TW202138917A - Method for producing active light sensitive or radiation sensitive resin composition, pattern forming method, and method for producing electronic device - Google Patents

Abstract

The present invention provides a method for producing an active light sensitive or radiation sensitive resin composition that is improved in terms of agglomeration defects caused by a starting material, a pattern forming method which uses this production method, and a method for producing an electronic device by means of: a method for producing an active light sensitive or radiation sensitive resin composition, said method sequentially comprising, in the following order, a step (1) wherein a resin, a compound that generates an acid upon irradiation with active light or radiation, an acid diffusion control agent and a solvent are put into a container, and a step (2) wherein at least one of the resin, the compound that generates an acid upon irradiation with active light or radiation, the acid diffusion control agent and the solvent is additionally put into the container that contains the resin, the compound that generates an acid upon irradiation with active light or radiation, the acid diffusion control agent and the solvent; a pattern forming method which uses this production method; and a method for producing an electronic device.

Description

Method for manufacturing sensitized radiation or radiation-sensitive resin composition, method for pattern formation, and method for manufacturing electronic component

The present invention relates to a method for manufacturing a photosensitive ray-sensitive or radiation-sensitive resin composition, a method for pattern formation, and a method for manufacturing an electronic component.

In the manufacturing process of semiconductor components such as Integrated Circuit (IC) and Large Scale Integrated Circuit (LSI), the use of photolithography using photosensitive radiation or radiation-sensitive resin composition Perform micro processing. As a method of photolithography, a method of forming a resist film from a sensitizing ray-sensitive or radiation-sensitive resin composition, exposing the obtained film, and then developing it can be mentioned.

As the photosensitive ray-sensitive or radiation-sensitive resin composition, there are known compositions containing resin, a compound that generates acid by irradiation with actinic rays or radiation (photoacid generator), an acid diffusion control agent, and a solvent ( For example, refer to Patent Document 1 and Patent Document 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-65488 [Patent Document 2] Japanese Patent Laid-Open No. 2006-152255

[The problem to be solved by the invention] However, according to the research of the present inventors, it is known that a sensitizing radiation-sensitive or radiation-sensitive resin composition (typically a resist Agent composition) according to its manufacturing method produces agglomeration defects caused by raw materials. Furthermore, the so-called "agglomeration defect caused by raw materials" refers to defects caused by the agglomeration of raw materials. The pattern formed by exposure and development of a radiation film (typically a resist film) can be evaluated using a defect evaluation device.

The subject of the present invention is to provide a method for producing a photosensitive ray-sensitive or radiation-sensitive resin composition with improved aggregation defects caused by raw materials, and a method for manufacturing the photosensitive ray-sensitive or radiation-sensitive resin composition using the same Pattern forming method and manufacturing method of electronic components. [Means to solve the problem]

The inventors found that the above-mentioned problem can be solved by the following structure.

＜1＞ A method for manufacturing a photosensitive ray-sensitive or radiation-sensitive resin composition, which sequentially includes: Step (1), put a resin, a compound that generates an acid by irradiation with actinic rays or radiation, an acid diffusion control agent, and a solvent into the container; and Step (2), adding the resin, the resin, and the solvent to a container containing the resin, the compound that generates acid by irradiation with actinic rays or radiation, the acid diffusion control agent, and the solvent. At least one of a compound that generates an acid by irradiation with actinic rays or radiation, the acid diffusion control agent, and the solvent. ＜2＞ The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to <1>, wherein the step (2) is performed after 30 minutes or more have passed after the step (1) is completed. ＜3＞ The method for producing a sensitized radiation-sensitive or radiation-sensitive resin composition according to <1> or <2>, wherein the step (1-2) is included between the step (1) and the step (2) ), The step (1-2) is to mix the resin, the compound that generates acid by irradiation with actinic rays or radiation, the acid diffusion control agent, and the solvent. ＜4＞ The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to <3>, wherein the mixing time in the step (1-2) is 2 hours or more. ＜5＞ The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to <3> or <4>, wherein the mixing time in the step (1-2) is 4 hours or more. ＜6＞ The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to any one of <3> to <5>, wherein the mixing time in the step (1-2) is 8 hours or more. ＜7＞ The method for producing a photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <6>, wherein the solid content concentration of the photosensitive ray-sensitive or radiation-sensitive resin composition is 10% by mass or more. ＜8＞ The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to any one of <1> to <7>, wherein the compound that generates an acid by irradiation with actinic rays or radiation is selected At least one of the compound represented by the following general formula (ZI-3) and the compound represented by the following general formula (ZI-4).

[化1]

In the general formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, Cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. Any two or more of R _1c to R _{5c , R 5c} and R _6c , R _6c and R _7c , R _5c and R _x, and R _x and R _y may be bonded to each other to form a ring structure, and the ring structures may each be It independently contains an oxygen atom, a sulfur atom, a keto group, an ester bond or an amide bond. Z _c ^- represents an anion.

[化2]

In the general formula (ZI-4), l represents an integer of 0-2. r represents an integer of 0-8. R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group. R ₁₄ represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group or a cycloalkylsulfonyl group. When _{there are a plurality of R 14} , they may be the same or different. R ₁₅ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, heteroatoms may also be included in the ring skeleton. Z ^- represents an anion. <9> The method for producing an sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of <1> to <8>, wherein, after the step (1), the The contents are divided into two or more fractions, and at least one of the fractions is used to evaluate the physical properties. <10> The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to <9>, wherein at least one of the partial groups is used to form an organic film, and the physical properties of the organic film are evaluated Evaluation, and the step (2) is performed based on the result of the evaluation, so as to adjust the physical properties of the target film. <11> The method for producing a sensitized radiation-sensitive or radiation-sensitive resin composition according to <10>, wherein the film physical properties are a combination of sensitivity, film thickness, contact angle, complex refractive index, transmittance, and refractive index. At least one. <12> The method for producing an sensitized radiation-sensitive or radiation-sensitive resin composition according to <9>, wherein at least one of the partial groups is used to evaluate the physical properties of the solution, and the evaluation is performed based on the result of the evaluation The step (2) in order to adjust the physical properties of the target solution. <13> The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to <12>, wherein the solution physical property is at least one of a complex refractive index, a transmittance, and a refractive index. <14> A pattern forming method, comprising: forming a resist on a substrate using an actinic radiation-sensitive or radiation-sensitive resin composition manufactured according to the manufacturing method described in any one of <1> to <13> The step of filming; the step of exposing the resist film to obtain an exposed resist film; and the step of developing the exposed resist film with a developing solution to form a pattern. <15> A manufacturing method of electronic components, including the pattern forming method as described in <14>. [Effects of the invention]

According to the present invention, it is possible to provide a method for manufacturing a photosensitive ray-sensitive or radiation-sensitive resin composition with improved aggregation defects caused by raw materials, and a method for manufacturing the photosensitive ray-sensitive or radiation-sensitive resin composition. Pattern forming method and manufacturing method of electronic components.

Hereinafter, an example of a form for implementing the present invention will be described. In this specification, the numerical range indicated by "～" means a range that includes the numerical values described before and after "～" as the lower limit and the upper limit. In the expression of the group (atomic group) in this specification, the expression that does not describe substituted or unsubstituted also includes a group having no substituent and a group having a substituent. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). In addition, the "organic group" in this specification refers to a group containing at least one carbon atom.

In addition, in this specification, the type of substituent, the position of the substituent, and the number of substituents when it is mentioned that "may have a substituent" are not particularly limited. The number of substituents may be one, two, three or more, for example. Examples of the substituent include a monovalent non-metal atomic group other than a hydrogen atom. For example, it can be selected from the following substituents T.

(Substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; phenoxy and p-tolyloxy, etc. Aryloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acetyloxy groups such as acetoxy, propoxy and benzyloxy; acetoxy, benzyl Alkyl hydrogen sulfide groups such as methyl sulfanyl group and tertiary butyl sulfanyl group; phenyl group Aromatic sulfhydryl groups such as sulfhydryl and p-tolylsulfhydryl; alkyl; cycloalkyl; aryl; heteroaryl; hydroxyl; carboxy; methionyl; sulfo; cyano; alkylaminocarbonyl ; Arylaminocarbonyl; sulfonamido; silyl; amine; monoalkylamino; dialkylamino; arylamino, nitro; methanoyl; and combinations of these.

The bonding direction of the divalent group described in this specification is not limited unless otherwise specified. For example, in the case where M in the compound represented by the general formula formed by "LMN" is -OCO-C(CN)=CH-, if the position of bonding with the L side is set to *1, it will be connected to the N side The bonding position is set to *2, then M can be *1-OCO-C(CN)=CH-*2, or *1-CH=C(CN)-COO-*2.

The "(meth)acrylic group" in this specification is a general term including an acrylic group and a methacrylic group, and means "at least one of an acrylic group and a methacrylic group". Similarly, the term "(meth)acrylic acid" is a general term including acrylic acid and methacrylic acid, and means "at least one of acrylic acid and methacrylic acid".

In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion (also described as molecular weight distribution) (Mw/Mn) of the resin are defined as the use of gel permeation chromatography (Gel Permeation Chromatography, GPC ) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh) by device (HLC-8120GPC manufactured by Tosoh) , Column temperature: 40℃, flow rate: 1.0 mL/min, detector: Refractive Index Detector (Refractive Index Detector) obtained by polystyrene conversion value.

The "actinic rays" or "radiation rays" in this specification refer to, for example, the bright-ray spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams ( EB: Electron Beam) and so on. The "light" in this specification refers to actinic rays or radiation. The "exposure" in this manual, unless otherwise specified, includes not only exposure using the bright line spectrum of a mercury lamp, extreme ultraviolet, extreme ultraviolet, X-ray, and EUV light represented by excimer lasers, but also Drawing using particle beams such as electron beams and ion beams.

[Manufacturing method of sensitizing radiation-sensitive or radiation-sensitive resin composition] The manufacturing method of the sensitized radiation-sensitive or radiation-sensitive resin composition of the present invention sequentially includes: Step (1), put a resin, a compound that generates an acid by irradiation with actinic rays or radiation, an acid diffusion control agent, and a solvent into the container; and Step (2), adding the resin, the resin, and the solvent to a container containing the resin, the compound that generates acid by irradiation with actinic rays or radiation, the acid diffusion control agent, and the solvent. At least one of a compound that generates an acid by irradiation with actinic rays or radiation, the acid diffusion control agent, and the solvent.

The present inventors have discovered that by adopting the following method as a compound containing resin, which generates acid by irradiation with actinic rays or radiation (photoacid generator), acid diffusion control agent, and solvent, the sensitizing radiation or radiation-sensitive The manufacturing method of the resin composition can improve the agglomeration defects caused by the raw materials. The method is to first put the resin, the photoacid generator, the acid diffusion control agent and the solvent into the container, and then to the container containing these At least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent is added to the container. The mechanism for solving the problem of the present invention by the manufacturing method of the present invention is not clear, but the present inventors considered as follows. When the resin, photoacid generator, acid diffusion control agent, and solvent that are the raw materials of the sensitized radiation or radiation-sensitive resin composition (typically a resist composition) are mixed, the intermolecular force or Ionic interactions and the like cause aggregation of raw materials, which results in aggregation defects caused by raw materials. In contrast to this, in the present invention, after the raw materials are put into the container in step (1), at least one of the raw materials is added in step (2) to produce sensitizing radiation or radiation sensitive lines. Resin composition. According to the present invention, in step (1), a certain amount of raw materials are put into the container in advance to form agglomerates, and then in step (2), the remaining raw materials are added, so that no more than the amount of agglomerates formed in advance is formed As a result, it is believed that the agglomeration defect caused by the raw material can be improved.

Hereinafter, each step will be described in detail.

<Step (1)> Step (1) is a step of putting a resin into a container, a photoacid generator, an acid diffusion control agent, and a solvent that generate acid by irradiation with actinic rays or radiation. The container in step (1) is not particularly limited, and, for example, a known container used in the production of an sensitizing ray-sensitive or radiation-sensitive resin composition can be used. As a container, as long as it can contain the said each component, it may have a lid, and may not have a lid. The container may be a sealed container or a container that can be sealed, or a container that is not sealed or a container that cannot be sealed. The material of the container is not particularly limited. The size of the container is not limited, and it may be as large as used in a normal laboratory, or may be a size suitable for industrial production. The container may also be a container that can perform operations such as heating, pressurizing, and stirring the components put therein. For example, a reaction vessel, a kettle (for example, a reaction vessel), a tank (for example, a stirring tank), etc. may also be used as a container. The container can be equipped with a mechanism for putting each component into the container (for example, introduction pipes, etc.), a mechanism for discharging from the container (for example, discharge pipes, etc.), and a mechanism for reintroducing those discharged from the container into the container. (Circulation mechanism) and so on. The manufacturing method of the present invention can be carried out using an apparatus for manufacturing a photosensitive ray-sensitive or radiation-sensitive resin composition. As the container of step (1), it is preferable to use a photosensitive ray-sensitive or radiation-sensitive resin composition. The stirring tank in the device. The manufacturing apparatus which can be used in this invention is not specifically limited, A well-known manufacturing apparatus can be used.

FIG. 1 shows a schematic diagram of an example of a manufacturing apparatus that can be used in the method of manufacturing the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention. In Figure 1, the manufacturing device 100 includes: a stirring tank 10; a stirring shaft 12 rotatably installed in the stirring tank 10; a stirring blade 14 mounted on the stirring shaft 12; a circulation pipe 16, one end connected to the bottom of the stirring tank 10 , The other end is connected to the upper part of the stirring tank 10; the filter 18 is arranged in the middle of the circulation pipe 16; the discharge pipe 20 is connected to the circulation pipe 16; and the discharge nozzle 22 is arranged at the end of the discharge pipe 20. The liquid contact part (the part in contact with the liquid) in the device is preferably lined or coated with a fluororesin or the like.

The stirring tank 10 is not particularly limited as long as it is a stirring tank capable of containing resin and generating acid by irradiation with actinic rays or radiation, a photoacid generator, an acid diffusion control agent, a solvent, etc., and known ones can be mentioned. Stirring tank. The shape of the bottom of the stirring tank 10 is not particularly limited, and examples include a dish-shaped mirror plate shape, a semi-elliptical mirror plate shape, a flat mirror plate shape, and a conical mirror plate shape, and a dish-shaped mirror plate shape or a semi-elliptical mirror plate shape is preferable. In the stirring tank 10, in order to improve the stirring efficiency, a baffle may also be provided. The number of baffle plates is not particularly limited, but it is preferably 2 to 8 plates. The width of the baffle is not particularly limited, but is preferably 1/8 to 1/2 of the diameter of the stirring tank. The length of the baffle plate in the height direction of the stirring tank is not particularly limited, but it is preferably 1/2 or more of the height from the bottom of the stirring tank to the liquid level of the input component, more preferably 2/3 or more, More preferably, it is 3/4 or more.

It is preferable to attach a driving source (for example, a motor, etc.) not shown in the drawings to the stirring shaft 12. By rotating the stirring shaft 12 by the drive source, the stirring blade 14 rotates, and each component put into the stirring tank 10 is stirred. The shape of the stirring blade 14 is not particularly limited, and examples thereof include paddle blades, propeller blades, and turbine blades.

The stirring tank 10 may have a material input port for inputting various materials into the stirring tank. The stirring tank 10 may have a gas introduction port for introducing gas into the stirring tank 10. The stirring tank 10 may also have a gas discharge port for discharging the gas inside the stirring tank to the outside of the stirring tank.

The structure of the manufacturing apparatus of the sensitizing radiation-sensitive or radiation-sensitive resin composition is not limited to FIG. 1, as long as it has at least a container (preferably a stirring tank). In addition, a cleaning nozzle (for example, a spray ball) may be arranged on the upper part of the tank in the stirring tank.

In step (1), when the ingredients are put into the container, the container may or may not be stirred. The method of stirring is not particularly limited, and it is preferably performed by the stirring blade. The rotation speed of the stirring blade is not particularly limited, and is preferably 20 rpm to 500 rpm (rotations per minute), more preferably 40 rpm to 350 rpm, and still more preferably 50 rpm to 300 rpm.

The method of putting each component into the container in step (1) is not particularly limited. For example, the method of inputting various components from the material input port of a stirring tank is mentioned. When adding various components, the components can be added sequentially or all at once. In addition, when one ingredient is put in, it can be put in multiple times. In addition, when each component is sequentially injected into the stirring tank, the order of injection is not particularly limited. Furthermore, the end of step (1) (the end of step (1)) is the resin that should be put into the container in step (1), which is produced by irradiation of actinic rays or radiation. The period of acid compound, acid diffusion control agent and solvent.

Hereinafter, the resin used in step (1), a compound that generates an acid by irradiation with actinic rays or radiation, an acid diffusion control agent, and a solvent will be described.

＜Resin＞ The resin is not particularly limited, and examples thereof include resins having groups that decompose and generate polar groups due to the action of an acid, alkali-soluble resins, surfactants, hydrophobic resins, and the like. The resin used in step (1) may be one type or two or more types.

[Resin with a group that decomposes due to the action of an acid to generate a polar group] The resin (also referred to as "resin (A)") having a group that decomposes and generates a polar group due to the action of an acid will be described.

The resin (A) preferably contains a repeating unit (A-a) having an acid-decomposable group (hereinafter, also simply referred to as "repeating unit (A-a)"). The acid-decomposable group refers to a group that is decomposed by the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a leaving group that is detached by the action of an acid. That is, the resin (A) preferably has a repeating unit (A-a), and the repeating unit (A-a) has a group that is decomposed by the action of an acid to generate a polar group. The resin having this repeating unit (A-a) increases in polarity due to the action of an acid, and has an increase in solubility in an alkaline developer, and a decrease in solubility in an organic solvent.

The polar group is preferably an alkali-soluble group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamido group, a sulfonamido group, (alkylsulfonyl) (alkane) (Alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imino, bis(alkylsulfonyl) Acidic groups such as sulfonyl)methylene, bis(alkylsulfonyl)imino, tris(alkylcarbonyl)methylene and tris(alkylsulfonyl)methylene, and alcoholic hydroxyl groups, etc. . Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

Examples of the leaving group to be released by the action of the acid include groups represented by formula (Y1) to formula (Y4). Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y3): -C (R ₃₆ )(R ₃₇ )(OR ₃₈ ) Formula (Y4): -C(Rn)(H)(Ar)

In the formula (Y1) and the formula (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic). Furthermore, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of _{Rx 1} to Rx _{3 are methyl groups.} Among them, Rx ₁ to Rx ₃ preferably each independently represent a linear or branched alkyl group, and Rx ₁ to Rx _{3 more} preferably each independently represent a linear alkyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic ring or a polycyclic ring. The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl. As _{the cycloalkyl group of Rx 1} to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. are preferred Polycyclic cycloalkyl. As _{the cycloalkyl formed by the two bonding of Rx 1} to Rx ₃ , monocyclic cycloalkyls such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, and tetracyclododecyl are preferred. A polycyclic cycloalkyl group such as an alkyl group and an adamantyl group is more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In _{the cycloalkyl group formed by two bonding of Rx 1} to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. The group represented by the formula (Y1) or the formula (Y2) is preferably, for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the cycloalkyl group.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent substituent. R ₃₇ and R ₃₈ may be bonded to each other to form a ring. As a monovalent substituent, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. R _{36 is} also preferably a hydrogen atom.

The formula (Y3) is preferably a group represented by the following formula (Y3-1).

[化3]

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these (for example, a group formed by combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may have a hetero atom, a cycloalkyl group that may have a hetero atom, an aryl group that may have a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination of these groups ( For example, a group formed by combining an alkyl group and a cycloalkyl group). Among the alkyl group and the cycloalkyl group, for example, one methylene group may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. Furthermore, it is preferable that one of L ₁ and L ₂ is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. At least two of Q, M and L ₁ may be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring). In terms of the refinement of the pattern, L _{2 is} preferably a secondary alkyl group or a tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, and examples of tertiary alkyl groups include tertiary butyl groups and adamantane ring groups. In these aspects, since Tg (glass transition temperature) and activation energy become higher, in addition to ensuring film strength, fog can also be suppressed.

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

The repeating unit (A-a) is also preferably a repeating unit represented by formula (Aa1).

[化4]

L ₁ represents a divalent linking group which may have a fluorine atom or an iodine atom, and R ₁ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom , R ₂ represents a leaving group that is released by the action of an acid and may have a fluorine atom or an iodine atom. Among them, _{at least one of L 1} , R ₁ and R ₂ has a fluorine atom or an iodine atom. L ₁ represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of the divalent linking group that may have a fluorine atom or an iodine atom include: -CO-, -O-, -S, -SO-, -SO ₂ -, and a hydrocarbon group that may have a fluorine atom or an iodine atom (for example, a Alkyl group, cycloalkylene group, alkenylene group, arylene group, etc.) and a linking group formed by linking a plurality of these. Among them, in terms of the more excellent effect of the present invention, as L ₁ , -CO- or -arylene group-an alkylene group having a fluorine atom or an iodine atom is preferable. As the arylene group, a phenylene group is preferred. The alkylene group may be linear or branched. The carbon number of the alkylene group is not particularly limited, and is preferably 1-10, more preferably 1-3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited. In terms of the more excellent effect of the present invention, it is preferably 2 or more, and more preferably 2 to 10, more preferably 3-6.

R ₁ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be linear or branched. The carbon number of the alkyl group is not particularly limited, but is preferably 1-10, more preferably 1-3. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited. In terms of the more excellent effect of the present invention, it is preferably 1 or more, more preferably 1 to 5 , More preferably 1-3. The alkyl group may have a hetero atom such as an oxygen atom other than a halogen atom.

R ₂ represents a leaving group which is released by the action of an acid and may have a fluorine atom or an iodine atom. Among them, as the leaving group, groups represented by formulas (Z1) to (Z4) can be cited. Formula (Z1): -C(Rx ₁₁ )(Rx ₁₂ )(Rx ₁₃ ) Formula (Z2): -C(=O)OC(Rx ₁₁ )(Rx ₁₂ )(Rx ₁₃ ) Formula (Z3): -C (R ₁₃₆ )(R ₁₃₇ )(OR ₁₃₈ ) Formula (Z4): -C(Rn ₁ )(H)(Ar ₁ )

In formula (Z1) and formula (Z2), Rx ₁₁ to Rx ₁₃ each independently represent an alkyl group (linear or branched) that may have a fluorine atom or an iodine atom, or a ring that may have a fluorine atom or an iodine atom Alkyl (monocyclic or polycyclic). Furthermore, when all of Rx ₁₁ to Rx ₁₃ are alkyl groups (linear or branched), it is preferable that at least two of _{Rx 11} to Rx _{13 are methyl groups.} Rx ₁₁ to Rx _{13 are the same as Rx 1} to Rx _{3 in} (Y1) and (Y2), except that they may have a fluorine atom or an iodine atom, and have the same definitions and preferred ranges of alkyl and cycloalkyl .

In formula (Z3), R ₁₃₆ to R ₁₃₈ each independently represent a hydrogen atom, or a monovalent substituent which may have a fluorine atom or an iodine atom. R ₁₃₇ and R ₁₃₈ may be bonded to each other to form a ring. Examples of the monovalent substituent which may have a fluorine atom or an iodine atom include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, and an aryl group which may have a fluorine atom or an iodine atom. , Aralkyl groups which may have a fluorine atom or an iodine atom, and a group formed by combining these (for example, a group formed by combining an alkyl group and a cycloalkyl group). In addition, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain heteroatoms such as oxygen atoms in addition to fluorine atoms and iodine atoms. That is, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

The formula (Z3) is preferably a group represented by the following formula (Z3-1).

[化5]

Here, L ₁₁ and L ₁₂ each independently represent a hydrogen atom; an alkyl group that may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; may have an alkyl group selected from a fluorine atom, an iodine atom, and Cycloalkyl groups with hetero atoms in the group consisting of oxygen atoms; aryl groups with hetero atoms selected from the group consisting of fluorine atoms, iodine atoms and oxygen atoms; or groups formed by combining these (For example, a group formed by combining an alkyl group and a cycloalkyl group that may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom). M ₁ represents a single bond or a divalent linking group. Q ₁ represents an alkyl group which may have a hetero atom selected from the group consisting of fluorine atom, iodine atom and oxygen atom; it may have a hetero atom selected from the group consisting of fluorine atom, iodine atom and oxygen atom Cycloalkyl groups; aryl groups which may have heteroatoms selected from the group consisting of fluorine atoms, iodine atoms and oxygen atoms; amino groups; ammonium groups; mercapto groups; cyano groups; aldehyde groups; or a combination of these (For example, a group formed by combining an alkyl group and a cycloalkyl group that may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom).

In formula (Y4), Ar ₁ represents an aromatic ring group which may have a fluorine atom or an iodine atom. Rn ₁ represents an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. Rn ₁ and Ar ₁ may be bonded to each other to form a non-aromatic ring.

The repeating unit (A-a) is also preferably a repeating unit represented by the general formula (AI).

[化6]

In the general formula (AI), Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic). Among them, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of _{Rx 1} to Rx _{3 are methyl groups.} Two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the optionally substituted alkyl group represented by Xa ₁ include a methyl group or a group represented by _{-CH 2} -R _11. R ₁₁ represents a halogen atom (fluorine atom, etc.), a hydroxyl group or a monovalent substituent, for example, an alkyl group with 5 or less carbons which can be substituted by a halogen atom, an acyl group with 5 or less carbons and a halogen which can be substituted by a halogen atom The alkoxy group having 5 or less carbon atoms which may be substituted is preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa _{1 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

As the divalent linking group of T, an alkylene group, an aromatic ring group, a -COO-Rt- group, an -O-Rt- group, and the like can be mentioned. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably -CH ₂ -group, -(CH ₂ ) ₂ -group or -(CH ₂ ) ₃ -base.

The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl. The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. Polycyclic cycloalkyl. The cycloalkyl group formed by the two bonding of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl. In addition to this, norbornyl and tetracyclodecyl are also preferred. Polycyclic cycloalkyl groups such as alkyl, tetracyclododecyl and adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. In _{the cycloalkyl group formed by two bonding of Rx 1} to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. The repeating unit represented by the general formula (AI) is preferably a state in which, for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the cycloalkyl group.

When each group has a substituent, examples of the substituent include an alkyl group (carbon number 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (carbon number 1 to 4), a carboxyl group, and an alkoxy group. Group carbonyl (carbon number 2-6) and so on. The number of carbon atoms in the substituent is preferably 8 or less.

The repeating unit represented by the general formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate repeating unit (Xa ₁ represents a hydrogen atom or a methyl group, and T represents a single bond).

The resin (A) may have one type of repeating unit (A-a) alone, or two or more types. Relative to all the repeating units in the resin (A), the content of the repeating unit (Aa) (in the case of two or more repeating units (Aa), the total content) is preferably 15 mol% to 80 mol% , More preferably 20 mol%～70 mol%.

The resin (A) preferably has at least one repeating unit selected from the group consisting of repeating units represented by the following general formula (A-VIII) to general formula (A-XII) as the repeating unit (A-a).

[化7]

In the general formula (A-VIII), R ₅ represents a tertiary butyl group, a 1,1'-dimethylpropyl group, or a -CO-O-(tertiary butyl) group. In the general formula (A-IX), R ₆ and R ₇ each independently represent a monovalent substituent. As a monovalent substituent, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. In the general formula (AX), p represents 1 or 2. In general formula (AX) to general formula (A-XII), R ₈ represents a hydrogen atom or an alkyl group having 1 to 3 carbons, and R ₉ represents an alkyl group having 1 to 3 carbons. In the general formula (A-XII), R ₁₀ represents an alkyl group having 1 to 3 carbon atoms or an adamantyl group.

In addition to the repeating unit (A-a) having an acid-decomposable group, the resin (A) may also contain a repeating unit having a polar group such as an acid group, a lactone structure, a sultone structure, a carbonate structure, and a hydroxyadamantane structure.

(Repeating unit with acid group) The resin (A) may also contain a repeating unit having an acid group. The repeating unit having an acid group is preferably a repeating unit represented by the following general formula (B).

[化8]

R ₃ represents a hydrogen atom, or a monovalent substituent which may have a fluorine atom or an iodine atom. The monovalent substituent which may have a fluorine atom or an iodine atom is preferably a group represented by _{-L 4} -R _8. L ₄ represents a single bond or an ester group. Examples of R ₈ include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group formed by combining these.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

L ₂ represents a single bond or an ester group. L ₃ represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be a monocyclic ring or a polycyclic ring group, for example, a cycloalkyl ring group. R ₆ represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Furthermore, when R ₆ is a hydroxyl group, L _{3 is} preferably an (n+m+1)-valent aromatic hydrocarbon ring group. R ₇ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. m represents an integer of 1 or more. m is preferably an integer of 1-3, more preferably an integer of 1-2. n represents an integer of 0 or more. n is preferably an integer of 1-4. Furthermore, (n+m+1) is preferably an integer of 1-5.

The repeating unit having an acid group is also preferably a repeating unit represented by the following general formula (I).

[化9]

In the general formula (I), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Among them, R ₄₂ may be _{bonded to Ar 4} to form a ring. In this case, R ₄₂ represents a single bond or an alkylene group. X ₄ represents a single bond, -COO- or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group. L ₄ represents a single bond or an alkylene group. Ar ₄ represents an (n+1)-valent aromatic ring group, and when it _{bonds with R 42} to form a ring, it represents an (n+2)-valent aromatic ring group. n represents an integer of 1-5.

_{As the alkyl group of R 41} , R ₄₂ and R ₄₃ in the general formula (I), methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethyl are preferred. The alkyl group having 20 or less carbon atoms such as hexyl, octyl, and dodecyl group is more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.

_{The cycloalkyl group of R 41} , R ₄₂ and R ₄₃ in the general formula (I) may be a monocyclic type or a polycyclic type. Among them, preferred are monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl. _{Examples of the halogen atom of R 41} , R ₄₂ and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The alkyl group contained in the alkoxycarbonyl group _{of R 41} , R ₄₂ and R ₄₃ in the general formula (I) is preferably the same alkyl group as the alkyl group of _{R 41} , R ₄₂ , and R ₄₃ .

Ar ₄ represents an (n+1)-valent aromatic ring group. When n is 1, the divalent aromatic ring group may have a substituent. For example, phenylene, phenylene, naphthylene, and anthracenyl are preferably arylene groups having 6 to 18 carbon atoms or containing thiophene rings, Furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring and thiazole ring and other heterocyclic aromatic rings base.

As a specific example of the (n+1)-valent aromatic ring group when n is an integer of 2 or more, a group obtained by removing (n-1) arbitrary hydrogen atoms from the specific example of the divalent aromatic ring group can be cited . The (n+1)-valent aromatic ring group may further have a substituent.

Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include R ₄₁ and R _{42 in the general formula (I)} And alkoxy groups such as alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy, exemplified in _{R 43; aryl groups such as phenyl and the like. Examples of the alkyl group of R 64} in -CONR _64- (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ include methyl, ethyl, propyl, isopropyl, n-butyl, and butyl Alkyl groups having 20 or less carbon atoms, such as hexyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, are preferably alkyl groups having 8 or less carbon atoms. X _{4 is} preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

The _{alkylene group in L 4} is preferably an alkylene group having 1 to 8 carbon atoms such as methylene, ethylene, propylene, butylene, hexylene, and octylene. Ar _{4 is} preferably an aromatic ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, and a biphenyl ring group.

Although the specific example of the repeating unit represented by general formula (I) is shown below, this invention is not limited to this. In the formula, a represents 1, 2 or 3.

[化10]

[化11]

(Repeating unit derived from hydroxystyrene (A-1)) The resin (A) preferably has a repeating unit (A-1) derived from hydroxystyrene as a repeating unit having an acid group. Examples of the repeating unit (A-1) derived from hydroxystyrene include repeating units represented by the following general formula (1).

[化12]

In the general formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, in When there are a plurality of them, they may be the same or different. In the case of having a plurality of Rs, they may form a ring in common with each other. As R, a hydrogen atom is preferred. a represents an integer of 1 to 3, and b represents an integer of 0 to (5-a).

The repeating unit (A-1) is preferably a repeating unit represented by the following general formula (A-I).

[化13]

The resist composition containing the resin (A) having the repeating unit (A-1) is preferably used for KrF exposure, EB exposure, or EUV exposure. Relative to all the repeating units in the resin (A), the content of the repeating unit (A-1) in this case is preferably 30 mol% to 99 mol%, more preferably 40 mol% to 99 mol% , And more preferably 50 mol% to 99 mol%.

(Having at least one repeating unit (A-2) selected from the group consisting of a lactone structure, a sultone structure, a carbonate structure, and a hydroxyadamantane structure) The resin (A) may also contain a repeating unit (A-2) having at least one selected from the group consisting of a lactone structure, a carbonate structure, a sultone structure, and a hydroxyadamantane structure.

The lactone structure or sultone structure in the repeating unit having a lactone structure or a sultone structure is not particularly limited, and is preferably a 5-membered cyclic lactone structure to a 7-membered cyclic lactone structure or a 5-membered cyclic sultone Structure-7-membered cyclic sultone structure, more preferably other ring structure to form a bicyclic structure, spiro structure formed by condensing a 5-membered cyclic lactone structure to a 7-membered cyclic lactone structure, or other ring The structure is formed by condensing rings in a 5-membered cyclic sultone structure to a 7-membered cyclic sultone structure in the form of a bicyclic structure or a spiro structure. Examples of the repeating unit having a lactone structure or a sultone structure include the repeating units described in paragraphs 0094 to 0107 of WO2016/136354.

The resin (A) may also contain a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure. Examples of the repeating unit having a carbonate structure include repeating units described in paragraphs 0106 to 0108 of WO2019/054311.

The resin (A) may also contain a repeating unit having a hydroxyadamantane structure. Examples of the repeating unit having a hydroxyadamantane structure include repeating units represented by the following general formula (AIIa).

[化14]

In the general formula (AIIa), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R ₂ c to R ₄ c each independently represent a hydrogen atom or a hydroxyl group. Among them, _{at least one of R 2} c to R ₄ c represents a hydroxyl group. Preferably, one or two of R ₂ c to R ₄ c are hydroxyl groups, and the rest are hydrogen atoms.

(Repeating unit with fluorine atom or iodine atom) The resin (A) may also contain a repeating unit having a fluorine atom or an iodine atom. As the repeating unit having a fluorine atom or an iodine atom, the repeating unit described in paragraph 0080 to paragraph 0081 of JP 2019-045864 A can be cited.

(Repeating unit with photoacid generating group) The resin (A) may contain a repeating unit having a group that generates an acid by irradiation with radiation as a repeating unit other than the above. As the repeating unit having a fluorine atom or an iodine atom, the repeating unit described in paragraph 0092 to paragraph 0096 of JP 2019-045864 A can be cited.

(Repeating unit with alkali-soluble group) The resin (A) may contain a repeating unit having an alkali-soluble group. Examples of alkali-soluble groups include carboxyl groups, sulfonamido groups, sulfonamido groups, bissulfonamido groups, and aliphatic alcohols substituted with electron-withdrawing groups at the α position (for example, hexafluoroisopropanol groups). Preferably it is a carboxyl group. Since the resin (A) contains a repeating unit having an alkali-soluble group, the resolution for contact hole applications is increased. Examples of the repeating unit having an alkali-soluble group include repeating units derived from acrylic acid and methacrylic acid, which are directly bonded to the main chain of the resin with an alkali-soluble group, or are connected to the main chain of the resin via a linking group. Repeating units bonded with alkali-soluble groups. Furthermore, the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. The repeating unit having an alkali-soluble group is preferably a repeating unit derived from acrylic acid or methacrylic acid.

(A repeating unit that does not have either an acid-decomposable group or a polar group) The resin (A) may further contain a repeating unit that does not have any of an acid-decomposable group and a polar group. It is preferable that the repeating unit which does not have any of an acid-decomposable group and a polar group has an alicyclic hydrocarbon structure.

As a repeating unit that does not have any of an acid-decomposable group and a polar group, for example, the repeating unit described in paragraphs 0236 to 0237 of the specification of U.S. Patent Application Publication No. 2016/0026083 and U.S. Patent Application Publication No. 2016 The repeating unit described in paragraph 0433 of specification No. /0070167.

In addition to the repeating structural unit, the resin (A) may also have various types for the purpose of adjusting dry etching resistance, standard developer compatibility, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity. Repeating structural units.

(Characteristics of resin (A)) As the resin (A), it is preferable that all the repeating units are composed of repeating units derived from a (meth)acrylate-based monomer (a monomer having a (meth)acrylic group). In this case, all the repeating units are derived from methacrylate-based monomers, all repeating units are derived from acrylate-based monomers, and all repeating units are derived from methacrylate-based monomers and acrylic ester-based monomers. Any resin that is a monomer. With respect to all the repeating units in the resin (A), the repeating unit derived from the acrylate-based monomer is preferably 50 mol% or less.

When the sensitizing or radiation-sensitive resin composition produced by the production method of the present invention is used for argon fluoride (ArF) exposure, the resin (A) is preferably It has substantially no aromatic group. More specifically, with respect to all the repeating units of the resin (A), the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally still more preferably 0 mol% %, that is, it does not contain repeating units with aromatic groups. In addition, when the sensitizing radiation-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is used for ArF exposure, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure. In addition, Preferably, it does not contain any of fluorine atoms and silicon atoms.

When the photosensitive ray-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is used for exposure to krypton fluoride (KrF), for EB exposure, or for EUV exposure, the resin (A) preferably contains aromatic The repeating unit of the group hydrocarbon group more preferably contains a repeating unit having a phenolic hydroxyl group. Examples of the repeating unit having a phenolic hydroxyl group include the repeating unit (A-1) derived from the hydroxystyrene and the repeating unit derived from hydroxystyrene (meth)acrylate. In addition, when the sensitizing radiation-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is used for KrF exposure, EB exposure, or EUV exposure, the resin (A) also preferably contains the following repeating unit: The repeating unit has a structure in which the hydrogen atom of the phenolic hydroxyl group is protected by a group that is decomposed and released by the action of an acid (a leaving group). When the sensitizing or radiation-sensitive resin composition produced by the production method of the present invention is used for KrF exposure, EB exposure, or EUV exposure, the resin (A) is The content of the repeating unit having an aromatic hydrocarbon group contained in) is preferably 30 mol%-100 mol%, more preferably 40 mol%-100 mol%, and still more preferably 50 mol%-100 mol% Ear%.

The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). The weight average molecular weight (Mw) of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and still more preferably 5,000 to 15,000. By setting the weight average molecular weight (Mw) of the resin (A) to 1,000 to 200,000, the deterioration of heat resistance and dry etching resistance can be prevented, and the deterioration of the developability and the increase in viscosity and the deterioration of film forming properties can be prevented. In addition, the weight average molecular weight (Mw) of resin (A) is a polystyrene conversion value measured by the said GPC method. The degree of dispersion (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, and more preferably 1.1 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, and the smoother the sidewalls of the pattern, the better the roughness.

In the sensitized radiation-sensitive or radiation-sensitive resin composition produced by the production method of the present invention, the content of the resin (A) is preferably 50% by mass to 99.9% by mass relative to the total solid content of the composition , More preferably 60% by mass to 99.0% by mass. Therefore, in the case of using resin (A) as the resin put into the container in step (1), it is preferable to adjust the addition amount of the resin (A) put into the container in step (1), The content of the resin (A) in the sensitizing ray-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is within the above-mentioned range. Moreover, resin (A) may be used individually by 1 type, and may use 2 or more types together. In addition, in this specification, the "solid content" means a component other than the solvent. Even if the properties of the components are liquid, they are regarded as solid components. The term "total solid content" refers to the sum of all solid content.

[Surfactant] The sensitizing radiation-sensitive or radiation-sensitive resin composition produced by the production method of the present invention may contain a surfactant (also described as "surfactant (E)"). By including a surfactant, a pattern with better adhesion and fewer development defects can be formed. The surfactant may be a resin or not. In the case of a resin, the surfactant may be used as the "resin" that is easily put in step (1) of the manufacturing method of the present invention. As the surfactant (E), fluorine-based and/or silicon-based surfactants are preferred. As the fluorine-based and/or silicon-based surfactants, for example, the surfactants described in paragraph 0276 of the specification of U.S. Patent Application Publication No. 2008/0248425 can be cited. In addition, Eftop EF301 or EF303 (manufactured by New Akita Chemical Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.) can also be used; Megafac F171 , F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC); Surflon S-382, SC101, 102, 103, 104, 105 or 106 ( Asahi Glass (manufactured by Asahi Glass (stock)); Troysol S-366 (manufactured by Troy Chemical (stock)); GF-300 or GF-150 (manufactured by Dongya Synthetic Chemical (stock)), Saffron ( Surflon) S-393 (manufactured by Seimi Chemical (Stock)); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (Jemco ( Jemco (stock) manufacturing); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); KH-20 (manufactured by Asahi Kasei Co., Ltd.); FTX-204G, 208G, 218G, 230G, 204D, 208D , 212D, 218D or 222D (manufactured by NEOS (Stock)). Furthermore, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition, the surfactant (E) can also be used by a short-chain polymerization (telomerization) method (also referred to as a telomerization method) or an oligomerization method ( Also known as the oligomer method) to produce fluoroaliphatic compounds. Specifically, a polymer containing a fluoroaliphatic group derived from the fluoroaliphatic compound can also be used as the surfactant (H). The fluorinated aliphatic compound can be synthesized, for example, by the method described in Japanese Patent Laid-Open No. 2002-90991. The polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene)) acrylate and/or (poly(oxyalkylene)) methacrylate , Even if it is irregularly distributed, block copolymerization can also be carried out. In addition, poly(oxyalkylene) groups include poly(oxyethylene) groups, poly(oxypropylene) groups, and poly(oxybutylene) groups. In addition, poly(oxyethylene, propylene oxide, and oxyethylene) groups may be used. Block linker) or poly(block linker of ethylene oxide and propylene oxide) is equal to the unit of alkylene having different chain lengths in the same chain length. Furthermore, the copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer, but also a combination of two or more different types of fluorine A ternary or more copolymer obtained by simultaneous copolymerization of monomers that substitute for aliphatic groups and two or more different (poly(oxyalkylene)) acrylates (or methacrylates), etc. For example, commercially available surfactants include: Megafac F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC) , Copolymers of acrylate (or methacrylate) and (poly(oxyalkylene)) acrylate (or methacrylate) with C ₆ F _{13 groups, acrylate (or methacrylate) with C 3} F ₇ groups Base acrylate), (poly(oxyethylene)) acrylate (or methacrylate) and (poly(oxypropylene)) acrylate (or methacrylate) copolymer. In addition, the fluorine-based and/or silicon-based surfactants described in paragraph [0280] of the specification of U.S. Patent Application Publication No. 2008/0248425 may also be used.

These surfactants (E) may be used alone or in combination of two or more.

When the sensitizing or radiation-sensitive resin composition produced by the production method of the present invention contains a surfactant (E), the ratio of the surfactant (E) to the total solid content of the composition The content is preferably 0.0001% by mass to 2% by mass, more preferably 0.0005% by mass to 1% by mass. Therefore, when the surfactant (E) is used as the resin put into the container in the step (1), it is preferable to add the surfactant (E) put into the container in the step (1) The amount is adjusted so that the content of the surfactant (E) in the sensitizing ray-sensitive or radiation-sensitive resin composition produced by the production method of the present invention falls within the above-mentioned range.

[Hydrophobic resin] The photosensitive ray-sensitive or radiation-sensitive resin composition produced by the production method of the present invention may include a hydrophobic resin (also described as “hydrophobic resin (F)”). The hydrophobic resin (F) is a hydrophobic resin different from the resin (A). The hydrophobic resin (F) can be used as the "resin" put into the container in the step (1) of the production method of the present invention. The hydrophobic resin (F) is preferably designed to be biased on the surface of the resist film, but unlike surfactants, it does not necessarily have a hydrophilic group in the molecule, and it does not help to evenly mix polar substances and non-polar substances. substance. Examples of the effect of adding the hydrophobic resin (F) include controlling the static and dynamic contact angle of the resist film surface with respect to water, and suppressing outgassing.

From the viewpoint of the existence of bias toward the film surface layer, the hydrophobic resin (F) preferably has any one of "fluorine atom", "silicon atom", and "CH ₃ partial structure contained in the side chain part of the resin" Above, it is more preferable to have two or more types. In addition, the hydrophobic resin (F) preferably has a hydrocarbon group with 5 or more carbon atoms. These groups may exist in the main chain of the resin, or may be substituted in the side chain.

When the hydrophobic resin (F) contains fluorine atoms and/or silicon atoms, the fluorine atoms and/or silicon atoms in the hydrophobic resin may be included in the main chain of the resin or may be included in the side chain.

When the hydrophobic resin (F) has a fluorine atom, the partial structure having a fluorine atom is preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have Substituents other than fluorine atoms. The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. Examples of the aryl group having a fluorine atom include a group in which at least one hydrogen atom of an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and it may further have a substituent other than a fluorine atom. As an example of the repeating unit having a fluorine atom or a silicon atom, the one exemplified in paragraph 0519 of US2012/0251948 can be cited.

In addition, as described above, it is also preferable that the hydrophobic resin (F) has a CH ₃ partial structure in the side chain portion. Here, the side chain portion of the hydrophobic resin has a partial structure containing ₃ CH ₃ having a partial structure such as ethyl and propyl CH. On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (F) (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) has a negative effect on the hydrophobic resin (F) due to the influence of the main chain. ) The contribution of the bias on the surface is small, so it is assumed that it is not included in the CH ₃ partial structure of the present invention.

Regarding the hydrophobic resin (F), reference can be made to the description of paragraphs 0348 to 0415 of JP 2014-010245 A, and these contents are incorporated into this specification.

Furthermore, as the hydrophobic resin (F), those described in Japanese Patent Laid-Open No. 2011-248019, Japanese Patent Laid-Open No. 2010-175859, and Japanese Patent Laid-Open No. 2012-032544 can also be preferably used. Resin.

A preferable aspect of the hydrophobic resin (F) is a resin having a repeating unit represented by the following general formula (F-1).

[化15]

In the general formula (F-1), RF ₁ represents a hydrogen atom or an alkyl group, and RF ₂ represents an alkyl group, a cycloalkyl group or an aryl group. The alkyl group of RF ₁ may be linear or branched, preferably an alkyl group having 1 to 10 carbons, more preferably an alkyl group having 1 to 6 carbons, and still more preferably a carbon number of 1 to 4的alkyl. The alkyl group of RF ₂ may be linear or branched, preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 5 to 25 carbon atoms, and still more preferably an alkyl group having 6 to 20 carbon atoms.的alkyl. The alkyl group as RF ₂ preferably has a substituent containing a fluorine atom or a silicon atom. The cycloalkyl group of RF ₂ may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 30 carbon atoms, more preferably a cycloalkyl group having 5 to 25 carbon atoms, and even more preferably a carbon number of 6 ~20 cycloalkyl. The cycloalkyl group as RF ₂ preferably has a substituent containing a fluorine atom or a silicon atom. The aryl group of RF ₂ is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 25 carbon atoms, and still more preferably an aryl group having 6 to 20 carbon atoms. The aryl group as RF ₂ preferably has a substituent containing a fluorine atom or a silicon atom.

When the photosensitive ray-sensitive or radiation-sensitive resin composition produced by the production method of the present invention contains a hydrophobic resin (F), the amount of the hydrophobic resin (F) relative to the total solid content of the composition The content is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 15% by mass. Therefore, when the hydrophobic resin (F) is used as the resin put into the container in the step (1), it is preferable to add the hydrophobic resin (F) put into the container in the step (1) The amount is adjusted so that the content of the hydrophobic resin (F) in the sensitizing ray-sensitive or radiation-sensitive resin composition produced by the production method of the present invention falls within the above-mentioned range.

<Compounds that generate acid by irradiation with actinic rays or radiation (photoacid generator)> The compound that generates acid by irradiation with actinic rays or radiation (also described as "photoacid generator (C)") will be described. The photoacid generator (C) is not particularly limited as long as it is a compound that generates acid by irradiating actinic rays or radiation. The photoacid generator (C) may be in the form of a low-molecular compound, or may be incorporated in a part of the polymer. In addition, the form of the low-molecular compound may be used in combination with the form incorporated into a part of the polymer. When the photoacid generator (C) is in the form of a low-molecular compound, the weight average molecular weight (Mw) is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less. The photoacid generator (C) may be incorporated into a part of the resin (A), or may be incorporated into a resin different from the resin (A). The photoacid generator (C) is preferably in the form of a low-molecular compound.

The photoacid generator (C) is preferably a compound that generates an organic acid by irradiation with actinic rays or radiation, more preferably a compound that generates an organic acid by irradiation with actinic rays or radiation, and has fluorine in the molecule. A compound of an atom or an iodine atom. As the organic acid, for example, sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphor sulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkyl carboxylic acid, etc.), Carbonylsulfonimidic acid, bis(alkylsulfonyl)imidic acid and tris(alkylsulfonyl)methide acid, etc.

Preferred aspects of the photoacid generator (C) include, for example, a compound represented by the following general formula (ZI), a compound represented by the following general formula (ZII), and a compound represented by the following general formula (ZIII) Represents the compound.

[化16]

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R _{203 is usually 1-30, preferably 1-20.} In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and may include an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group in the ring. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include alkylene (for example, butylene, pentylene) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -. Z ^- represents an anion.

(Cation in the compound represented by the general formula (ZI)) Preferred aspects of the cation in the general formula (ZI) include the compound (ZI-1), compound (ZI-2), and compound (ZI) described later. -3) and the corresponding group in the compound (ZI-4). In addition, the photoacid generator (C) may be a compound having a plurality of structures represented by the general formula (ZI). _{For example, at least one of R 201} to R ₂₀₃ of the compound represented by general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by general formula (ZI) may be connected via a single bond or a linking group. A compound of the structure formed by bonding.

(Compound (ZI-1)) First, the compound (ZI-1) will be described. The compound (ZI-1) is _{an aryl alumium compound in which at least one of R 201} to R ₂₀₃ in the general formula (ZI) is an aryl group, that is, a compound having an aryl alumium as a cation. In the aryl amber compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, or part of R ₂₀₁ to R ₂₀₃ may be aryl groups and the rest may be alkyl or cycloalkyl groups. As the aryl alumium compound, for example, a triaryl alumium compound, a diarylalkyl alumium compound, an aryl dialkyl alumium compound, a diaryl cycloalkyl alumium compound, and an aryl dicycloalkyl alumium compound are mentioned.

The aryl group of the aryl alumium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl alumium compound has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the aryl cyanide compound has as necessary is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, for example Examples include methyl, ethyl, propyl, n-butyl, second butyl, tertiary butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ may each independently have an alkyl group (for example, carbon number 1-15), cycloalkyl group (for example, carbon number 3-15), aryl group (for example carbon number 6). -14), an alkoxy group (for example, carbon number 1-15), a halogen atom, a hydroxyl group or a thiophenyl group as a substituent.

(Compound (ZI-2)) Next, the compound (ZI-2) will be described. The compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the general formula (ZI) each independently represent an organic group that does not have an aromatic ring. Here, the term "aromatic ring" also includes aromatic rings containing heteroatoms. The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxy group The carbonylcarbonylmethyl group is more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ preferably include straight chain alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl Group, butyl group and pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group and norbornyl group). R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, a carbon number of 1 to 5), a hydroxyl group, a cyano group, or a nitro group.

(Compound (ZI-3)) Next, the compound (ZI-3) will be described. The compound (ZI-3) is a compound represented by the following general formula (ZI-3) and having a benzylmethyl sulfonate structure.

[化17]

In the general formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, Cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. Any two or more of R _1c to R _{5c , R 5c} and R _6c , R _6c and R _7c , R _5c and R _x, and R _x and R _y may be bonded to each other to form a ring structure, and the ring structures may each be It independently contains an oxygen atom, a sulfur atom, a keto group, an ester bond or an amide bond. Z _c ^- represents an anion.

Any two or more of R _1c to R _{5c , R 5c} and R _6c , R _6c and R _7c , R _5c and R _x, and R _x and R _y may be bonded to each other to form a ring structure, which may be independent of each other Ground contains an oxygen atom, a sulfur atom, a keto group, an ester bond or an amide bond. Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring structure include a 3-membered ring to a 10-membered ring, preferably a 4-membered ring to an 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

Examples of groups formed by bonding any two or more of R _1c to R _{5c , R 6c} and R _7c, and R _x and R _{y include butylene and pentylene.} The group formed by bonding R _5c and R _6c and R _5c and R _{x is} preferably a single bond or an alkylene group. As an alkylene group, a methylene group, an ethylene group, etc. are mentioned.

The alkyl group of R _6c and R _7c is not particularly limited, and may be linear or branched, preferably an alkyl group having 1 to 20 carbons, more preferably an alkyl group having 1 to 15 carbons, and still more preferably An alkyl group having 1 to 10 carbon atoms. The alkyl group may have a substituent.

The cycloalkyl group of R _6c and R _7c is not particularly limited, and may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbons, more preferably a cycloalkyl group having 3 to 15 carbons, and further Preferably, it is a cycloalkyl group having 3 to 10 carbon atoms. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl. The cycloalkyl group may have a substituent.

The aryl group of R _6c and R _7c is not particularly limited, and may be monocyclic or polycyclic, preferably an aryl group having 6 to 20 carbons, more preferably an aryl group having 6 to 15 carbons, and Preferably, it is an aryl group having 6 to 10 carbons. The aryl group may have a substituent.

R _6c and R _7c are each independently preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group.

The alkyl group of R _x and R _y is not particularly limited, and may be linear or branched, preferably an alkyl group having 1 to 20 carbons, more preferably an alkyl group having 1 to 15 carbons, and still more preferably An alkyl group having 1 to 10 carbon atoms. The alkyl group may have a substituent.

The cycloalkyl group of R _x and R _y is not particularly limited, and may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbons, more preferably a cycloalkyl group having 3 to 15 carbons, and further Preferably, it is a cycloalkyl group having 3 to 10 carbon atoms. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl. The cycloalkyl group may have a substituent.

The 2-oxoalkyl group of R _x and R _y is not particularly limited, but is preferably a 2-oxoalkyl group having 1 to 20 carbons, and more preferably a 2-oxoalkyl group having 1 to 15 carbons, More preferably, it is a 2-oxoalkyl group having 1 to 10 carbon atoms. The 2-oxoalkyl group may have a substituent.

The 2-oxocycloalkyl group for R _x and R _y is not particularly limited, but is preferably a 2-oxocycloalkyl group having 3 to 20 carbons, and more preferably a 2-oxocycloalkyl group having 3 to 15 carbons. The alkyl group is more preferably a 2-oxocycloalkyl group having 3 to 10 carbon atoms. The 2-oxocycloalkyl group may have a substituent.

The alkoxycarbonylalkyl group of R _x and R _y is not particularly limited, but is preferably an alkoxycarbonylalkyl group having 3 to 22 carbon atoms, more preferably an alkoxycarbonylalkyl group having 3 to 17 carbon atoms, More preferably, it is an alkoxycarbonylalkyl group having 3 to 12 carbons. The alkoxycarbonylalkyl group may have a substituent.

R _x and R _y may be linked to each other to form a ring, and the ring structure may include an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, and an amide bond. The ring structure preferably contains an oxygen atom. Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring structure include a 3-membered ring to a 10-membered ring, preferably a 4-membered ring to an 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

(Compound (ZI-4)) Next, the compound (ZI-4) will be described. The compound (ZI-4) is represented by the following general formula (ZI-4).

[化18]

In the general formula (ZI-4), l represents an integer of 0-2. r represents an integer of 0-8. R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group. R ₁₄ represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group or a cycloalkylsulfonyl group. When _{there are a plurality of R 14} , they may be the same or different. R ₁₅ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, heteroatoms may also be included in the ring skeleton. Z ^- represents an anion.

In the general formula (ZI-4), _{the alkyl groups of R 13} , R ₁₄ and R ₁₅ are linear or branched, preferably having 1 to 10 carbon atoms, more preferably methyl, ethyl, or normal Butyl or tertiary butyl, etc.

The alkyl group for R ₁₃ is not particularly limited, and may be linear or branched, preferably an alkyl group having 1 to 20 carbons, more preferably an alkyl group having 1 to 15 carbons, and still more preferably a carbon number of 1. Specifically, the alkyl group of -10 is preferably a methyl group, an ethyl group, a n-butyl group or a tertiary butyl group. The alkyl group may have a substituent.

The cycloalkyl group for R ₁₃ is not particularly limited, and may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbons, more preferably a cycloalkyl group having 3 to 15 carbons, and still more preferably carbon A cycloalkyl group of 3-10. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl. The cycloalkyl group may have a substituent.

The alkoxy group of R ₁₃ is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbons, more preferably an alkoxy group having 1 to 15 carbons, and still more preferably an alkoxy group having 1 to 10 carbons. . The alkoxy group may have a substituent.

The alkoxycarbonyl group for R ₁₃ is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 21 carbons, more preferably an alkoxycarbonyl group having 2 to 16 carbons, and still more preferably a carbon number of 2-11 Alkoxycarbonyl. The alkoxycarbonyl group may have a substituent.

The alkyl group for R ₁₄ is not particularly limited, and may be linear or branched, preferably an alkyl group having 1 to 20 carbons, more preferably an alkyl group having 1 to 15 carbons, and still more preferably a carbon number of 1. Specifically, the alkyl group of -10 is preferably a methyl group, an ethyl group, a n-butyl group or a tertiary butyl group. The alkyl group may have a substituent.

The cycloalkyl group for R ₁₄ is not particularly limited, and may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbons, more preferably a cycloalkyl group having 3 to 15 carbons, and still more preferably carbon A cycloalkyl group of 3-10. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl. The cycloalkyl group may have a substituent.

The alkoxy group of R ₁₄ is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbons, more preferably an alkoxy group having 1 to 15 carbons, and still more preferably an alkoxy group having 1 to 10 carbons. . The alkoxy group may have a substituent.

The alkoxycarbonyl group for R ₁₄ is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 21 carbons, more preferably an alkoxycarbonyl group having 2 to 16 carbons, and still more preferably a carbon number of 2 to 11 Alkoxycarbonyl. The alkoxycarbonyl group may have a substituent.

The alkylcarbonyl group for R ₁₄ is not particularly limited, but is preferably an alkylcarbonyl group having 2 to 21 carbons, more preferably an alkylcarbonyl group having 2 to 16 carbons, and still more preferably an alkylcarbonyl group having 2 to 11 carbons . The alkylcarbonyl group may have a substituent.

The alkylsulfonyl group for R ₁₄ is not particularly limited, but is preferably an alkylsulfonyl group having 1 to 20 carbons, more preferably an alkylsulfonyl group having 1 to 15 carbons, and still more preferably a carbon number of 1. ~10 alkylsulfonyl. The alkylsulfonyl group may have a substituent.

The cycloalkylsulfonyl group for R ₁₄ is not particularly limited, but is preferably a cycloalkylsulfonyl group having 3 to 20 carbons, more preferably a cycloalkylsulfonyl group having 3 to 15 carbons, and still more preferably A cycloalkylsulfonyl group having 3 to 10 carbon atoms. The cycloalkylsulfonyl group may have a substituent.

When there are a plurality of R ₁₄ , the plurality of R ₁₄ may be the same as or different from each other.

The alkyl group for R ₁₅ is not particularly limited, and may be linear or branched, preferably an alkyl group having 1 to 20 carbons, more preferably an alkyl group having 1 to 15 carbons, and still more preferably a carbon number of 1. Specifically, the alkyl group of -10 is preferably a methyl group, an ethyl group, a n-butyl group or a tertiary butyl group. The alkyl group may have a substituent.

The cycloalkyl group for R ₁₅ is not particularly limited, and may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbons, more preferably a cycloalkyl group having 3 to 15 carbons, and still more preferably a carbon A cycloalkyl group of 3-10. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl. The cycloalkyl group may have a substituent.

The naphthyl group as R ₁₅ may have a substituent.

Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, the ring structure may contain heteroatoms such as oxygen, sulfur, and nitrogen, and may also contain oxygen, nitrogen, sulfur, ketone, ether, and ester bonds. , Amide bond. The ring structure preferably contains an oxygen atom. Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring structure include a 3-membered ring to a 10-membered ring, preferably a 4-membered ring to an 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

In a preferred aspect, it is preferable that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure.

(Cation in the compound represented by general formula (ZII) or general formula Z(III)) Next, general formula (ZII) and general formula (ZIII) will be described. In general formula (ZII) and general formula (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group, or a cycloalkyl group. The aryl group of R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. As _{the alkyl group and cycloalkyl group of R 204} to R ₂₀₇ , preferably, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl , Butyl and pentyl), C3-10 cycloalkyl (such as cyclopentyl, cyclohexyl and norbornyl).

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R _{207 may each independently have a substituent.} Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include alkyl groups (for example, carbon numbers 1 to 15), cycloalkyl groups (for example, carbon numbers 3 to 15), and aryl groups. Group (for example, carbon number 6-15), alkoxy (for example, carbon number 1-15), halogen atom, hydroxyl group, thiophenyl group, etc. Z ^- represents an anion.

(The anion in the compound represented by general formula (ZI), general formula (ZII), general formula (ZI-3) or general formula (ZI-4)) As Z ^- in general formula (ZI), general formula ( anion, preferably the following general formula (3) represented by ^- ZII) of Z ^-, of the general formula (ZI-3) is Z _c ^- and the formula (Z ZI-4) is.

[化19]

In the general formula (3), o represents an integer of 1-3. p represents an integer of 0-10. q represents an integer of 0-10. Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R ₄ and R _{5, they} may be the same or different. L represents a divalent linking group, and when there are a plurality of L, they may be the same or different. W represents an organic group. o represents an integer of 1-3. p represents an integer of 0-10. q represents an integer of 0-10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The carbon number of the alkyl group is preferably 1-10, more preferably 1-4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is more preferably a fluorine atom or CF ₃ . In particular, two Xf are fluorine atoms.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R ₄ and R ₅ , each may be the same or different. The alkyl group as R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R _{5 are} preferably hydrogen atoms. The specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in the general formula (3).

L represents a divalent linking group, and when there are a plurality of L, they may be the same or different. Examples of the divalent linking group include: -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-,- SO-, -SO ₂ -, alkylene (preferably carbon number 1 to 6), cycloalkylene (preferably carbon number 3 to 15), alkenylene group (preferably carbon number 2 to 6) And a divalent linking group formed by combining a plurality of these. Among these, preferred are -COO-, -OCO-, -CONH-, -NHCO- _{, -CO-, -O-, -SO 2} -, -COO-alkylene-, -OCO-alkylene -, -CONH-alkylene- or -NHCO-alkylene-, more preferably -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene alkyl-.

W represents an organic group. The carbon number of the organic group is not particularly limited, and is usually 1-30, preferably 1-20. It does not specifically limit as an organic group, For example, an alkyl group, an alkoxy group, etc. are represented. The alkyl group is not particularly limited, and may be linear or branched, preferably an alkyl group having 1 to 10 carbons, more preferably an alkyl group having 1 to 6 carbons, and still more preferably an alkyl group having 1 to 4 carbons. base. The alkyl group and alkoxy group may have a substituent. May have substituents. The substituent is not particularly limited. For example, the substituent T may be mentioned above, and a fluorine atom is preferred.

W preferably represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl group, tricyclodecyl group, tetracyclodecyl group, tetracyclododecyl group, and adamantyl group, are preferred.

The aryl group may be monocyclic or polycyclic. As this aryl group, a phenyl group, a naphthyl group, a phenanthryl group, and an anthracenyl group are mentioned, for example. The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further inhibit the diffusion of acid. In addition, the heterocyclic group may be aromatic or not. Examples of the aromatic heterocyclic ring include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the resin. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), cycloalkyl (which may be any one of monocyclic, polycyclic, and spirocyclic rings, Preferably it is carbon number 3-20), aryl group (preferably carbon number 6-14), hydroxyl group, alkoxy group, ester group, amide group, urethane group, urea group, thioether group, Sulfonamide group and sulfonate group. Furthermore, the carbon (carbon that contributes to ring formation) constituting the cyclic organic group may be a carbonyl carbon.

Preferred examples of the alumnium cation in the general formula (ZI) and the iodonium cation in the general formula (ZII) are shown below.

[化20]

Formula shown below (ZI), the general formula (ZII) the anion Z ^-, of the general formula (ZI-3) is Z _c ^- preferred embodiment ^- and the general formula (ZI-4) in Z.

[化21]

Any combination of the cation and anion can be used as a photoacid generator. In the present invention, the compound that generates acid by irradiation with actinic rays or radiation is preferably selected from the compound represented by the general formula (ZI-3) and the compound represented by the general formula (ZI-4) At least one of the compounds.

As the photoacid generator (C), a compound represented by the following general formula (iP) can also be used.

[化22]

In the general formula (iP), R ₁₀₁ to R ₁₀₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

The alkyl group of R ₁₀₁ to R ₁₀₆ is not particularly limited, and may be linear or branched, preferably an alkyl group having 1 to 20 carbons, more preferably an alkyl group having 1 to 15 carbons, and still more preferably An alkyl group having 1 to 10 carbon atoms. The alkyl group may have a substituent.

The cycloalkyl group of R ₁₀₁ to R ₁₀₆ is not particularly limited, and may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbons, more preferably a cycloalkyl group having 3 to 15 carbons, and further Preferably, it is a cycloalkyl group having 3 to 10 carbon atoms. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl. The cycloalkyl group may have a substituent.

The aryl group of R ₁₀₁ to R ₁₀₆ is not particularly limited, and may be monocyclic or polycyclic, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and further Preferably, it is an aryl group having 6 to 10 carbons. The aryl group may have a substituent.

The volume of the acid generated by the photoacid generator (C) is not particularly limited. In terms of suppressing the diffusion of the acid generated by exposure to the non-exposed part and improving the resolution, it is preferably 240 Å ³ or more, and more It is preferably 305 Å ³ or more, more preferably 350 Å ³ or more, and particularly preferably 400 Å ³ or more. Furthermore, in terms of sensitivity or solubility in the coating solvent, the volume of acid generated by the photoacid generator (C) is preferably 1500 Å ³ or less, more preferably 1000 Å ³ or less, and still more preferably It is 700 Å ³ or less. The value of the volume is obtained using "WinMOPAC" manufactured by Fujitsu Co., Ltd. When calculating the value of the volume, firstly, input the chemical structure of the acid, and secondly, use the structure as the initial structure, and determine the molecular force field calculation using the 3 method of Molecular Mechanics (MM) to determine the The most stable three-dimensional configuration, and then the most stable three-dimensional configuration is calculated using the parameterized model number (PM) 3 method to calculate the "accessible volume" of each acid.

The structure of the acid generated by the photoacid generator (C) is not particularly limited. In terms of suppressing the diffusion of the acid and improving the resolution, the acid generated by the photoacid generator (C) and the resin ( A) The interaction is strong. From this point of view, in the case where the acid generated by the photoacid generator (C) is an organic acid, it is preferable to exclude organic acid groups (for example, sulfonic acid groups, carboxylic acid groups, carbonylsulfonimidic acid groups). , Bissulfonimidic acid group, trisulfonyl methide acid group, etc.), and further has a polar group. Examples of the polar group include ether groups, ester groups, amide groups, amide groups, sulfo groups, sulfonyloxy groups, sulfonylamino groups, thioether groups, thioester groups, ureido groups, and carbonate groups. , Urethane group, hydroxyl group, mercapto group, etc. The number of polar groups that the acid generated by the photoacid generator (C) has is not particularly limited, but it is preferably one or more, and more preferably two or more. Among them, from the viewpoint of suppressing excessive development, the number of polar groups is preferably less than 6, more preferably less than 5, and still more preferably less than 4.

Among them, in terms of more excellent effects of the present invention, the photoacid generator (C) is preferably a photoacid generator containing an anion part and a cation part. As the photoacid generator (C), the photoacid generator described in paragraph 0144 to paragraph 0173 of JP 2019-045864 A can be cited.

In the sensitizing radiation-sensitive or radiation-sensitive resin composition produced by the production method of the present invention, the content of the photoacid generator (C) is preferably 0.1% by mass to the total solid content of the composition. 20% by mass, more preferably 0.5% by mass to 15% by mass, and still more preferably 1.0% by mass to 10% by mass. Therefore, it is preferable to adjust the addition amount of the photoacid generator (C) put into the container in the step (1) so that the photosensitive ray-sensitive or radiation-sensitive resin produced by the production method of the present invention The content of the photoacid generator (C) in the composition is within the above range.

The photoacid generator (C) may be used individually by 1 type, and may use 2 or more types together. When two or more photoacid generators (C) are used in combination, it is preferable that the total amount is within the above-mentioned range.

＜Acid diffusion control agent (D)＞ The acid diffusion control agent (also described as "acid diffusion control agent (D)") will be described. The acid diffusion control agent (D) functions as a quencher that captures the acid generated by the photoacid generator (C) during exposure and suppresses the resin in the unexposed part caused by the excess acid generation ( A) Reaction of (acid decomposable resin). As the acid diffusion control agent (D), for example, a basic compound (DA), a basic compound (DB) whose basicity decreases or disappears by irradiation with actinic rays or radiation, and a photoacid generator ( C) An onium salt (DC) that becomes a relatively weak acid, a low-molecular compound (DD) that has a nitrogen atom and a group detached by the action of an acid, an onium salt compound (DE) that has a nitrogen atom in the cation part, and the like. In the present invention, a known acid diffusion control agent can be suitably used. For example, paragraphs [0627] to paragraph [0664] of the specification of U.S. Patent Application Publication No. 2016/0070167, paragraphs [0095] to paragraph [0187] of the specification of U.S. Patent Application Publication No. 2015/0004544, and U.S. Patent Application Publication may be preferably used. Known compounds disclosed in paragraph [0403] to paragraph [0423] of the specification of 2016/0237190 and paragraph [0259] to paragraph [0328] of the specification of U.S. Patent Application Publication 2016/0274458 are used as acid diffusion control agents (D) .

As the basic compound (DA), the compounds described in paragraphs 0188 to 0208 of JP 2019-045864 A can be cited.

In the present invention, an onium salt (DC) which is a relatively weak acid with respect to the photoacid generator (C) can also be used as the acid diffusion control agent (D). When the photoacid generator (C) is used in combination with an onium salt that generates an acid that is relatively weak compared to the acid generated by the photoacid generator (C), if the The acid generated by the photoacid generator (C) upon irradiation collides with an unreacted onium salt having a weak acid radical anion, and the weak acid is released by the salt exchange and an onium salt having a strong acid radical anion is generated. In this process, the strong acid is exchanged into a weak acid with lower catalytic ability. Therefore, it is considered that the acid is deactivated in appearance and the acid diffusion can be controlled.

As an onium salt which becomes a relatively weak acid with respect to the photoacid generator (C), the onium salt described in paragraph 0224 to paragraph 0233 of JP 2019-070676 A can be cited.

As the basic compound (DA), preferably, a compound having a structure represented by the following formula (A) to formula (E) is mentioned.

[化23]

In general formula (A) and general formula (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably with 1 to 20 carbon atoms), and a cycloalkyl group (Preferably with 3 to 20 carbons), aryl (preferably with 6 to 20 carbons), alkylcarbonyl (preferably with 2 to 21 carbons), cycloalkylcarbonyl (preferably with 4 to 20 carbons) 21), arylcarbonyl (preferably carbon number 7-21), alkylsulfonyl (preferably carbon number 1-20), cycloalkylsulfonyl (preferably carbon number 3-20) or Arylsulfonyl (preferably carbon number 6-20). At least two of R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be bonded to form a ring, and may include at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, a carbonyl group, and a sulfonyl group in the ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

As for the alkyl group, the alkyl group having a substituent is preferably 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. The alkyl group in general formula (A) and general formula (E) is more preferably unsubstituted.

The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc., and more preferably has an imidazole structure , Diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure compound, alkylamine derivative with hydroxyl and/or ether bond, or hydroxyl and / Or aniline derivatives of ether linkages, etc.

The basic compound (DB) (hereinafter, also referred to as "compound (DB)") whose basicity decreases or disappears by irradiation with actinic rays or radiation is a compound that has a proton-accepting functional group and is Irradiation of actinic rays or radiation decomposes and the proton acceptor property decreases or disappears, or the proton acceptor property changes to acidity.

The so-called proton-accepting functional group is a functional group having a group or electrons that can electrostatically interact with protons, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group that has no contribution to π conjugation. The non-covalent electron pair is the functional group of the nitrogen atom. The nitrogen atom having a non-covalent electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[化24]

Examples of preferred partial structures of the proton-accepting functional group include crown ethers, aza crown ethers, primary to tertiary amines, pyridine, imidazole, and pyrazine structures.

The compound (DB) is decomposed by irradiation with actinic rays or radiation to produce a compound in which the proton acceptor property decreases or disappears, or the proton acceptor property changes to acidity. Here, the decrease or disappearance of proton acceptor, or the change from proton acceptor to acidity, is the change in proton acceptor caused by the addition of protons to the proton acceptor functional group. Specifically, This means that when a compound having a proton-accepting functional group (DB) and a proton generate a proton adduct, the equilibrium constant in the chemical equilibrium decreases. The proton acceptor property can be confirmed by performing a pH measurement.

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

The so-called acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in Handbook of Chemistry (II) (Revised 4th edition, 1993, The Chemical Society of Japan, Maruzen Co., Ltd.), for example. The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can also be used to obtain values from a database based on Hammett's substituent constants and well-known literature values through calculations. The values of pKa described in this manual all indicate values obtained by calculations using this software package.

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

In the composition of the present invention, an onium salt (DC) which is a relatively weak acid with respect to the acid generator can be used as an acid diffusion control agent. When an acid generator is used in combination with an onium salt that generates an acid that is relatively weak compared to the acid generated by the acid generator, if the acid generator is irradiated with actinic rays or radiation, it is generated by the acid generator. When the acid collides with an unreacted onium salt with a weak acid anion, the weak acid is released by salt exchange and an onium salt with a strong acid anion is produced. In this process, the strong acid is exchanged into a weak acid with lower catalytic ability, so the acid is apparently deactivated and the acid diffusion can be controlled.

As an onium salt which becomes a relatively weak acid with respect to an acid generator, the compound represented by the following general formula (d1-1)-general formula (d1-3) is preferable.

[化25]

In the formula, R ⁵¹ is an optionally substituted hydrocarbon group, Z ^2c is an optionally substituted hydrocarbon group of 1 to 30 carbon atoms (wherein, the fluorine atom is unsubstituted on the carbon adjacent to S), and R ⁵² is The organic group, Y ³ is a linear, branched or cyclic alkylene or arylene group, Rf is a hydrocarbon group containing a fluorine atom, and M ^{+ is} each independently an ammonium cation, a sulfonium cation, or an iodonium cation.

Preferable examples of the amenium cation or the iodonium cation represented by M ⁺ include the amenium cation exemplified in the general formula (ZI) and the iodonium cation exemplified in the general formula (ZII).

The onium salt (DC) which becomes a relatively weak acid with respect to the acid generator may also be a compound having a cation site and an anion site in the same molecule, and the cation site and anion site are linked by a covalent bond (hereinafter, Also known as "Compound (DCA)"). The compound (DCA) is preferably a compound represented by any of the following general formulas (C-1) to (C-3).

[化26]

In general formula (C-1) to general formula (C-3), R ₁ , R _2, and R ₃ each independently represent a substituent having 1 or more carbon atoms. L ₁ represents a divalent linking group or a single bond connecting a cation site and an anion site. -X ^- represents a group selected ^{_{-COO -, -SO 3 -, -SO}} 2 - and -N ^- anionic sites in -R _4. R ₄ represents that it has a carbonyl group (-C(=O)-), a sulfinyl group (-S(=O) ₂ -) and a sulfinyl group (-S(=O) at the connection site with the adjacent N atom -) is a monovalent substituent of at least one of them. R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In addition, in the general formula (C-3), combining two of R ₁ to R ₃ represents a divalent substituent, which may be bonded to the N atom by a double bond.

Examples of substituents having 1 or more carbon atoms in R ₁ to R ₃ include alkyl groups, cycloalkyl groups, aryl groups, alkoxycarbonyl groups, cycloalkoxycarbonyl groups, aryloxycarbonyl groups, and alkylaminocarbonyl groups. , Cycloalkylaminocarbonyl and arylaminocarbonyl, etc. Preferably, it is an alkyl group, a cycloalkyl group, or an aryl group.

_{Examples of L 1} as the divalent linking group include linear or branched alkylene, cycloalkylene, arylene, carbonyl, ether bond, ester bond, amide bond, urethane bond, urea A bond and a base formed by combining two or more of these. L _{1 is} preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a combination of two or more of these.

The low-molecular compound (DD) having a nitrogen atom and a group released by the action of an acid (hereinafter also referred to as "compound (DD)") preferably has a group released by the action of an acid on the nitrogen atom Amine derivatives. The group to be removed by the action of an acid is preferably an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether (hemiaminal ether) group, and more preferably Urethane group or semiamine acetal ether group. The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, and still more preferably 100-500. The compound (DD) may contain a urethane group having a protective group on the nitrogen atom. The protecting group constituting the urethane group can be represented by the following general formula (d-1).

[化27]

In the general formula (d-1), R _b each independently represents a hydrogen atom, an alkyl group (preferably with a carbon number of 1 to 10), a cycloalkyl group (preferably with a carbon number of 3 to 30), an aryl group (more Preferably it is a carbon number of 3-30), an aralkyl group (preferably a carbon number of 1-10) or an alkoxyalkyl group (preferably a carbon number of 1-10). R _b may be connected to each other to form a ring. The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R _b can each independently pass through a hydroxyl group, a cyano group, an amino group, a pyrrolidinyl group, N-hexahydropyridinyl group, a morpholinyl group, a pendant oxy group, etc. Functional group, alkoxy group or halogen atom substitution. The same applies to the alkoxyalkyl group represented by _{R b.}

As R _b , a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group, or a cycloalkyl group is more preferable. Examples of the ring formed by linking two R _b with each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof. As a specific structure of the group represented by general formula (d-1), the structure disclosed in paragraph [0466] of the specification of U.S. Patent Publication US2012/0135348A1 can be cited, but it is not limited to this.

The compound (DD) preferably has a structure represented by the following general formula (6).

[化28]

In the general formula (6), l represents an integer from 0 to 2, and m represents an integer from 1 to 3, and satisfies l+m=3. R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When 1 is 2, two _Ras may be the same or different, and two _Ras may be connected to each other and form a heterocyclic ring together with the nitrogen atom in the formula. Heteroatoms other than the nitrogen atom in the formula may be included in the heterocyclic ring. R _b in the general formula (d-1) is the same meaning as R _b is, preferred embodiments are also the same. In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group _{as R a} may be independently substituted with a group that is related to the alkyl group and cycloalkane group which _{may be substituted as R b} The groups of the group, the aryl group and the aralkyl group are the same as those described above.

Examples of the R _a is alkyl, cycloalkyl, aryl and aralkyl group (the group may be substituted with those of the group) Specific examples include the same specific examples of R _b and described in regard to the same group. As a specific structure of the particularly desirable compound (DD) in the present invention, the compound disclosed in paragraph [0475] of the specification of U.S. Patent Application Publication No. 2012/0135348A1 can be cited, but it is not limited to this.

The onium salt compound (DE) having a nitrogen atom in the cation part (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic part including a nitrogen atom in the cation part. The basic part is preferably an amine group, and more preferably an aliphatic amine group. More preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. In addition, from the viewpoint of improving basicity, it is preferable that the electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to the nitrogen atom. As a preferable specific structure of the compound (DE), the compound disclosed in paragraph [0203] of the specification of U.S. Patent Application Publication No. 2015/0309408A1 can be cited, but it is not limited to this.

In the sensitizing radiation-sensitive or radiation-sensitive resin composition produced by the production method of the present invention, the content of the acid diffusion control agent (D) relative to the total solid content of the composition (in the case of multiple Total) 0.1% by mass to 10.0% by mass is preferable, and 0.1% by mass to 5.0% by mass is more preferable. Therefore, it is preferable to adjust the addition amount of the acid diffusion control agent (D) put into the container in step (1) so that the sensitizing radiation or radiation-sensitive resin produced by the production method of the present invention The content of the acid diffusion control agent (D) in the composition is within the above range. In the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more.

＜Solvent＞ The solvent (also described as "solvent (S)") is explained. The solvent (S) preferably contains at least one of (M1) propylene glycol monoalkyl ether carboxylate and (M2), and the (M2) is selected from the group consisting of propylene glycol monoalkyl ether, lactate, acetate, At least one of the group consisting of alkoxy propionate, chain ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent in this case may further include components other than the component (M1) and the component (M2). If a solvent containing component (M1) or component (M2) is used in combination with the resin (A), the coatability of the sensitized radiation or radiation-sensitive resin composition is improved, and the number of development defects can be reduced. The pattern is therefore better.

In addition, as the solvent (S), for example, an alkanediol monoalkyl ether carboxylate, an alkanediol monoalkyl ether, an alkyl lactate, an alkyl alkoxypropionate, and a cyclic lactone ( Organic solvents such as mono-ketone compounds having 4 to 10 carbon atoms, which may contain a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxy acetate, and alkyl pyruvate, etc. .

In the sensitizing radiation-sensitive or radiation-sensitive resin composition produced by the production method of the present invention, the content of the solvent (S) is preferably adjusted so that the solid content concentration of the composition becomes 0.5% by mass to 40% by mass It is more preferable to adjust to 3% by mass to 30% by mass. In particular, in terms of the more excellent effects of the present invention, the solid content concentration of the sensitized radiation-sensitive or radiation-sensitive resin composition produced by the production method of the present invention is preferably 10% by mass or more, and most preferably 10% by mass to 30% by mass. Therefore, it is preferable to adjust the addition amount of the solvent (S) put into the container in step (1) so that the sensitized radiation or radiation sensitive resin composition produced by the production method of the present invention is The solid content concentration falls within the aforementioned range. Furthermore, the so-called solid content concentration refers to the mass of other components (components that can constitute the sensitizing radiation or radiation-sensitive film) other than the solvent relative to the total mass of the sensitizing radiation or radiation-sensitive resin composition percentage.

In the production method of the present invention, in step (1), in addition to the resin, photoacid generator (C), acid diffusion control agent (D), and solvent (S), other than these may be used The ingredients are added to the container. Examples of other components include crosslinking agents, alkali-soluble resins, dissolution inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in developing solutions. Furthermore, other ingredients may be added to the container in step (1), or may not be added in step (1), but may be added in steps other than step (1).

<Step (1-2)> The manufacturing method of the present invention preferably includes step (1-2) between step (1) and step (2), The step (1-2) is to mix the resin, the photoacid generator, the acid diffusion control agent and the solvent put into the container in the step (1). In step (1-2), in addition to the resin, photoacid generator, acid diffusion control agent, and solvent put into the container in step (1), other components may be further mixed. The mixing method in step (1-2) is not particularly limited. For example, it is preferable to stir and mix by the stirring blade. Step (1-2) starts after the end of step (1). Step (1-2) can be performed continuously with the step (1) (step (1-2) can be started at the end of step (1)), or step (1) can be started after a period of time ( 1-2) From the viewpoint of productivity, it is preferable to proceed continuously with step (1). In addition, when the resin, photoacid generator, acid diffusion control agent, and solvent are put into the container in step (1), the stirring blade in the container may be operated in advance to put all the ingredients into the container. While in the container (at the same time as the end of step (1)), start step (1-2) (that is, continue stirring in the container from the start of step (1) to the end of step (1-2)).

The mixing time in step (1-2) (ie, the time for performing step (1-2)) is not particularly limited, and is preferably 30 minutes or more, more preferably 1 hour or more, and still more preferably 2 hours or more, especially It is preferably more than 4 hours, particularly preferably more than 8 hours. It is considered that by setting the mixing time to 30 minutes or more, the aggregation state of the raw materials is stabilized, and the effects of the present invention are more likely to be exhibited. The upper limit of the mixing time is not particularly limited, but from the viewpoint of productivity, it is preferably 24 hours or less, more preferably 18 hours or less, and still more preferably 12 hours or less.

The temperature during mixing (the temperature of the contents in the container) is not particularly limited, but is preferably 15°C to 32°C, more preferably 20°C to 24°C. In addition, during mixing, the temperature of the contents in the container is preferably kept constant, preferably within ±10°C from the set temperature, more preferably within ±5°C, and even more preferably within ±1°C. The rotation speed of the stirring blade during stirring and mixing is not particularly limited, and is preferably 20 rpm to 500 rpm (rotations per minute), more preferably 40 rpm to 350 rpm, and further preferably 50 rpm to 300 rpm. When the mixing is stopped, it is preferable to confirm that each component is dissolved or uniformly dispersed in the solvent. When mixing, ultrasonic waves can also be applied to the contents in the container.

<Step (2)> Step (2) is to add at least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent to the container containing the resin, the photoacid generator, the acid diffusion control agent, and the solvent A step of.

In the present invention, step (2) is performed after step (1) is completed, preferably after step (1) is completed, step (2) is performed after more than 30 minutes have passed. The interval between step (1) and step (2) is preferably 30 minutes or more, more preferably 1 hour or more, more preferably 2 hours or more, particularly preferably 4 hours or more, particularly preferably Open for more than 8 hours. It is considered that by leaving the space between step (1) and step (2) for more than 30 minutes, the aggregation state of the raw materials is stabilized, and the effects of the present invention are more likely to be exhibited. The upper limit of the time between step (1) and step (2) is not particularly limited, but from the viewpoint of productivity, it is preferably 48 hours or less, more preferably 36 hours or less, and still more preferably 24 hours or less.

In the present invention, it is preferable to perform step (1-2) after step (1), and then perform step (2). Step (2) can be carried out continuously with the step (1-2), or can be carried out with a time interval after step (1-2). Furthermore, when steps (1-2) and (2) are continuously performed, it is set at the time of starting step (2) (that is, to the resin, photoacid generator, acid diffusion control agent and solvent contained therein). When at least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent is added to the container) Step (1-2) ends. However, in this case, during the step (2), the mixing of the contents in the container may be continued immediately after the step (1-2). Regarding the addition of at least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent in step (2), it may be contained in the container used in step (1) It can also be carried out relative to the contents transferred to other containers, etc. In step (2), when at least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent is added, the contents may be stirred or not, but From the viewpoint of improving the uniformity of the obtained sensitizing radiation or radiation-sensitive resin composition, it is preferable to stir. In the manufacturing method of the present invention, the stirring can be continued in the container from the beginning of step (1) to the end of step (2). In addition, after step (2) is completed (after the addition of at least one of the resin, the photoacid generator, the acid diffusion control agent, and the solvent is completed), it may be stirred in the container.

The amount of raw materials added in step (2) (in the case of multiple raw materials to be added, the total amount) is preferably the resin, photoacid generator, and acid diffusion control agent added to the container in step (1) 0.001% by mass to 100% by mass of the total amount of the solvent, more preferably 0.001% by mass to 50% by mass, and still more preferably 0.001% by mass to 30% by mass.

As one of the preferred aspects of the present invention, after step (1), the contents (composition containing resin, photoacid generator, acid diffusion control agent and solvent) in the container can be divided into two or more types The partial group is an aspect in which at least one of the partial groups is used for the evaluation of the physical properties. In this case, it is preferable to perform step (2) on a partial group different from the partial group used in the evaluation. In this aspect, "divide the contents in the container into two or more partial groups performed between step (1) and step (2), and use at least one of the partial groups to perform physical properties The "step of evaluation" is called step (B).

The evaluation in the step (B) is not particularly limited, and examples include: evaluation of the film properties of an organic film formed using at least one of the partial groups, or evaluation of the properties of the organic film in the partial group At least one kind of evaluation of the physical properties of the solution, etc.

That is, as one of the preferred aspects of the present invention, the following aspects may be cited: at least one of the partial groups is used to form an organic film, and the film physical properties of the organic film are evaluated, and based on the evaluation As a result, the step (2) is performed to adjust the physical properties of the target film. The physical properties of the film are preferably at least one of sensitivity, film thickness, contact angle (for example, water contact angle), complex refractive index, transmittance, and refractive index. In order to adjust the sensitivity, for example, it is considered to add an acid diffusion control agent. In order to adjust the film thickness, for example, it is considered to add a solvent. In order to adjust the contact angle, for example, adding resin is considered. In order to adjust the complex refractive index, for example, it is considered to add a photoacid generator. In order to adjust the transmittance, for example, it is considered to add a photoacid generator. In order to adjust the refractive index, for example, adding resin is considered.

In addition, as one of the preferred aspects of the present invention, the following aspect may be cited: using at least one of the partial groups to evaluate the physical properties of the solution, and performing the step (2) based on the result of the evaluation, so that Adjust the physical properties of the target solution. The physical properties of the solution are preferably at least one of complex refractive index, transmittance, and refractive index. In order to adjust the complex refractive index, for example, it is considered to add a photoacid generator. In order to adjust the transmittance, for example, it is considered to add a photoacid generator. In order to adjust the refractive index, for example, adding resin is considered.

＜Other steps＞ In addition to the steps (1), (1-2), (B), and (2), the manufacturing method of the present invention may also include other steps. For example, step (3) may also be included after step (2), and the step (3) is to further mix the contents in the container. In addition, the following step may also be included: filtering (for example, filter filtering) before step (1) or any time point after step (1) is performed.

[Pattern Formation Method] The actinic radiation-sensitive or radiation-sensitive resin composition produced by the production method of the present invention can be used, for example, for pattern formation in the production steps of semiconductor devices. The photosensitive ray-sensitive or radiation-sensitive resin composition manufactured by the manufacturing method of the present invention is typically a resist composition (preferably a chemically amplified resist composition), and may be a positive resist The composition may also be a negative resist composition. In addition, the sensitizing radiation-sensitive or radiation-sensitive resin composition produced by the production method of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development.

The pattern formation method using the sensitizing radiation-sensitive or radiation-sensitive resin composition manufactured by the manufacturing method of the present invention is not particularly limited, and preferably includes the following steps. Step a: A step of forming a resist film on a substrate using the sensitized radiation-sensitive or radiation-sensitive resin composition manufactured by the manufacturing method of the present invention Step b: A step of exposing the resist film to obtain an exposed resist film Step c: a step of developing the exposed resist film with a developing solution to form a pattern Hereinafter, the steps are described in detail.

(Step a: Resist film formation step) Step a is a step of forming a resist film on a substrate using the photosensitive ray-sensitive or radiation-sensitive resin composition manufactured by the manufacturing method of the present invention.

As a method of forming a resist film on a substrate using the sensitizing radiation-sensitive or radiation-sensitive resin composition manufactured by the manufacturing method of the present invention, a method of applying the composition on the substrate is exemplified. Furthermore, it is preferable to filter the composition as necessary before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. In addition, the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

The sensitized radiation-sensitive or radiation-sensitive resin composition manufactured by the manufacturing method of the present invention can be applied to those used in the manufacture of integrated circuit devices by an appropriate coating method such as a spinner or a coater. Substrate (e.g. silicon, silicon dioxide coating). As the coating method, spin coating using a spinner is preferred. After coating the composition, the substrate may be dried to form a resist film. Furthermore, if necessary, various base films (inorganic film, organic film, or anti-reflection film) may be formed on the lower layer of the resist film.

As a drying method, the method of heating (pre-baking: PB (PreBake)) is mentioned. Heating can be performed using a mechanism provided in a normal exposure machine and/or a developing machine, or can be performed using a hot plate or the like. The heating temperature is preferably 80°C to 150°C, more preferably 80°C to 140°C. The heating time is preferably 30 seconds to 1000 seconds, more preferably 40 seconds to 800 seconds.

The thickness of the resist film is not particularly limited. In the case of a resist film for KrF exposure, it is preferably 0.2 μm to 12 μm, more preferably 0.3 μm to 5 μm. In addition, in the case of a resist film for ArF exposure or EUV exposure, it is preferably 30 nm to 700 nm, and more preferably 40 nm to 400 nm.

Furthermore, a top coating composition may be used on the upper layer of the resist film to form a top coating. The top coat composition is preferably not mixed with the resist film, and can be evenly coated on the upper layer of the resist film. The film thickness of the top coating layer is preferably 10 nm to 200 nm, more preferably 20 nm to 100 nm. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, the top coat can be formed based on the description of paragraphs 0072 to 082 of Japanese Patent Laid-Open No. 2014-059543 Floor.

(Step b: Exposure step) Step b is a step of exposing the resist film to obtain an exposed resist film. As a method of exposure, a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask is mentioned. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, extreme ultraviolet light, extreme ultraviolet light, X-rays, and electron beams (Electron Beam, EB). The wavelength is preferably 250 nm or less, more preferably The far ultraviolet light below 220 nm, and more preferably 1 nm to 200 nm, specifically includes: KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), EUV (13 nm), X-ray and EB.

It is preferable to bake after exposure and before development (post exposure bake: PEB (Post Exposure Bake)). The heating temperature is preferably 80°C to 150°C, more preferably 80°C to 140°C. The heating time is preferably 10 seconds to 1000 seconds, more preferably 10 seconds to 180 seconds. Heating can be performed using a mechanism provided in a normal exposure machine and/or a developing machine, or can be performed using a hot plate or the like. This step is also described as post-exposure baking.

(Step c: development step) Step c is a step of developing the exposed resist film using a developing solution to form a pattern.

Examples of the development method include: a method of immersing the substrate in a bath filled with developer for a certain period of time (dipping method); a method of developing the substrate by depositing the developer on the surface of the substrate and standing still for a certain period of time by using surface tension (coating liquid) (Puddle) method); the method of spraying developer on the surface of the substrate (spray method); and the method of continuously spraying the developer on the substrate rotating at a certain speed while scanning the developer spray nozzle at a certain speed (dynamic distribution method) ). In addition, after performing the development step, a step of stopping the development while replacing the side with another solvent may be performed. The development time is not particularly limited as long as the resin in the unexposed part is fully dissolved, and it is preferably 10 seconds to 300 seconds, and more preferably 20 seconds to 120 seconds. The temperature of the developer is preferably 0°C to 50°C, more preferably 15°C to 35°C.

Examples of the developer include alkaline developer and organic solvent developer. As the alkaline developer, it is preferable to use an alkaline aqueous solution containing an alkali. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by Tetramethyl Ammonium Hydroxide (TMAH). An appropriate amount of alcohols, surfactants, etc. can also be added to the alkaline developer. The alkali concentration of the alkaline developer is usually 0.1% by mass to 20% by mass. In addition, the pH of the alkaline developer is usually 10.0 to 15.0.

The so-called organic solvent developer is a developer containing an organic solvent. Examples of the organic solvent used in the organic solvent developer include well-known organic solvents, including ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

(Other steps) The pattern forming method preferably includes a step of cleaning with an eluent after step c. As the rinsing liquid used in the rinsing step after the step of performing development using an alkaline developer, for example, pure water can be cited. Furthermore, an appropriate amount of surfactant can also be added to the eluent.

The rinsing liquid used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. The eluent is preferably an eluent containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents. Furthermore, an appropriate amount of surfactant can also be added to the eluent.

In addition, the formed pattern may be used as a mask to perform the etching treatment of the substrate. That is, the pattern formed in step c may be used as a mask, and the substrate (or the underlying film and the substrate) may be processed to form a pattern on the substrate. The processing method of the substrate (or the underlying film and the substrate) is not particularly limited, and it is preferable to dry-etch the substrate (or the underlying film and the substrate) by using the pattern formed in step c as a mask to form a pattern on the substrate. method. Dry etching may be one-stage etching, or may include multiple-stage etching. When the etching includes multiple stages of etching, the etching of each stage may be the same treatment or different treatments. Etching can use any of the well-known methods, and various conditions and the like can be appropriately determined according to the type and use of the substrate, and the like. For example, etching can be performed in accordance with "Proceeding of Society of Photo-optical Instrumentation Engineers (Proc. of SPIE)" Vol. 6924, 692420 (2008), Japanese Patent Laid-Open No. 2009-267112, etc. In addition, you can also follow the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook Fourth Edition 2007 Issuer: Japan Semiconductor Equipment and Materials International (SEMI)". Among them, as dry etching, oxygen plasma etching is preferred.

Various materials used in the present invention (for example, solvents, developing solutions, rinsing solutions, compositions for forming anti-reflection film, composition for forming top coat, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million, one part per million) or less, and more preferably 10 mass ppb (parts per billion, one part per million) or less, Furthermore, it is preferably less than 100 quality ppt (parts per trillion, one trillion), particularly preferably less than 10 quality ppt, and most preferably less than 1 quality ppt. Here, as metal impurities, Na, K, Ca, Fe, Cu, Mn, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Mo, Zr, Pb, Ti, V, W, Zn, etc.

As a method of removing impurities such as metals from the various materials, for example, filtration using a filter can be cited. The pore diameter of the filter is preferably 0.20 μm or less, more preferably 0.05 μm or less, and still more preferably 0.01 μm or less. The material of the filter is preferably fluororesins such as polytetrafluoroethylene (PTFE) and perfluoroalkoxy alkane (PFA), polyolefin resins such as polypropylene and polyethylene, nylon 6 and nylon 66 and other polyamide resins. The filter can also be a filter that has been cleaned in advance with an organic solvent. In the filter filtration step, multiple or multiple filters can also be connected in series or in parallel for use. When multiple filters are used, filters with different pore sizes and/or materials can be used in combination. In addition, various materials can be filtered multiple times, and the step of multiple filtering can also be a cyclic filtering step. As the circulating filtration step, for example, the method disclosed in Japanese Patent Laid-Open No. 2002-62667 is preferable. As the filter, a filter with reduced elution disclosed in Japanese Patent Application Laid-Open No. 2016-201426 is preferable. In addition to filter filtration, adsorption materials can also be used to remove impurities, and filter filtration and adsorption materials can also be used in combination. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. As a metal adsorbent, the metal adsorbent disclosed in Unexamined-Japanese-Patent No. 2016-206500 can be mentioned, for example. In addition, as a method of reducing impurities such as metals contained in the various materials, there can be mentioned: selecting raw materials with a low metal content as the raw materials constituting the various materials, filtering the raw materials constituting the various materials, or using a fluororesin. Methods such as lining or coating in the device, and distillation and other methods are carried out under the condition of suppressing pollution as much as possible. The preferred conditions for filter filtration of raw materials constituting various materials are the same as the above-mentioned conditions. In order to prevent the mixing of impurities, the various materials are preferably stored in the specifications described in U.S. Patent Application Publication No. 2015/0227049, Japanese Patent Laid-Open No. 2015-123351, Japanese Patent Laid-Open No. 2017-13804, etc. In the container. Various materials can be used after being diluted by the solvent used in the composition.

In addition, the present invention also relates to a manufacturing method of an electronic component including the pattern forming method and an electronic component manufactured by the manufacturing method. The electronic component of the present invention can be preferably mounted in electrical and electronic equipment (home appliances, office automation (OA), media-related equipment, optical equipment, communication equipment, etc.). [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the examples shown below.

<Resin> In Examples and Comparative Examples, the following resins were used. The following resins all use resins synthesized based on well-known techniques. Polymer-A～Polymer-E, Polymer-G～Polymer-J are resin (A), and Polymer-F is alkali-soluble resin. In addition, the weight average molecular weight (Mw) and the dispersion degree (Mw/Mn) of the resin are polystyrene conversion values measured by the above-mentioned GPC method (carrier: tetrahydrofuran (THF)). In addition, the composition ratio (mole% ratio) of the repeating units in the resin is ^{measured by 13} C-nuclear magnetic resonance (NMR).

[化29]

[化30]

＜Photoacid generator (C)＞ The structure of the compound used as a photoacid generator in an Example and a comparative example is shown below.

[化31]

＜Acid diffusion control agent (D)＞ The structure of the compound used as an acid diffusion control agent in an Example and a comparative example is shown below.

[化32]

＜Surface active agent (E)＞ As the surfactant, polymer (Polymer)-X or polymer (Polymer)-Y as a resin is used.

[化33]

Polymer-Y: Megafac R-41 (manufactured by DIC (Stock))

<Hydrophobic resin (F)> The structure of the polymer (Polymer)-Z used as the hydrophobic resin (F) is shown below. Polymer-Z uses those synthesized based on well-known techniques. In addition, the weight average molecular weight (Mw) of Polymer-Z is a polystyrene conversion value measured by the said GPC method (carrier: tetrahydrofuran (THF)). In addition, the composition ratio (mole% ratio) of the repeating units in the resin is ^{measured by 13} C-nuclear magnetic resonance (NMR).

[化34]

＜Solvent (S)＞ The solvents used in the examples and comparative examples are shown below. PGMEA: Propylene Glycol Monomethyl Ether Acetate PGME: Propylene Glycol Monomethyl Ether EL: Ethyl Lactate CyHx: Cyclohexanone GBL: γ-butyrolactone

(Example 1 KrF exposure, positive development) <Manufacturing of sensitizing radiation or radiation-sensitive resin composition> The manufacturing apparatus shown in FIG. 1 was used as the manufacturing apparatus of a resist composition, and the resist composition was manufactured as follows.

Step (1): Put the resin, photoacid generator (C), acid diffusion control agent (D), solvent (S) and added polymer shown in Table 1 into a stirring tank (volume 100 L). The input amount of each component except the solvent (S) in step (1) was adjusted so that the ratio (mass %) to the sum of all the components except the solvent (S) became the value shown in Table 1, respectively. In addition, the input amount of the solvent (S) was adjusted so that the solid content concentration (mass%) of the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 1) obtained through the step (2) described later was shown as a table 1 is the value shown.

Step (1-2): Stir the contents in the stirring tank at 23° C. and 150 rpm for 2 hours by means of a stirring blade.

Step (B): Divide 0.1 kg from the contents after step (1-2). Using the fractional group of 0.1 kg divided, the evaluation of the physical properties shown below was performed. In addition, the result of the evaluation of the physical properties shown below is not described in this specification. -Evaluation of membrane properties- On the Si substrate, the fractional group of 0.1 kg is spin-coated at a certain rotation speed by the spin coating method, and baked at a temperature of 80°C to 150°C for 45 seconds to 120 seconds to form an organic film (For example, in Example 1, baking was performed at 130°C for 90 seconds). Furthermore, for the Si substrate, hexamethyldisilazane treatment can be implemented, and Bottom Anti Reflection Coat (BARC) treatment for suppressing reflection can also be implemented. With respect to the obtained organic film, the sensitivity, film thickness, contact angle, complex refractive index, transmittance, and refractive index were evaluated as follows.

‧Sensitivity A pattern for sensitivity evaluation was formed on the organic film, and a scanning electron microscope (Scanning Electron Microscope, SEM) (S-9380II; manufactured by Hitachi) was used to perform critical dimension (CD) measurement. Sensitivity indicates the amount of exposure (dose amount) in the target CD value. The formation method of the pattern for sensitivity evaluation is as follows. For wafers with organic film, use KrF excimer laser scanner (made by ASML, PAS5500/850C, wavelength 248 nm, numerical aperture (Numerical Aperture, NA) 0.50), separated exposure mask To perform pattern exposure (for example, a line width of 150 nm, a 1:1 line and space pattern was formed in Example 1). Then, baking (Post Exposure Bake; PEB) is performed at a temperature of 80°C to 140°C for 45 seconds to 120 seconds (for example, in Example 1, baking is performed at 130°C for 60 seconds). Then, it develops for 30 to 60 seconds with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) (hereinafter, also referred to as "TMAHaq") as a developer, and spin-drying. In this way, a pattern for sensitivity evaluation was obtained.

‧Film thickness The organic film was measured at multiple points with a film thickness meter (VM-3210; made by SCREEN), and the average value was used as the film thickness.

‧Contact angle The contact angle of the organic film to pure water was measured by a contact angle meter (DM-700; manufactured by Xiehe Interface Science Co., Ltd.) and used as the contact angle.

‧Complex refractive index, transmittance, refractive index The organic film was measured (1.2 eV to 7.0 eV) with an ellipsometer (M-2000D; manufactured by J.A. Woollam Japan) to obtain the complex refractive index, refractive index, and transmittance.

-Evaluation of solution physical properties- For the fractional group of 0.1 kg, an absorbance photometer (manufactured by Shimadzu Corporation) was used to measure the complex refractive index, transmittance, and refractive index (200 nm to 400 nm).

Step (2): Add additional raw material 1 (Polymer-X) shown in Table 2 to the contents in the stirring tank. The addition amount of the additional raw material 1 (Polymer-X) in step (2) is adjusted to the additional raw material 1 (Polymer-X) relative to the resin and photoacid added in step (1). The addition amount (mass %) of the total amount of the agent, the acid diffusion control agent, and the solvent (in Table 2, described as the "total amount in step (1)") becomes the value shown in Table 2. From the beginning of step (1) to the end of step (2), use the stirring blade to continue stirring in the container. In addition, immediately after step (2) is completed (after all additional raw materials are added), the contents are continuously stirred for 4 hours. Then, the contents (solution) obtained through step (2) are passed through a filter containing a nylon membrane with a pore size of 0.01 μm to 0.15 μm, or a filter containing a polyolefin resin or a fluororesin with a pore size of 0.003 μm to 0.10 μm Membrane filter to produce sensitized radiation-sensitive or radiation-sensitive resin composition (resist composition 1). For the filter filtration, for example, a filter with a pore size of 0.1 μm including a nylon membrane and a filter with a pore size of 0.03 μm made of polyethylene may be used, and the filtration can be performed under a pressurized condition of 0.12 MPa. Multiple filters can be arranged in series or circulated. The solid content concentration of the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 1) is the value shown in Table 1 (8.4% by mass).

＜Evaluation of aggregation defects caused by raw materials＞ [Pattern formation KrF exposure, positive development] On the Si substrate (manufactured by Advanced Materials Technology Co., Ltd.) that has been treated with hexamethyldisilazane, the anti-reflection layer is not provided to achieve the target film thickness (for example, 700 nm in Example 1) The prepared resist composition was spin-coated at a rotation speed of (for example, 1500 rpm in Example 1), and baked at a temperature of 80°C to 150°C for 45 seconds to 120 seconds (PreBake; PB), Formation of sensitizing radiation or radiation-sensitive film (resist film). For the wafer on which the resist film is formed, a KrF excimer laser scanner (manufactured by ASML, PAS5500/850C, wavelength 248 nm, NA 0.50) is used for pattern exposure ( For example, in Example 1, a line width of 150 nm, a 1:1 line and space pattern was formed). Then, baking (Post Exposure Bake; PEB) is performed at a temperature of 80°C to 140°C for 45 seconds to 120 seconds (for example, in Example 1, baking is performed at 130°C for 60 seconds). Then, it is developed by TMAHaq for 30 to 60 seconds, and spin-dried. The pattern for defect evaluation was obtained in this way.

[Evaluation] The pattern was formed as described above, and the defect evaluation device (KLA2360; manufactured by KLA-Tencor) was used for defect evaluation. Re-inspect SEM (SEMVisionG3E FIB; manufactured by American Applied Materials (AMAT)) to obtain re-inspection images and count the number of condensation defects caused by raw materials. The results are shown in Table 2 below.

In the following Tables 1 and 2, all of the "%" described as the unit of the input amount of each raw material, the addition amount of additional raw materials (additional raw material 1 to additional raw material 4), and the solid content concentration of the resist composition Is the quality benchmark (ie, "quality %"). The unit "h" of the stirring time means "hour". The ratio of the solvents used is the mass ratio of various solvents to all solvents. The same applies to Tables 3 to 5 described later.

(Example 2～Example 19 KrF exposure, positive development) The type and amount of each component used, the stirring time in step (1-2), the type and amount of additional raw materials, and the solid content concentration of the obtained sensitized radiation or radiation-sensitive resin composition Except having changed to the content shown in Table 1 and Table 2, it carried out similarly to Example 1, and obtained the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 2-resist composition 19). In addition, a pattern was formed in the same manner as in Example 1, and evaluation of aggregation defects caused by the raw material was performed.

(Example 20 KrF exposure, negative development) The type and amount of each component used, the stirring time in step (1-2), the type and amount of additional raw materials, and the solid content concentration of the obtained sensitized radiation or radiation-sensitive resin composition Except having changed to the content shown in Table 1 and Table 2, it carried out similarly to Example 1, and obtained the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 20). Using the exposure mask obtained by reversing the light-transmitting part and the light-shielding part of the exposure mask used in Example 1 (positive development), n-butyl acetate (nBA) was used as the developer and methyl isobutyl was used Except that methanol was used as the eluent, the pattern was formed in the same manner as in Example 1, and the evaluation of the aggregation defect caused by the raw material was performed.

[Table 1] No. Resin Photo acid generator (C) Acid diffusion control agent (D) Add polymer Solvent (S) Solid content concentration type input type input type input type input Example 1 Polymer-A 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 2 Polymer-A 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 3 Polymer-A 97.68% PAG-A 2.00% Quencher-A 0.22% Polymer-X 0.10% PGMEA/80% PGME/20% 16.0% Example 4 Polymer-A 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 5 Polymer-A 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 6 Polymer-A 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 7 Polymer-A 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-Y 0.10% PGMEA/80% PGME/20% 8.4% Example 8 Polymer-A 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/100% 8.4% Example 9 Polymer-A 94.60% PAG-A/40% PAG-B/60% 4.50% Quencher-A 0.80% Polymer-Y 0.10% PGMEA/80% PGME/20% 8.4% Example 10 Polymer-A/50% Polymer-B/50% 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 11 Polymer-A 94.60% PAG-A 4.50% Quencher (Quencher)-A/40% Quencher (Quencher)-B/60% 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 12 Polymer-A 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 13 Polymer-A 94.60% PAG-A 4.50% Quencher (Quencher)-B 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 14 Polymer-B 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 15 Polymer-A 97.68% PAG-A 2.00% Quencher-A 0.22% Polymer-X 0.10% PGMEA/80% PGME/20% 16.0% Example 16 Polymer-A 97.68% PAG-A 2.00% Quencher-A 0.22% Polymer-X 0.10% PGMEA/80% PGME/20% 16.0% Example 17 Polymer-A 97.68% PAG-A 2.00% Quencher-A 0.22% Polymer-X 0.10% PGMEA/80% PGME/20% 16.0% Example 18 Polymer-A 96.13% PAG-C 3.55% Quencher-A 0.22% Polymer-X 0.10% PGMEA/80% PGME/20% 16.0% Example 19 Polymer-A 96.13% PAG-D 3.55% Quencher-A 0.22% Polymer-X 0.10% PGMEA/80% PGME/20% 16.0% Example 20 Polymer-C 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4%

[Table 2] No. Step (1-2) mixing time Additional raw materials 1 Additional raw materials 2 Additional raw materials 3 Additional raw materials 4 Exposure light source Developer The number of agglomeration defects caused by raw materials type The amount added relative to the total amount in step (1) type The amount added relative to the total amount in step (1) type The amount added relative to the total amount in step (1) type The amount added relative to the total amount in step (1) Example 1 2 h Polymer-X 0.003% KrF TMAHaq 6 Example 2 1 h Polymer-X 0.003% KrF TMAHaq 9 Example 3 2 h Polymer-X 0.006% KrF TMAHaq 5 Example 4 2 h Quencher-A 0.004% PGMEA 0.202% PGME 0.005% KrF TMAHaq 4 Example 5 2 h Polymer-A 0.067% PAG-A 0.007% Quencher-A 0.002% Polymer-X 0.001% KrF TMAHaq 4 Example 6 2 h Quencher-A 0.003% KrF TMAHaq 6 Example 7 2 h Quencher-A 0.003% KrF TMAHaq 6 Example 8 2 h Quencher-A 0.003% KrF TMAHaq 6 Example 9 2 h PAG-A 0.007% PAG-B 0.010% Quencher-A 0.003% KrF TMAHaq 5 Example 10 2 h Quencher-A 0.003% KrF TMAHaq 6 Example 11 2 h Quencher-A 0.003% KrF TMAHaq 6 Example 12 2 h Quencher-A 0.008% KrF TMAHaq 5 Example 13 2 h Quencher-B 0.008% KrF TMAHaq 5 Example 14 2 h Polymer-X 0.059% KrF TMAHaq 4 Example 15 4 h Polymer-X 0.006% KrF TMAHaq 5 Example 16 8 h Polymer-X 0.006% KrF TMAHaq 3 Example 17 4 h PAG-A 0.016% KrF TMAHaq 4 Example 18 2 h Quencher-A 0.008% KrF TMAHaq 4 Example 19 2 h PAG-D 0.013% Quencher-A 0.008% KrF TMAHaq 6 Example 20 2 h Quencher-A 0.003% KrF nBA 5

(Example 21 to Example 28 ArF exposure, positive development) The type and amount of each component used, the stirring time in step (1-2), the type and amount of additional raw materials, and the solid content concentration of the obtained sensitized radiation or radiation-sensitive resin composition Except having changed to the content shown in Table 3 and Table 4, it carried out similarly to Example 1, and obtained the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 21-resist composition 28). In addition, in addition to using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 0.85, Annular, outer sigma 0.9, inner sigma 0.6) as the exposure light source, the same as in Example 1. The pattern was formed in the same manner, and the evaluation of the aggregation defect caused by the raw material was performed. In addition, ultrapure water was used as the liquid immersion liquid.

(Example 29 ArF exposure, negative development) The type and amount of each component used, the stirring time in step (1-2), the type and amount of additional raw materials, and the solid content concentration of the obtained sensitized radiation or radiation-sensitive resin composition Except having changed to the content shown in Table 3 and Table 4, it carried out similarly to Example 1, and obtained the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 29). An exposure mask obtained by reversing the light-transmitting part and the light-shielding part of the exposure mask used in Example 21 (positive development), using n-butyl acetate (nBA) as the developer, and methyl isobutyl Except that methanol was used as the eluent, the pattern was formed in the same manner as in Example 21, and the evaluation of the aggregation defect caused by the raw material was performed.

(Example 30 ArF exposure, negative development) The type and amount of each component used, the stirring time in step (1-2), the type and amount of additional raw materials, and the solid content concentration of the obtained sensitized radiation or radiation-sensitive resin composition Except having changed to the content shown in Table 3 and Table 4, it carried out similarly to Example 1, and obtained the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 30). Except for using 2-heptanone (MAK) as the developer, a pattern was formed in the same manner as in Example 29, and evaluation of aggregation defects caused by the raw material was performed.

(Example 31 i-ray exposure, positive development) The type and amount of each component used, the stirring time in step (1-2), the type and amount of additional raw materials, and the solid content concentration of the obtained sensitized radiation or radiation-sensitive resin composition Except having changed to the content shown in Table 3 and Table 4, it carried out similarly to Example 1, and obtained the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 31). In addition, except that an i-line stepper (FPA-3000i5+ manufactured by Canon Co., Ltd.) was used as the exposure light source, the pattern was formed in the same manner as in Example 1, and the aggregation caused by the raw material was performed. Defect evaluation.

(Example 32 to Example 34 EUV exposure, positive development) The type and amount of each component used, the stirring time in step (1-2), the type and amount of additional raw materials, and the solid content concentration of the obtained sensitized radiation or radiation-sensitive resin composition Except having changed to the content shown in Table 3 and Table 4, it carried out similarly to Example 1, and obtained the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 32-resist composition 34). In addition, in addition to using EUV exposure equipment (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, External Sigma 0.68, Internal Sigma 0.36) as the exposure light source, and the implementation of In Example 1, the pattern was formed in the same manner, and the evaluation of the aggregation defect caused by the raw material was performed.

(Example 35 EUV exposure, negative development) The type and amount of each component used, the stirring time in step (1-2), the type and amount of additional raw materials, and the solid content concentration of the obtained sensitized radiation or radiation-sensitive resin composition Except having changed to the content shown in Table 3 and Table 4, it carried out similarly to Example 1, and obtained the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 35). An exposure mask obtained by reversing the light-transmitting part and the light-shielding part of the exposure mask used in Example 32 (positive development), using n-butyl acetate (nBA) as the developer, and methyl isobutyl Except that methanol was used as the eluent, a pattern was formed in the same manner as in Example 32, and evaluation of aggregation defects caused by the raw material was performed.

(Example 36~Example 37 Electron beam exposure, positive development) The type and amount of each component used, the stirring time in step (1-2), the type and amount of additional raw materials, and the solid content concentration of the obtained sensitized radiation or radiation-sensitive resin composition Except having changed to the content shown in Table 3 and Table 4, it carried out similarly to Example 1, and obtained the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition 36-resist composition 37). In addition, except that an electron beam drawing device (manufactured by Elionix Co., Ltd.; ELS-7500, acceleration voltage 50 keV) was used as the exposure light source, the pattern was formed in the same manner as in Example 1, and the Evaluation of agglomeration defects caused by raw materials.

[table 3] No. Resin Photo acid generator (C) Acid diffusion control agent (D) Add polymer Solvent (S) Solid content concentration type input type input type input type input Example 21 Polymer-D 90.50% PAG-A 8.20% Quencher-A 1.20% Polymer-X 0.10% PGMEA/80% PGME/20% 3.9% Example 22 Polymer-D 90.50% PAG-A 8.20% Quencher-A 1.20% Polymer-X 0.10% PGMEA/80% PGME/20% 3.9% Example 23 Polymer-D 90.50% PAG-B 8.20% Quencher-A 1.20% Polymer-X 0.10% PGMEA/80% PGME/20% 3.9% Example 24 Polymer-D 90.50% PAG-A 8.20% Quencher-A 1.20% Polymer-X 0.10% PGMEA/80% PGME/20% 3.9% Example 25 Polymer-E 95.10% PAG-A 4.00% Quencher (Quencher)-B 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 12.8% Example 26 Polymer-D 90.50% PAG-A 8.20% Quencher-A 1.20% Polymer-X 0.10% PGMEA/60% CyHx/40% 3.9% Example 27 Polymer-D 92.60% PAG-A 6.20% Quencher-A 1.10% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% Example 28 Polymer-D 92.50% PAG-A 6.20% Quencher-A 1.10% Polymer-Z 0.20% PGMEA/95% GBL/5% 3.9% Example 29 Polymer-D 90.50% PAG-A 8.20% Quencher-A 1.20% Polymer-X 0.10% PGMEA/80% PGME/20% 3.9% Example 30 Polymer-D 90.50% PAG-A 8.20% Quencher-A 1.20% Polymer-X 0.10% PGMEA/80% PGME/20% 3.9% Example 31 Polymer-F 94.10% PAG-E 5.40% Quencher (Quencher)-C 0.40% Polymer-X 0.10% PGMEA/80% PGME/20% 30.0% Example 32 Polymer-G 81.60% PAG-A 15.90% Quencher-A 2.40% Polymer-Y 0.10% PGMEA/80% PGME/20% 1.9% Example 33 Polymer-G 81.60% PAG-A 15.90% Quencher-A 2.40% Polymer-Y 0.10% PGMEA/80% PGME/20% 1.9% Example 34 Polymer-H 81.60% PAG-A 15.90% Quencher-A 2.40% Polymer-Y 0.10% PGMEA/80% PGME/20% 1.9% Example 35 Polymer-I 76.30% PAG-A 20.20% Quencher-A 3.40% Polymer-Y 0.10% PGMEA/80% PGME/20% 1.9% Example 36 Polymer-J 94.45% PAG-A 4.60% Quencher-A 0.85% Polymer-X 0.10% PGMEA/80% EL/20% 2.2% Example 37 Polymer-J 94.45% PAG-A 4.60% Quencher-A 0.85% Polymer-X 0.10% PGMEA/80% EL/20% 2.2%

[Table 4] No. Step (1-2) mixing time Additional raw materials 1 Additional raw materials 2 Additional raw materials 3 Exposure light source Developer The number of agglomeration defects caused by raw materials type The amount added relative to the total amount in step (1) type The amount added relative to the total amount in step (1) type The amount added relative to the total amount in step (1) Example 21 2 h Quencher-A 0.002% ArF TMAHaq 8 Example 22 2 h Quencher-A 0.004% ArF TMAHaq 6 Example 23 2 h PAG-B 0.004% ArF TMAHaq 8 Example 24 8 h Quencher-A 0.002% ArF TMAHaq 6 Example 25 2 h Quencher (Quencher)-B 0.005% PGMEA 0.006% ArF TMAHaq 7 Example 26 2 h PGMEA 0.034% CyHx 0.023% Polymer-X 0.00039% ArF TMAHaq 7 Example 27 2 h PAG-A 0.006% Quencher-A 0.003% ArF TMAHaq 9 Example 28 2 h Polymer-D 0.002% PAG-A 0.001% ArF TMAHaq 8 Example 29 2 h Quencher-A 0.002% ArF nBA 7 Example 30 2 h PAG-A 0.004% Quencher-A 0.002% ArF MAK 7 Example 31 8 h Quencher (Quencher)-C 0.012% PGMEA 0.900% PGME 0.225% i-Line TMAHaq 18 Example 32 2 h PAG-A 0.008% EUV TMAHaq 4 Example 33 6 h PAG-A 0.008% EUV TMAHaq 3 Example 34 2 h PAG-A 0.003% Quencher-A 0.001% EUV TMAHaq 4 Example 35 2 h PAG-A 0.007% EUV nBA 4 Example 36 2 h Polymer-J 0.019% Quencher-A 0.001% EB TMAHaq 4 Example 37 4 h Quencher-A 0.001% PGMEA 0.053% EL 0.013% EB TMAHaq 3

(Comparative example 1 to comparative example 3, comparative example 10, comparative example 11 KrF exposure, positive development) The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained sensitizing radiation or radiation sensitive resin composition were changed to those shown in Table 5. , Except that the addition of additional raw materials was not carried out, except that the sensitizing radiation-sensitive or radiation-sensitive resin composition (resist composition r1 to resist composition r3, resist composition R10, resist composition r11). In addition, a pattern was formed in the same manner as in Example 1, and evaluation of aggregation defects caused by the raw material was performed.

(Comparative Example 4 KrF exposure, negative development) The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained sensitizing radiation or radiation sensitive resin composition were changed to those shown in Table 5. Except that the addition of additional raw materials was not performed, in the same manner as in Example 1, a sensitizing ray-sensitive or radiation-sensitive resin composition (resist composition r4) was obtained. Using the exposure mask obtained by reversing the light-transmitting part and the light-shielding part of the exposure mask used in Example 1 (positive development), n-butyl acetate (nBA) was used as the developer and methyl isobutyl was used Except that methanol was used as the eluent, the pattern was formed in the same manner as in Example 1, and the evaluation of the aggregation defect caused by the raw material was performed.

(Comparative Example 5 to Comparative Example 6 ArF exposure, positive development) The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained sensitizing radiation or radiation sensitive resin composition were changed to those shown in Table 5. Except that no additional raw materials were added, a sensitizing ray-sensitive or radiation-sensitive resin composition (resist composition r5 to resist composition r6) was obtained in the same manner as in Example 1. In addition, in addition to using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 0.85, Annular, outer sigma 0.9, inner sigma 0.6) as the exposure light source, the same as in Example 1. The pattern was formed in the same manner, and the evaluation of the aggregation defect caused by the raw material was performed. In addition, ultrapure water was used as the liquid immersion liquid.

(Comparative Example 7 i-ray exposure, positive development) The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained sensitizing radiation or radiation sensitive resin composition were changed to those shown in Table 5. Except that the addition of additional raw materials was not performed, in the same manner as in Example 1, a sensitizing ray-sensitive or radiation-sensitive resin composition (resist composition r7) was obtained. In addition, except that an i-line stepper (FPA-3000i5+ manufactured by Canon Co., Ltd.) was used as the exposure light source, the pattern was formed in the same manner as in Example 1, and the aggregation caused by the raw material was performed. Defect evaluation.

(Comparative Example 8 EUV exposure, positive development) The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained sensitizing radiation or radiation sensitive resin composition were changed to those shown in Table 5. Except that the addition of additional raw materials was not performed, in the same manner as in Example 1, a sensitizing ray-sensitive or radiation-sensitive resin composition (resist composition r8) was obtained. In addition, in addition to using EUV exposure equipment (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, External Sigma 0.68, Internal Sigma 0.36) as the exposure light source, and the implementation of In Example 1, the pattern was formed in the same manner, and the evaluation of the aggregation defect caused by the raw material was performed.

(Comparative Example 9 Electron beam exposure, positive development) The type and amount of each component used, the stirring time in step (1-2), and the solid content concentration of the obtained sensitizing radiation or radiation sensitive resin composition were changed to those shown in Table 5. Except that the addition of additional raw materials was not performed, a sensitizing ray-sensitive or radiation-sensitive resin composition (resist composition r9) was obtained in the same manner as in Example 1. In addition, except that an electron beam drawing device (manufactured by Elionix Co., Ltd.; ELS-7500, acceleration voltage 50 keV) was used as the exposure light source, the pattern was formed in the same manner as in Example 1, and the Evaluation of agglomeration defects caused by raw materials.

[table 5] No. Resin Photo acid generator (C) Acid diffusion control agent (D) Add polymer Solvent (S) Solid content concentration Exposure light source Developer Engineering (1-2) mixing time The number of agglomeration defects caused by raw materials type input type input type input type input Comparative example 1 Polymer-A 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% KrF TMAHaq 2 h 18 Comparative example 2 Polymer-A 97.68% PAG-A 2.00% Quencher-A 0.22% Polymer-X 0.10% PGMEA/80% PGME/20% 16.0% KrF TMAHaq 2 h 59 Comparative example 3 Polymer-A 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% KrF TMAHaq 8 h 14 Comparative example 4 Polymer-C 94.60% PAG-A 4.50% Quencher-A 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 8.4% KrF nBA 2 h 17 Comparative example 5 Polymer-D 90.50% PAG-A 8.20% Quencher-A 1.20% Polymer-X 0.10% PGMEA/80% PGME/20% 3.9% ArF TMAHaq 2 h 20 Comparative example 6 Polymer-E 95.10% PAG-A 4.00% Quencher (Quencher)-B 0.80% Polymer-X 0.10% PGMEA/80% PGME/20% 12.8% ArF TMAHaq 2 h 84 Comparative example 7 Polymer-F 94.10% PAG-E 5.40% Quencher (Quencher)-C 0.40% Polymer-X 0.10% PGMEA/80% PGME/20% 30.0% i-Line TMAHaq 8 h 144 Comparative example 8 Polymer-G 81.60% PAG-A 15.90% Quencher-A 2.40% Polymer-Y 0.10% PGMEA/80% PGME/20% 1.9% EUV TMAHaq 2 h 15 Comparative example 9 Polymer-J 94.45% PAG-A 4.60% Quencher-A 0.85% Polymer-X 0.10% PGMEA/80% EL/20% 2.2% EB TMAHaq 2 h 20 Comparative example 10 Polymer-A 96.13% PAG-C 3.55% Quencher-A 0.22% Polymer-X 0.10% PGMEA/80% PGME/20% 16.0% KrF TMAHaq 2 h 52 Comparative example 11 Polymer-A 96.13% PAG-D 3.55% Quencher-A 0.22% Polymer-X 0.10% PGMEA/80% PGME/20% 16.0% KrF TMAHaq 2 h 61

Compared with the resist composition manufactured by Comparative Example 1 to Comparative Example 11 of the manufacturing method without adding additional raw materials, the resist composition of the Examples manufactured using the manufacturing method of the present invention is composed of raw materials. The agglomeration defect caused is improved. [Industrial availability]

According to the present invention, it is possible to provide a method for manufacturing a photosensitive ray-sensitive or radiation-sensitive resin composition with improved aggregation defects caused by raw materials, and a method for manufacturing the photosensitive ray-sensitive or radiation-sensitive resin composition. Pattern forming method and manufacturing method of electronic components.

The present invention has been described in detail with reference to specific embodiments, and it is clear to those skilled in the art that various changes or modifications can be added without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2020-032275) filed on February 27, 2020, and the content is incorporated into this application as a reference.

10: Stirring tank 12: Mixing shaft 14: Mixing blade 16: Circulation piping 18: filter 20: Discharge piping 22: discharge nozzle 100: Manufacturing device

FIG. 1 is a schematic diagram of an example of a manufacturing apparatus that can be used in a method of manufacturing a sensitized radiation-sensitive or radiation-sensitive resin composition.

10: Stirring tank

12: Mixing shaft

14: Mixing blade

16: Circulation piping

18: filter

20: Discharge piping

22: discharge nozzle

100: Manufacturing device

Claims (15)

A method for manufacturing a photosensitive ray-sensitive or radiation-sensitive resin composition, which sequentially includes: Step (1), put a resin, a compound that generates an acid by irradiation with actinic rays or radiation, an acid diffusion control agent, and a solvent into the container; and Step (2), adding the resin, the resin, and the solvent to a container containing the resin, the compound that generates acid by irradiation with actinic rays or radiation, the acid diffusion control agent, and the solvent. At least one of a compound that generates an acid by irradiation with actinic rays or radiation, the acid diffusion control agent, and the solvent. The method for producing an sensitized radiation-sensitive or radiation-sensitive resin composition according to claim 1, wherein the step (2) is performed after 30 minutes or more have passed after the step (1) is completed. The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the step (1-2) is included between the step (1) and the step (2), The step (1-2) is to mix the resin, the compound that generates acid by irradiation with actinic rays or radiation, the acid diffusion control agent, and the solvent. The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to claim 3, wherein the mixing time in the step (1-2) is 2 hours or more. The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to claim 3 or 4, wherein the mixing time in the step (1-2) is 4 hours or more. The method for producing an sensitized radiation-sensitive or radiation-sensitive resin composition according to any one of claims 3 to 5, wherein the mixing time in the step (1-2) is 8 hours or more. The method for producing a photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein the solid content concentration of the photosensitive ray-sensitive or radiation-sensitive resin composition is 10 mass %above. The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein the compound that generates an acid by irradiation with actinic rays or radiation is selected from the group consisting of At least one of the compound represented by the general formula (ZI-3) and the compound represented by the following general formula (ZI-4);

In the general formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, Cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group; R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group ; R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group; R _1c ～R _5c of any two or more, R & lt _5c and R _6c, R _6c and R _7c, R _5c and R _x and R _y and R _x represent each may be bonded to form a ring structure, the ring structure may independently contain oxygen Atom, sulfur atom, ketone group, ester bond or amide bond; Z _c ^- represents an anion;

In the general formula (ZI-4), l represents an integer from 0 to 2; r represents an integer from 0 to 8; R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxy group a carbonyl group; R ₁₄ represents a hydroxyl, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl or cycloalkyl group alkylsulfonyl group; R ₁₄ in the case where there is a plurality of, May be the same or different; R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group; two R ₁₅ may be bonded to each other to form a ring; when two R ₁₅ are bonded to each other to form a ring, they may also be The ring skeleton contains heteroatoms; Z ^- represents an anion. The method for producing a sensitized radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8, wherein, after the step (1), The contents in the container are divided into two or more partial groups, and at least one of the partial groups is used to evaluate the physical properties. The method for producing a sensitized radiation-sensitive or radiation-sensitive resin composition according to claim 9, wherein at least one of the partial groups is used to form an organic film, and the film physical properties of the organic film are evaluated, and The step (2) is performed based on the result of the evaluation so as to adjust the physical properties of the target film. The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to claim 10, wherein the film physical properties are at least one of sensitivity, film thickness, contact angle, complex refractive index, transmittance, and refractive index. The method for producing a sensitized radiation-sensitive or radiation-sensitive resin composition according to claim 9, wherein at least one of the partial groups is used to evaluate the physical properties of the solution, and the step is performed based on the result of the evaluation (2) In order to adjust the physical properties of the target solution. The method for producing an actinic radiation-sensitive or radiation-sensitive resin composition according to claim 12, wherein the solution physical property is at least one of a complex refractive index, a transmittance, and a refractive index. A pattern forming method includes: A step of forming a resist film on a substrate using the sensitized radiation-sensitive or radiation-sensitive resin composition manufactured according to the manufacturing method according to any one of claims 1 to 13; A step of exposing the resist film to obtain an exposed resist film; and A step of developing the exposed resist film using a developing solution to form a pattern. A manufacturing method of an electronic component includes the pattern forming method as described in claim 14.

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