compositions for forming topcoats, etc.) are preferably free of impurities such as metals. The content of impurities in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. Examples of metallic impurities include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Mo, Zr, Pb, Ti, V, W, and Zn.

[0615] As a method for removing impurities such as metals from the various materials mentioned above, filtration using a filter can be cited as an example. The filter pore size is preferably 0.20 μm or less, more preferably 0.05 μm or less, and even more preferably 0.01 μm or less.

[0616] As the filter material, fluoropolymers such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkylene (PFA), polyolefin resins such as polypropylene and polyethylene, and polyamide resins such as nylon 6 and nylon 66 are preferred. Filters that have been pre-cleaned with an organic solvent can be used. In the filter filtration process, multiple or various filters can be connected in series or parallel. When using multiple filters, filters with different pore sizes and / or materials can be used in combination. Furthermore, various materials can be filtered multiple times, and the multiple filtration process can be a circulating filtration process. As a circulating filtration process, the method disclosed in Japanese Patent Application Publication No. 2002-62667 is preferred, for example.

[0617] As a filter, a filter that reduces the amount of dissolved substances, as disclosed in Japanese Patent Application Publication Nos. 2016-201426, is preferred.

[0618] Besides filtration, impurities can be removed by adsorption materials, and filtration and adsorption materials can be used in combination. Known adsorption materials can be used, such as inorganic adsorption materials like silica gel or zeolite, or organic adsorption materials like activated carbon. For example, the adsorption materials disclosed in Japanese Patent Application Publication No. 2016-206500 can be cited as examples of metal adsorbents.

[0619] Furthermore, as methods to reduce impurities such as metals contained in the aforementioned materials, examples include selecting raw materials with low metal content as constituent materials, filtering the constituent materials using filters, or performing distillation under conditions that minimize contamination, such as lining or coating the apparatus with fluoropolymers. The preferred conditions for filtering the constituent materials are the same as those described above.

[0620] To prevent the introduction of impurities, the aforementioned materials are preferably stored in containers described in U.S. Patent Application Publication No. 2015 / 0227049, Japanese Patent Application Publication No. 2015-123351, and Japanese Patent Application Publication No. 2017-13804.

[0621] Various materials can be used after being diluted with the solvents used in the composition.

[0622] Furthermore, the present invention relates to a method for manufacturing an electronic device including the aforementioned pattern forming method.

[0623] The electronic device of the present invention is an electronic device that is suitably mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[0624] Example

[0625] The present invention will now be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. The scope of the present invention should not be construed as limited to the embodiments shown below.

[0626] <Resin (A) and Resin (B)>

[0627] The following acid-degradable resins were used as resins (A) and (B).

[0628] The number-average molecular weight (Mn), weight-average molecular weight (Mw), Z-average molecular weight (Mz), and molecular weight distribution (Mw / Mn) of each resin were determined using the aforementioned methods. Furthermore, the composition ratio (in mol%) of repeating units in each resin was determined by... 13 It is measured using C-NMR (nuclear magnetic resonance).

[0629] [Chemical Formula 25]

[0630]

[0631] [Chemical Formula 26]

[0632]

[0633] [Chemical Formula 27]

[0634]

[0635] [Chemical Formula 28]

[0636]

[0637] [Chemical Formula 29]

[0638]

[0639] [Chemical Formula 30]

[0640]

[0641] <Photo-acid generator (C)>

[0642] The structure of the compound used as a photoacid generator is shown below.

[0643] [Chemical Formula 31]

[0644]

[0645] [Chemical Formula 32]

[0646]

[0647] <Acid Diffusion Control Agent (D)>

[0648] The structure of the compound used as an acid diffusion control agent is shown below.

[0649] [Chemical Formula 33]

[0650]

[0651] [Chemical Formula 34]

[0652]

[0653] <Surfactant (E)>

[0654] The following EX and EY were used as surfactants.

[0655] Example: Megaface (registered trademark) R-41 (manufactured by DIC Corporation)

[0656] [Chemical Formula 35]

[0657]

[0658] Solvent (S)

[0659] The solvents used are shown below.

[0660] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0661] PGME: Propylene Glycol Monomethyl Ether

[0662] CyHx: Cyclohexanone

[0663] <Preparation of Anti-corrosion Composition>

[0664] The resin (A), resin (B), photoacid generator (C), acid diffusion control agent (D), surfactant (E), and solvent (S) shown in Tables 1 and 2 below were placed into a 100 L stirred tank. The contents of the stirred tank were stirred at 23 °C and 150 rpm for 12 hours. Then, the stirred contents (solution) were passed through a polyethylene filter with a pore size of 0.10 μm to prepare a photosensitive radioactive or radiosensitive linear resin composition (resist composition).

[0665] The percentages of each component in Tables 1 and 2 are percentages relative to the total solids content of each resist composition. "%" is the mass basis (i.e., "mass %"). Solids concentration refers to the mass percentage of the components other than the solvent, relative to the total mass of each resist composition.

[0666] As solvent (S), the compounds shown in Tables 1 and 2 were used at the mass ratios shown in Tables 1 and 2, respectively.

[0667] In Example 6, two compounds were used as resin (B) at the mass ratios recorded in Table 1. In Examples 11 and 18, two compounds were used as photoacid generators (C) at the mass ratios recorded in Tables 1 and 2. In Example 17, two compounds were used as acid diffusion control agents (D) at the mass ratios recorded in Table 2.

[0668] [Table 1]

[0669]

[0670] [Table 2]

[0671]

[0672] |G related to resin (A) and resin (B) contained in each resist composition A -G B| Are the structures of acid-decomposing groups the same or different? S A / S B |Mw A -Mw B |、|Mw A / Mn A -Mw B / Mn B |and|Mz A -Mz B The results are described in Table 3 below. Furthermore, the viscosity of each resist composition is also described in Table 3 below. Viscosities were measured using an E-type viscometer (RE-85L type, manufactured by Toki Sangyo Co., Ltd.) at 25°C.

[0673] |G A -G B |The molar percentage G of repeating units with acid-degradable groups in resin (A) A The molar content G of repeating units with acid-degradable groups in resin (B) B The absolute value of the difference.

[0674] S A / S B The content S of resin (A) relative to the total solids content in the resist composition is a mass basis. A The content S of resin (B) relative to the total solids content in the resist composition is based on the mass of the resin (B). B than.

[0675] |Mw A -Mw B | represents the weight-average molecular weight Mw of resin (A). A The weight-average molecular weight Mw of resin (B) B The absolute value of the difference.

[0676] |Mw A / Mn A -Mw B / Mn B |for Mw A Divide by the number-average molecular weight Mn of resin (A) A The obtained value is the molecular weight distribution Mw of resin (A). A / Mn A With Mw B Divide by the number-average molecular weight Mn of resin (B) B The obtained value is the molecular weight distribution Mw of resin (B). B / Mn B The absolute value of the difference.

[0677] |MzA -Mz B | is the Z-average molecular weight Mz of resin (A) A and the Z-average molecular weight Mz of resin (B) B The absolute value of the difference.

[0678] [Table 3]

[0679]

[0680] <Pattern formation>

[0681] On a Si substrate (manufactured by Advanced Materials Technology) that has been treated with hexamethyldisilazane, a resist composition shown in Table 4 below was spin-coated at a rotation speed of 1500 rpm without setting an anti-reflection layer, and baked at a temperature of 120 °C for 60 seconds (PreBake; PB (pre-baking)) to form a photosensitive or radiation-sensitive film (resist film). The film thickness of the resist film was set to the thickness described in Table 4 below. For the wafers on which the resist films were formed, in Examples 1 to 18 and Comparative Examples 1 to 10, a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C, wavelength 248 nm, NA 0.50) was used, and in Example 19, an ArF excimer laser scanner (manufactured by ASML, PAS5500 / 1100, wavelength 193 nm, NA 0.50) was used to perform pattern exposure of 225 points on the wafer through an exposure mask. Then, it was baked at a temperature of 110 °C for 60 seconds (Post Exposure Bake; PEB (post-exposure baking)), and then developed with the developer shown in Table 4 below for 60 seconds, and then rinsed with the rinsing solution shown in Table 4 below for 30 seconds, and spin-dried. In this way, wafers with 225 evaluation patterns (line and space patterns with a pitch of 700 nm and a space width of 300 nm) formed in the plane were obtained.

[0682] In Table 4, "TMAHaq" is an aqueous solution of tetramethylammonium hydroxide (concentration 2.38% by mass), "nBA" is butyl acetate, and "MIBC" is methyl isobutyl carbinol (4-methyl-2-pentanol).

[0683] <Evaluation of CDU>

[0684] The dimensional deviation (CD) of the 225-point evaluation pattern (lines and spatial patterns with a spacing of 700 nm and a spatial width of 300 nm) was measured using a scanning electron microscope (SEM) (S-9380II, Hitachi, Ltd.). The standard deviation (SD) was calculated from the obtained CD values, and 3σ was used as the index of the dimensional deviation (CDU). A smaller CDU indicates a smaller deviation and a better CDU.

[0685] [Table 4]

[0686]

[0687] As shown in Table 4, the resist composition of the embodiments can form excellent CDU patterns.

[0688] Industrial availability

[0689] According to the present invention, a photosensitive radioactive or radioactive linear resin composition capable of forming excellent patterns of CDUs can be provided, as well as a resist film using the above-mentioned photosensitive or radioactive linear resin composition, a pattern forming method, and a method for manufacturing electronic devices.

[0690] The present invention has been described in detail with reference to specific embodiments, but various changes or modifications can be made without departing from the spirit and scope of the invention, which will be apparent to those skilled in the art.

[0691] This application is based on Japanese patent application filed on July 29, 2020 (Japanese Patent Application 2020-128367), the contents of which are incorporated herein by reference.

Claims

1. A photosensitive or radiosensitive linear resin composition comprising resin A and resin B, wherein resin A comprises repeating units having acid-degrading groups, and resin B comprises repeating units having acid-degrading groups. The molar percentage G of the repeating units with acid-degradable groups in resin A A The molar content G of the repeating unit with acid-degradable groups in resin B B The absolute value of the difference is |G A -G B | is 5 mol% or more and 20 mol% or less. The acid-degrading groups in resin A have the same structure as the acid-degrading groups in resin B. The content S of resin A as a mass basis relative to the total solids content in the photosensitive or radiosensitive linear resin composition. A The content S of the resin B based on its mass B The ratio of S A / S B It is 10 / 90 to 90 / 10. The weight-average molecular weight Mw of resin A A The weight-average molecular weight Mw of the resin B B The absolute value of the difference is |Mw A -Mw B | is between 700 and 5000 The Mw A Divide by the number-average molecular weight Mn of resin A A The obtained value is the molecular weight distribution Mw of resin A. A / Mn A With the Mw B Divide by the number-average molecular weight Mn of the resin B B The obtained value is the molecular weight distribution Mw of resin B. B / Mn B The absolute value of the difference is |Mw A / Mn A -Mw B / Mn B | is above 0.05, The acid-decomposable group refers to a group that decomposes to produce a polar group through the action of an acid. The acid-decomposable group has a structure in which the polar group is protected by a group that is removed by the action of an acid. The group that is removed by the action of an acid is selected from the following groups represented by formulas (Y1) to (Y4): Equation (Y1): -C(Rx1)(Rx2)(Rx3) Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3): -C(R 36 )(R 37 )(OR 38 ) Equation (Y4): -C(Rn)(H)(Ar) In formulas (Y1) and (Y2), Rx1 to Rx3 independently represent straight-chain or branched alkyl groups or monocyclic or polycyclic cycloalkyl groups, and two of Rx1 to Rx3 may optionally be bonded together to form a monocyclic or polycyclic ring. In formula (Y3), R 36 ~R 38 R represents either a hydrogen atom or a monovalent substituent independently. 37 With R 38 They can be arbitrarily bonded together to form a ring. In formula (Y4), Ar represents an aromatic cycloalgyl group, Rn represents an alkyl, cycloalkyl, or aryl group, and Rn and Ar are optionally bonded to each other to form a non-aromatic ring.

2. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1, wherein, The repeating units containing acid-degradable groups in resin A and resin B are represented by the following general formula (Aa2). In the general formula (Aa2), R 101 R represents a hydrogen atom, fluorine atom, iodine atom, alkyl group, or aryl group. 102 This indicates a group that is released through the action of an acid.

3. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The S A / S B It ranges from 40 / 60 to 60 / 40.

4. The photosensitive or radiosensitive linear resin composition according to claim 1 or 2, wherein the viscosity at 25°C is 10 mPa·s to 100 mPa·s.

5. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The |G A -G B | is between 10 mol% and 20 mol%.

6. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The G A It is less than 30 mol%.

7. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The |Mw A / Mn A -Mw B / Mn B | is above 0.

10.

8. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The |Mw A -Mw B | is between 1000 and 5000.

9. The photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The Z-average molecular weight Mz of resin A A The Z-average molecular weight Mz of the resin B B The absolute value of the difference is |Mz A -Mz B | is above 100.

10. The photosensitive radioactive or radiosensitive linear resin composition according to claim 9, wherein, The |Mz A -Mz B | is above 1000.

11. A resist film formed using the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2.

12. A method for forming a pattern, comprising the following steps: The process of forming a resist film on a substrate using the photosensitive radioactive or radiosensitive linear resin composition according to any one of claims 1 to 10; The process of exposing the resist film to obtain an exposed resist film; The process of developing the exposed resist film with a developer to form a pattern.

13. The pattern forming method according to claim 12, wherein, The light source used for the exposure is KrF.

14. The pattern forming method according to claim 12 or 13, wherein, The thickness of the resist film formed on the substrate is 500 nm or more.

15. A method for manufacturing an electronic device, comprising the pattern forming method according to any one of claims 12 to 14.

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