TW201914991A - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and production method for electronic device - Google Patents

Abstract

Provided are: an actinic ray-sensitive or radiation-sensitive resin composition which has excellent storage stability and high sensitivity, and with which a pattern having excellent LWR is formed; a resist film; a pattern forming method; and a production method for an electronic device. This actinic ray-sensitive or radiation-sensitive resin composition contains an acid generation agent which, when irradiated with an actinic ray or a radiation, generates an acid, a resin the polarity of which increases due to an action of an acid, and a solvent, wherein the acid generation agent contains at least one selected from the group consisting of acid generation agents A containing cations having a lowest unoccupied orbital level of not less than -7.0 eV but less than -5.0 eV, acid generation agents B which generate imide compounds having a pKa of -3.0 to 5.0 as generated acids, and acid generation agents C which generate carboxylic acid group- or sulfonic acid group-containing compounds having a pKa of -3.0 to 3.5 as generated acids.

Description

Photosensitive or radiation sensitive resin composition, resist film, pattern forming method, and method of manufacturing electronic component

The present invention relates to a sensitized radiation or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method of manufacturing an electronic component.

Conventionally, in the manufacturing process of semiconductor elements such as IC (Integrated Circuit) and LSI (Large Scale Integrated Circuit), the use of photoresist compositions (hereinafter also referred to as "Photosensitive or radiosensitive resin composition".) Fine processing of lithography. In recent years, with the increasing integration of integrated circuits, it has been gradually required to form ultra-fine patterns in sub-micron regions or quarter-micron regions. At the same time, it was found that the exposure wavelength also tended to change from g-rays to i-rays, and further to short wavelengths such as KrF excimer laser light. Furthermore, currently, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV (Extreme Ultra Violet, extreme ultraviolet).

As the photosensitive radiation-sensitive or radiation-sensitive resin composition, for example, Patent Document 1 discloses a resist composition that can be applied to EUV exposure or the like. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2012-137565

However, when compared with, for example, ArF excimer laser light (wavelength 193 nm), due to the short wavelength of EUV (wavelength 13.5 nm), the exposure of the resist film has a characteristic that the number of incident photons is small when the same sensitivity is set. As a result, in EUV-based lithography, the number of photons randomly changes and the influence of "photon shot noise" is large, which becomes the main cause of the degradation of LWR (Line Width Roughness) . The same applies to lithography based on electron beams. In order to reduce the photon shot noise, it is effective to increase the number of incident photons by increasing the exposure (in other words, by lowering the sensitivity), but this is a trade-off relationship with the current need for higher sensitivity. Therefore, as a method of reducing photon shot noise without reducing sensitivity, the present inventors studied the use of an acid generator containing a cation with a low energy level of the lowest unoccupied molecular orbital (LUMO: Lowest Unoccupied Molecular Orbital) (In other words, an acid generator containing cations with high electron acceptability). It is considered that the acid generator containing the above-mentioned cation with a low LUMO energy level absorbs secondary electrons generated by resin and the like with high efficiency to generate acid when exposed to high-energy rays such as EUV and electron beams. The LWR can be improved without reducing the sensitivity. However, on the other hand, the inventors also found that the lower the LUMO level of the acid generator, the worse the storage stability. That is, it was found that the photosensitizing radiation or radiation-sensitive resin composition containing the acid generator is difficult to store for a long period of time due to decomposition of the acid generator.

Therefore, an object of the present invention is to provide a sensitized radiation or radiation-sensitive resin composition having excellent storage stability, high sensitivity, and excellent LWR of the formed pattern. In addition, an object of the present invention is to provide a resist film, a pattern forming method, and a method of manufacturing an electronic component using the above-mentioned photosensitive ray-sensitive or radiation-sensitive resin composition.

The inventors have conducted intensive studies in order to achieve the above-mentioned problems, and have found that the photosensitive radiation-sensitive or radiation-sensitive resin composition contains an acid generator (acid containing a cation having a predetermined LUMO energy level as an acid generator). Generator A), and selected from amide imide compounds having a predetermined range of pKa as acid generating agents (acid generator B) and carboxylic acid group-containing compounds having a predetermined range of pKa or having a predetermined range The pKa-containing sulfonic acid group-containing compound is used as one or more types of acid generators (acid generators C) to solve the above-mentioned problems, and the present invention has been completed. That is, it was found that the above-mentioned object can be achieved by the following configuration.

[1] A sensitized radiation or radiation sensitive resin composition, comprising: an acid generator that generates an acid by irradiation with actinic rays or radiation, a resin and a solvent whose polarity increases by the action of an acid, and a solvent, The above acid generator includes: an acid generator A containing a cation with a minimum unoccupied molecular orbital energy level of -7.0 eV or more and less than -5.0 eV; and selected from compounds containing amide imides with a pKa of -3.0 to 5.0 One or more types of acid generator B generating an acid and a compound containing a carboxylic acid group or a sulfonic acid group having a pKa of -3.0 to 3.5 as the acid generator C generating an acid. [2] The sensitized radiation or radiation sensitive resin composition according to [1], wherein the acid generator A contains a cation represented by the general formula (ZI) described later. [3] The sensitized radiation or radiation-sensitive resin composition according to [2], wherein at least one of R ^c described later is a substituent containing a fluorine atom. [4] The sensitized radiation or radiation-sensitive resin composition according to [2] or [3], wherein the cation represented by the above general formula (ZI) is a cation represented by the following general formula (ZII) . [5] The sensitized radiation or radiation-sensitive resin composition according to any one of [1] to [4], wherein the acid-generating pKa of the acid generator B and the acid-generating pKa of the acid generator C It is larger than the acid-generating pKa produced by the above-mentioned acid generator A. [6] The sensitized radiation or radiation sensitive resin composition according to any one of [1] to [5], wherein the acid generator B and the acid generator C are onium salts. [7] The sensitized radiation or radiation sensitive resin composition according to any one of [1] to [6], wherein the resin contains a halogen atom. [8] The sensitized radiation or radiation sensitive resin composition according to [7], wherein the halogen atom is a fluorine atom or an iodine atom. [9] A resist film formed of the sensitizing radiation or radiation-sensitive resin composition according to any one of [1] to [8]. [10] A pattern forming method, comprising: a resist film forming process, using the sensitized radiation or radiation sensitive resin composition described in any one of [1] to [8] to form a resist film The exposure process exposes the resist film; and the development process uses a developing solution to develop the exposed resist film. [11] A method of manufacturing an electronic component, including the pattern forming method described in [10]. [Effect of invention]

According to the present invention, it is possible to provide a sensitized radiation or radiation-sensitive resin composition having excellent storage stability, high sensitivity, and excellent LWR of the formed pattern. In addition, according to the present invention, it is possible to provide a resist film, a pattern forming method, and a method of manufacturing an electronic component using the above-mentioned sensitized radiation or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet, extreme ultraviolet (EUV: Extreme Ultraviolet), X-ray, and electron beam (EB) represented by an excimer laser. : Electron Beam) etc. "Light" in this specification means actinic rays or radiation. Unless otherwise specified, "exposure" in this manual includes not only the bright line spectrum using a mercury lamp, but also the extreme ultraviolet, extreme ultraviolet (EUV), and X-ray exposures represented by excimer lasers. Tracing by particle beams such as electron beams and ion beams. In this specification, "~" is used with the meaning including the numerical value described before and after it as a lower limit value and an upper limit value.

In this specification, (meth) acrylate represents acrylate and methacrylate, and (meth) acrylic acid represents acrylic acid and methacrylic acid.

In the label of the group (atomic group) in this specification, the undescribed substitution and the unsubstituted label include both a group without a substituent and a group with a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In addition, the "organic group" in this specification means the group containing at least 1 carbon atom.

In addition, in the present specification, the type of the substituent, the position of the substituent, and the number of substituents are not particularly limited, such as "may have a substituent". The number of substituents may be, for example, 1, 2, 3 or more. Examples of the substituent include non-metallic radicals other than the monovalent hydrogen atom. For example, the following substituent group T can be selected. (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 group, ethoxy group and third butoxy group; phenoxy group and Aryloxy group such as p-tolyloxy group; alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acetyloxy group such as acetyloxy group, propyloxy group and benzoyloxy group; acetyl group Acyl, benzyl, isobutyl, acryloyl, methacryloyl, and methoxalyl; methyl sulfanyl and tertiary butylsulfanyl ( tert-butyl sulfanyl) and other alkyl sulfanyl; phenyl sulfanyl and phenyl sulfanyl and p-tolyl sulfanyl and other aryl sulfanyl; aryl sulfanyl; alkyl Cycloalkyl; Aryl; Heteroaryl; Hydroxy; Carboxy; Methyl; Sulfo; Cyano; Alkylaminocarbonyl; Arylaminocarbonyl; Sulfonylamino; Silyl; Amino; Mono Alkylamino; dialkylamino; arylamino; and combinations of these.

[Photosensitizing radiation or radiation sensitive resin composition] As the characteristic points of the photoactive radiation or radiation sensitive resin composition of the present invention (hereinafter, also referred to as "the composition of the present invention."), There can be mentioned Examples of the acid generator that generates an acid by irradiation with actinic rays or radiation include the following acid generator A and the following acid generator B or the following acid generator C. Acid generator A: acid generator containing cations with a minimum unoccupied molecular orbital level (LUMO level) of -7.0 eV or more and less than -5.0 eV Acid generator B: the pKa (acid dissociation constant) is -3.0 ～ 5.0 amide imine compound as acid generator for acid generation Acid generator C: A compound containing a carboxylic acid group or sulfonic acid group with a pKa (acid dissociation constant) of -3.0 to 3.5 is used as an acid generator for acid generation The inventors have studied the storage stability of the photosensitive radiation-sensitive or radiation-sensitive resin composition, and it is clear that one of the reasons for the decomposition of the acid generator that generates cations having a low LUMO level is that the composition The nucleophilic attack caused by the so-called acid diffusion control agents (mainly basic compounds) contained in them. The acid diffusion control agent refers to trapping the acid generated from an acid generator or the like during exposure and suppressing the quenching of the reaction of the acid-degradable resin in the unexposed portion caused by the remaining generated acid The ingredients of the agent (quencher). The research results of the present inventors clearly showed that the sensitivity of the sensitizing ray or radiation-sensitive resin composition contains any one of the acid generator A and the acid generator B and the acid generator C as the quencher. High, and excellent storage stability. In addition, the LWR of the pattern formed by the above composition is also excellent.

The mechanism by which the composition of the present invention exhibits the above effect is not limited to this, but it is presumed as follows. For example, an acid generator B having an onium salt structure represented by X ⁺ Y ^-will be described as an example. In the acid generator B, it means that it generates acid (refers to the acid generated from the acid generator by actinic rays or radiation, represented by YH.) The larger the pKa, the stronger the nucleophilic property. That is, the nucleophilicity of Y ^- as the anion part constituting the acid generator B becomes stronger, and as a result, the cation in the acid generator A becomes vulnerable to nucleophilic attack. Now, the present inventors clearly know that when the LUMO level of the cation in the acid generator (equivalent to acid generator A) is less than -5.0 eV, if the amide imine compound is used as the acid generator for generating acid (equivalent In the acid generator B), when the pKa of the acid generator is 5.0 or less, the sensitivity of the obtained sensitizing radiation or radiation-sensitive resin composition is high, and the storage stability is also excellent. Also, it is clear that if a compound containing a carboxylic acid group or a sulfonic acid group is used as an acid generator that generates an acid (corresponding to the acid generator C), if the pKa of the acid generator is 3.5 or less, the obtained The sensitized radiation or radiation-sensitive resin composition has high sensitivity and excellent storage stability. In addition, from the viewpoint of ensuring the function as the acid-generating quencher, the lower limit of the pKa of the amide imine compound, the carboxylic acid group-containing compound, and the sulfonic acid group-containing compound is about -3.0. In addition, the lower limit of the LUMO level of the cation in the acid generator A is usually about -7.0 eV. Furthermore, since the sensitivity of the above-mentioned sensitizing ray or radiation-sensitive resin composition is high, the LWR of the obtained pattern is also excellent.

Hereinafter, the components contained in the composition of the present invention will be described in detail. In addition, the composition of the present invention is a so-called resist composition, which may be a positive resist composition or a negative resist composition. In addition, it may be a resist composition for alkaline development or a resist composition for organic solvent development. Among them, a positive resist composition and a resist composition for alkaline development are preferred. Typically, the composition of the present invention is a chemically amplified resist composition.

<Acid generator> The composition of the present invention contains the following acid generator A, the following acid generator B or the following acid as a compound (acid generator) that generates an acid by irradiation with actinic rays or radiation (acid generator) Producer C. Acid generator A: Acid generator containing cations with a minimum unoccupied molecular orbital level (LUMO level) of -7.0 eV or more and less than -5.0 eV Acid generator B: Acetate with pKa of -3.0 to 5.0 An amine compound as an acid generator that generates an acid Acid generator C: A compound containing a carboxylic acid group or a sulfonic acid group with a pKa of -3.0 to 3.5 is used as an acid generator that generates an acid

In the resist film (coating film of the sensitized radioactive or radiation-sensitive resin composition), the acid generated from the acid generator A (hereinafter, also referred to as "generated acid A1") mainly contributes to acid decomposition Deprotection of sex-based resins.

The acid generated from the acid generator B (hereinafter, also referred to as "generated acid B1") and the acid generated from the acid generator C (hereinafter, also referred to as "generated acid C1") are mainly used as Neutralizer functions. That is, the generated acid B1 and the generated acid C1 function as a quencher for suppressing the reaction of the acid-decomposable resin in the unexposed portion by the generated acid A1 and the like. Therefore, from the viewpoint of being excellent in function as a quencher, the pKa of the generated acid B1 and the generated acid C1 is larger than the pKa of the generated acid A1 (in other words, the generated acid B1 and the generated acid C1 are more important than the generated Acid A1 is a relatively weak acid). Hereinafter, the acid generator A, the acid generator B, and the acid generator C will be described separately.

(Acid generator A) Hereinafter, the acid generator A will be described first. The acid generator A may be in the form of a low-molecular compound, or may be in the form of being incorporated into a part of the polymer. In addition, the form of the low-molecular compound and the form incorporated in a part of the polymer may be used together. When the acid generator A is in the form of a low-molecular compound, its molecular weight is preferably 3000 or less, more preferably 2000 or less, and further preferably 1000 or less. When the acid generator A is in the form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (X) described later, or it may be incorporated into a resin different from the above-mentioned resin (X). Among them, the form in which the acid generator A is a low-molecular compound is preferred. The acid generator A is not particularly limited as long as it contains cations having a minimum unoccupied molecular orbital level (LUMO level) of -7.0 eV or more and less than -5.0 eV. By actinic rays Or a compound that generates organic acid by irradiation of radiation (preferably EUV and electron beam) is preferred. As the organic acid, for example, at least any one of sulfonic acid, bis (alkylsulfonyl) imide, and tri (alkylsulfonyl) methylate is preferable. Hereinafter, the acid generator A will be described as being divided into a cation portion and an anion portion.

<< Cation Part >> The cation part of the acid generator A is not particularly limited as long as the LUMO energy level is -7.0 eV or more and less than -5.0 eV. For example, it can be represented by the following general formula (ZI) Cationic and LUMO energy level is -7.0eV or more and less than -5.0eV. In addition, in this specification, the LUMO energy level of the acid generator A is a value measured using the quantum chemistry calculation program Gaussian09 (manufactured by American Gaussian Corporation) under the following conditions. · Density functional method · Generic function: B3LYP · Base function: TZVP

[Chemical Formula 1]

In the general formula (ZI), R ^a , R ^b and R ^c each independently represent a substituent. o and p each independently represent an integer of 0 to 5. q represents an integer of 1 to 5. case o is 2 or more, the plural R ^a may be the same, may be also different, and at least two R ^a may be bonded to each other to form a ring. When p is 2 or more, plural R ^b may be the same as or different from each other, and at least two R ^b may be bonded to each other to form a ring. When q is 2 or more, a plurality of R ^c may be the same as or different from each other, and at least two R ^c may be bonded to each other to form a ring. And, R ^a and R ^b, R ^b and R ^c and R ^a and R ^c may each be bonded to form a ring.

Can be further reduced from the viewpoint of the LUMO level, and the absorption efficiency on the electron beam and EUV superior viewpoint, as represented by R ^a, R ^b and R ^c of the substituent include a halogen atom (preferably It is a fluorine atom or an iodine atom, more preferably a fluorine atom.), An alkyl group (preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 6.), an alkyl group substituted by a halogen atom such as a fluorine atom Group (preferably, the carbon number is 1-10, more preferably, the carbon number is 1-6. In addition, perfluoroalkyl group is preferred.), Alkylsulfonyl group (preferably, the carbon number is 1-10, More preferably, the carbon number is 1 to 6.), cycloalkyl sulfonyl group (preferably, the carbon number is 1 to 10, more preferably, the carbon number is 1 to 6.), and alkoxy group (preferably, the carbon number It is 1-10, more preferably the carbon number is 1-6.) Etc. As the above-mentioned substituents, halogen atoms (preferably fluorine atoms or iodine atoms, more preferably fluorine atoms), or halogen atoms such as fluorine atoms are considered from the viewpoint of more excellent absorption efficiency for EUV and electron beams Substituted alkyl groups (preferably carbon numbers of 1 to 10, more preferably carbon numbers of 1 to 6. Furthermore, perfluoroalkyl groups are preferred.) Are preferred, alkyl groups substituted with halogen atoms such as fluorine atoms (Preferably, the carbon number is 1 to 10, and more preferably, the carbon number is 1 to 6. In addition, perfluoroalkyl group is more preferable.) It is more preferable.

From the viewpoint of being able to further reduce the LUMO energy level, it is preferable that the general formula (ZI) is a triphenylammonium cation containing at least one substituent. That is, in the general formula (ZI), the q represents an integer of 1 to 5, and the o and p each independently represent an integer of 0 to 5. In addition, from the viewpoint of further reducing the LUMO energy level and from the viewpoint of more excellent absorption efficiency for EUV and electron beams, in the general formula (ZI), at least one of the substituents is a substituent containing a fluorine atom Is better. That is, in the general formula (ZI), at least one of the substituents represented by R ^c is preferably a substituent containing a fluorine atom (that is, in the general formula (ZI), q is 1 Below, the substituent represented by R ^c represents a substituent containing a fluorine atom, and when q is 2 or more, the substituent represented by R ^c represents at least one substituent containing a fluorine atom). As a substituent containing a fluorine atom, a fluorine atom or an alkyl group substituted with a fluorine atom (preferably the carbon number is 1 to 10, more preferably the carbon number is 1 to 6. In addition, perfluoroalkyl group is preferred.) Is better. From the viewpoint that the LUMO level can be further reduced, the above q is preferably 1 to 3. From the viewpoint of being able to further reduce the LUMO energy level, it is preferable that the o and the p are independently 0 to 3, and more preferably 1 to 3.

Further, o is 2 or more the case, a plurality of R ^a may be the same, may be also different, and at least two R ^a may be bonded to each other to form a ring. In addition, when p is 2 or more, a plurality of R ^b may be the same as or different from each other, and at least two R ^b may be bonded to each other to form a ring. In addition, when q is 2 or more, a plurality of R ^c may be the same as or different from each other, and at least two R ^c may be bonded to each other to form a ring.

From the viewpoint that the LUMO energy level can be further reduced and the absorption efficiency of EUV and electron beams is more excellent, as the cation represented by the above general formula (ZI), the cation represented by the following general formula (ZII) is Better.

[Chemical Formula 2]

In the general formula (ZII), with R ^a in the general formula (ZI) in the same meaning as R ^a, preferred aspects are also the same. In the above general formula (ZII), R ^b1 , R ^b2 , R ^c1 and R ^c2 each independently represent a substituent containing a fluorine atom. As the substituent containing a fluorine atom, as described above. In the above general formula (ZII), o represents an integer of 1 to 3.

Hereinafter, specific examples of the cation represented by the above general formula (ZI) will be illustrated, but the present invention is not limited thereto. In addition, in this specification, "Me" represents a methyl group.

[Chemical Formula 3]

[Chemical Formula 4]

"Anion Department" It is preferable that the acid generator A contains a non-nucleophilic anion (anion having a significantly low ability to cause a nucleophilic reaction). Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anion, aromatic sulfonic acid anion, camphorsulfonic acid anion, etc.), carboxylic acid anions (aliphatic carboxylic acid anion, aromatic carboxylic acid anion and (Aralkyl carboxylic acid anions, etc.), sulfonyl amide imide anions, bis (alkyl sulfonyl) amide imide anions and tri (alkyl sulfonyl) methide anions.

The aliphatic part of the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, a linear or branched alkyl group having a carbon number of 1 to 30, or a carbon number of Cycloalkyl groups of 3 to 30 are preferred.

As the aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion, an aryl group having 6 to 14 carbon atoms is preferred, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. The substituent is not particularly limited, and specific examples include halogen atoms such as a nitro group and a fluorine atom, carboxyl groups, hydroxyl groups, amine groups, cyano groups, and alkoxy groups (preferably having 1 to 15 carbon atoms), Alkyl group (preferably carbon number 1-10), cycloalkyl group (preferably carbon number 3-15), aryl group (preferably carbon number 6-14), alkoxycarbonyl group (preferably Is carbon number 2-7), acetyl group (preferably carbon number 2-12), alkoxycarbonyloxy (preferably carbon number 2-7), alkylthio group (preferably carbon number Is 1-15), alkylsulfonyl (preferably carbon number 1-15), alkyliminosulfonyl (preferably carbon number 1-15), and aryloxysulfonyl (Preferably, the carbon number is 6 to 20).

As the aralkyl group in the aralkyl carboxylate anion, an aralkyl group having 7 to 14 carbon atoms is preferred, and examples thereof include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthyl Butyl.

Examples of the sulfonylate imide anions include saccharin anions.

As the alkyl group in the bis (alkylsulfonyl) amide imide anion and the tri (alkylsulfonyl) methylate anion, an alkyl group having 1 to 5 carbon atoms is preferred. Examples of the substituent of such alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxy groups. Sulfonyl, a fluorine atom or an alkyl group substituted with a fluorine atom are preferred. In addition, the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. By this, the acid strength increases.

As other non-nucleophilic anion, and examples thereof include fluorinated phosphorus (e.g., PF ₆ ^-), boron trifluoride (e.g., BF ₄ ^-) and antimony fluoride (e.g., SbF ₆ ^-).

From the viewpoint of acid strength, in order to improve the sensitivity, it is preferable that the pKa of the generated acid be 2.0 or less. In addition, the lower limit value of the pKa that generates an acid is not particularly limited, and is, for example, about -20. The acid-generating pKa can be measured by the method described later.

In addition, as the non-nucleophilic anion, an anion represented by the following general formula (SA1) is also preferable.

[Chemical Formula 5]

In the general formula (SA1), Ar represents an aryl group, and may further have a substituent other than a sulfonic acid anion and a-(D-B) group. Examples of the substituent that may be further included include a fluorine atom and a hydroxyl group.

n represents an integer of 0 or more. As n, 1 to 4 is preferable, 2 to 3 is more preferable, and 3 is still more preferable.

D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfenyl group, a sulfonic acid group, a sulfonic acid ester group, an ester group, and a group composed of two or more of these.

B represents a hydrocarbon group. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Among them, aliphatic hydrocarbon groups are preferred, and cyclic aliphatic hydrocarbon groups are more preferred. As the D-B group, D is a single bond, and B is an aliphatic hydrocarbon group. B is preferably isopropyl or cyclohexyl.

In addition, as the non-nucleophilic anion, an anion represented by the following general formula (AN1) is also preferable.

[Chemical Formula 6]

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. When a plurality of R ¹ and R ² are present, they may be the same or different. L represents a divalent linking group, and L may be the same or different when there are plural. A represents a cyclic organic group. x represents an integer of 1-20, y represents an integer of 0-10, and z represents an integer of 0-10.

The general formula (AN1) will be described in further detail. The carbon number of the alkyl group in the alkyl group substituted with the fluorine atom of Xf is preferably 1-10, and more preferably 1-4. In addition, as the alkyl group substituted with a fluorine atom of Xf, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group. Specific examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ etc., wherein the fluorine atom, or CF ₃ is Better. In particular, Xf of both is preferably a fluorine atom.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and the number of carbons in the substituent is preferably 1 to 4. As the substituent, a C 1-4 perfluoroalkyl group is preferred. Specific examples of the alkyl group having a substituent of R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F _7. CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ etc. Among them, CF ₃ is preferred. As R ¹ and R ² , a fluorine atom or CF ₃ is preferred.

x is preferably 1-10, more preferably 1-5. y is preferably from 0 to 4, and 0 is more preferably. z is preferably 0 to 5, and 0 to 3 is more preferable. The divalent linking group of L is not particularly limited, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO _2- , alkylene, Cycloalkylene, alkenyl, and a plurality of these linking groups, etc., and a linking group having a total carbon number of 12 or less are preferred. Among them, -COO-, -OCO-, -CO-, or -O- is preferred, and -COO-, or -OCO- is more preferred.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aromatic ring group, and a heterocyclic group (including not only those having aromaticity but also those having no Aromatic ones) etc. The alicyclic group may be monocyclic or polycyclic, and monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl are preferred. In addition, norbornyl, tricyclodecyl , Polycyclocycloalkyl such as tetracyclodecyl, tetracyclododecyl and adamantyl are preferred. Among them, cyclohexyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, adamantyl and other alicyclic groups having a bulky structure with a carbon number of 7 or more can prevent the post-exposure heating process The diffusivity of the film in the process is better from the viewpoint of improving MEEF (Mask Error Enhancement Factor). Examples of the aromatic ring group include benzene ring, naphthalene ring, phenanthrene ring and anthracene ring. Examples of the heterocyclic group include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, those derived from furan ring, thiophene ring or pyridine ring are preferred.

In addition, examples of the cyclic organic group include a lactone structure, and specific examples include a lactone structure represented by the following general formulas (LC1-1) to (LC1-17). In addition, in the following general formulas (LC1-1) to (LC1-17), examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 4 to 7 carbon atoms. , C 1-8 alkoxy, C 2-8 alkoxycarbonyl, carboxyl, halogen atom, hydroxyl, cyano and acid-decomposable groups, etc., C 1-4 alkyl, A cyano group or an acid-decomposable group is preferred. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. In addition, there are a plurality of substituents (Rb ₂ ) that can be bonded to each other to form a ring.

[Chemical Formula 7]

The cyclic organic group may have a substituent. Examples of the substituents include alkyl groups (which may be linear, branched, or cyclic, and the number of carbons is preferably 1 to 12). Cycloalkyl groups (which may be monocyclic or polycyclic) Any one of the rings may be a spiro ring when it is polycyclic. A carbon number of 3 to 20 is preferred.), An aryl group (a carbon number of 6 to 14 is preferred.), A hydroxyl group, an alkoxy group , Ester group, amide group, urethane group, urea group, thioether group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be a carbonyl carbon.

Also, as the acid generator A, from the viewpoint of improving the resolution by suppressing the diffusion of the acid generated during exposure to the non-exposed part, the volume size of 130 Å ³ or more is generated by EUV or electron beam irradiation Acid (preferably sulfonic acid) compounds are preferred. As an acid generator, among them, compounds that generate an acid with a volume of 190Å ³ or more (more preferably sulfonic acid) are more preferable, and compounds that generate an acid with a volume of 270Å ³ or more (more preferably sulfonic acid) are more Preferably, compounds that produce acids (more preferably sulfonic acids) with a volume size of 400Å ³ or more are particularly preferred. Wherein, from the viewpoint of sensitivity or solubility in the coating solvent consideration the volume of 2000Å ³ or less is preferred, 1500Å ³ or less is more preferred. In addition, the value of the volume mentioned above was obtained using "WinMOPAC" manufactured by Fujitsu Limited. When calculating the volume value, first of all, input the chemical structure of the acid related to each case, and then, use this structure as the initial structure and determine it by molecular force field calculation using MM (Molecular Mechanics) 3 method The most stable three-dimensional shape of each acid, and then, by performing molecular orbital calculation using the PM (Parameterized Model) 3 method for these most stable three-dimensional coordination, the “accessible volume (accessible volume) of each acid can be calculated volume) ".

Hereinafter, specific examples of the acid generated by the acid generator A (acid having a proton bonded to the anion portion) and its volume are shown, but the present invention is not limited to this. In addition, the volume shown in the following example is a calculated value (unit Å ³ ). Also, 1Å is 1 × 10 ^-10 m.

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

[Chemical Formula 11]

One type of acid generator A may be used alone, or two or more types may be used simultaneously. In the composition of the present invention, the content of the acid generator A (in the case of plural types, the total amount thereof) is preferably 0.1 to 50% by mass relative to the total solid content of the composition, and more preferably 5 to 40% by mass Preferably, 5 to 30% by mass is more preferable.

(Acid generator B) Next, the acid generator B will be described. The acid generator B is an acid generator that uses an amide imine compound having a pKa of -3.0 to 5.0 as an acid generator. In addition, in this specification, the acid dissociation constant pKa means the acid dissociation constant pKa in the aqueous solution. For example, it is described in the Chemical Handbook (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Company, Limited). The lower the value, the higher the acid strength. The acid dissociation constant pKa in the aqueous solution can be specifically measured by using an infinitely diluted aqueous solution and measuring the acid dissociation constant at 25 ° C, and can also be calculated based on Hammett using the following software Substituent constants and database values of well-known literature values. All pKa values described in this specification represent values calculated by calculation using the software. Software: Advanced Chemistry Development (ACD / Labs) pKa Database V8.0

The acid generator B generates an acid as an imide compound. In the present specification, the amide imine compound refers to a compound having a bonding group represented by any one of (1X-1) to (1X-3) shown below. In addition, in (1X-1) to (1X-3), * represents a bonding position.

[Chemical Formula 12]

The acid generator B preferably has an acid-generating pKa of -2.0 to 4.8.

It is preferable that the acid generator B is a low molecule, and its molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and further preferably 1,000 or less.

As the acid generator B, an onium salt structure is preferable, and a compound represented by the following general formula (ZIII) or a compound represented by the following general formula (ZIV) is preferable.

[Chemical Formula 13]

In the general formula (ZIII), L ¹¹ represents a bonding group represented by any one of (2X-1) to (2X-3) shown below. In addition, in (2X-1) to (2X-3), * represents a bonding position. R ^d and R ^e each independently represents a hydrocarbon group may have a substituent. In addition, R ^d and R ^e may be bonded to each other to form a ring. M _B ⁺ represents a cation.

[Chemical Formula 14]

As the hydrocarbon group represented by the sum R ^d and R ^e, it may be any one of aliphatic hydrocarbon group and aromatic hydrocarbon group. The aliphatic hydrocarbon group is not particularly limited, and an alkyl group (which may be linear, branched, or cyclic.) Is preferred. The carbon number of the aliphatic hydrocarbon group is not particularly limited. For example, 1 to 15 is preferred, 1 to 10 is more preferred, and 1 to 6 is further preferred. The aromatic hydrocarbon group is not particularly limited, and its carbon number is, for example, 1 to 20, and phenyl is preferred.

R ^d and R ^e may be bonded to each other to form a ring. Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a polycyclic condensed ring formed by combining two or more such rings. Examples of the ring include a 3 to 10 member ring, a 4 to 8 member ring is preferred, and a 5 or 6 member ring is more preferred.

The R ^d represents a hydrocarbon group and R ^e, R ^d and by a ring, and R ^e are bonded to each other to form the group may have a substituent. Examples of the substituent include halogen atoms (preferably fluorine atoms). Wherein the pKa is set from the viewpoint of the predetermined range, by ¹¹ L (2X-2) represents the case of the hydrocarbon group represented by the R ^d and R ^e is a carbon atom and L of the location ^11, It is preferable that the substituent does not have a halogen atom.

M _B ⁺ represents a cation. The M _B ⁺ is not particularly limited. For example, a cation represented by the following general formula (WI) or a cation represented by the general formula (WII) is preferred.

[Chemical Formula 15]

In the above general formula (WI), 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 to 30, preferably 1 to 20. In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group may be included in the ring. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, butyl group and pentyl group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

As the cation represented by the general formula (WI), the cation represented by the general formula (WI-1) described later, or the cation represented by the general formula (WI-2) described later is preferable.

First, the cation represented by the general formula (WI-1) will be described. The cation represented by the general formula (WI-1) is an aryl amide cation in which at least one of R ₂₀₁ to R ₂₀₃ in the general formula (WI) is an aryl group. Aryl sulfonium cation R ₂₀₁ ~ R ₂₀₃ all may be an aryl group, can be thought R ₂₀₁ ~ R ₂₀₃ is an aryl group and the remaining part is alkyl or cycloalkyl. Examples of the aryl amide cation include triaryl amide cation, diarylalkyl amide cation, aryl dialkyl amide cation, diarylcycloalkyl amide cation and aryl dicycloalkyl amide cation.

As the aryl group included in the aryl cation, phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group may be an aryl group having a heterocyclic structure containing 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. In addition, when the aryl amide cation has two or more aryl groups, the presence of two or more aryl groups may be the same or different. The aryl benzyl cation has, as required, an alkyl group or a cycloalkyl group having a straight-chain alkyl group having 1 to 15 carbon atoms, a branched-chain alkyl group having 3 to 15 carbon atoms, or a ring having 3 to 15 carbon atoms. The alkyl group is preferred, and examples thereof include methyl, ethyl, propyl, n-butyl, second butyl, third butyl, cyclopropyl, cyclobutyl, and cyclohexyl groups.

The aryl group, alkyl group and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ may each independently have an alkyl group (for example, carbon number of 1 to 15), a cycloalkyl group (for example, carbon number of 3 to 15), an aromatic group As a substituent, a 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.

Next, the cation represented by the general formula (WI-2) will be described. The cation represented by the general formula (WI-2) is a cation in which R ₂₀₁ to R ₂₀₃ in the general formula (WI) each independently represent an organic group having no aromatic ring. Among them, the aromatic ring refers to the aromatic ring containing hetero atoms. As the organic group not having an aromatic ring of R ₂₀₁ to R ₂₀₃ , the carbon number is usually 1 to 30, and the carbon number is preferably 1 to 20. R ₂₀₁ to R ₂₀₃ each independently represent an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkyl group is preferred The oxycarbonylmethyl group is more preferred, and the linear or branched 2-oxoalkyl group is further preferred.

As the alkyl group and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ , a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, Propyl, butyl, and pentyl) or cycloalkyl having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, and norbornyl) are preferred. R ₂₀₁ to R ₂₀₃ may be further substituted by 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.

Next, the cation represented by the general formula (WII) will be described. In the general formula (WII), R ₂₀₄ and R ₂₀₅ each independently represent an aryl group, an alkyl group, or a cycloalkyl group. As the aryl group represented by R ₂₀₄ and R ₂₀₅ , phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group represented by R ₂₀₄ and R ₂₀₅ may be an aryl group having a heterocyclic structure including an oxygen atom, a nitrogen atom, or a sulfur atom. 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 represented by R ₂₀₄ and R ₂₀₅ , a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, Propyl, butyl, and pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, and norbornyl) is preferred.

The aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₄ and R ₂₀₅ may each independently have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₄ and R ₂₀₅ may have include, for example, alkyl groups (for example, carbon number of 1 to 15) and cycloalkyl groups (for example, carbon number It is 3-15), an aryl group (for example, carbon number 6-15), an alkoxy group (for example, carbon number 1-15), a halogen atom, a hydroxyl group, a phenylthio group, etc.

[Chemical Formula 16]

In the general formula (ZIV), R ²¹ represents an alkyl group or an alkyl group substituted with at least one fluorine atom. L ¹¹ and L ¹¹ in the formula the meaning (ZIII) are the same. Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. L ¹² represents a divalent linking group. W represents an organic group containing a cyclic structure. s represents an integer of 1-3. t represents an integer of 0-10.

The alkyl group represented by R ²¹ may have a substituent, and the carbon number is preferably 1 to 4. As the alkyl group represented by R ²¹ substituted with at least one fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms is preferred.

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, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred, and CF ₃ is more preferred. Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group, and a fluorine atom or CF ₃ is more preferable. In particular, Xf of both is more preferably a fluorine atom.

L ¹² represents a divalent linking group. L ¹² of the presence of a plurality, L ¹² may be the same, also be different. Examples of the divalent linking group include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO _2- , and An alkyl group (preferably having a carbon number of 1 to 6) and a cycloalkyl group in which a carbon atom can be substituted with a hetero atom (preferably having a carbon number of 3 to 15).

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

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl, and anthracenyl. The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can more suppress the diffusion of acid. In addition, the heterocyclic group may or may not be aromatic. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.

The cyclic organic group may have a substituent. Examples of the substituent include alkyl groups (which may be linear or branched, and preferably have 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic and Any one of the spiro rings, with a carbon number of 3-20 being preferred), an aryl group (with a carbon number of 6-14 being preferred), a hydroxyl group, an alkoxy group, an ester group, an amide group, a carbamate Group, urea group, sulfide group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be a carbonyl carbon.

s represents an integer of 1-3. t represents an integer of 0 to 10, preferably an integer of 1 to 5.

One type of acid generator B may be used alone, or two or more types may be used simultaneously.

Hereinafter, specific examples of the acid generator B will be illustrated, but the present invention is not limited thereto.

[Chemical Formula 17]

(Acid generator C) Next, the acid generator C will be described. The acid generator C is a compound containing a carboxylic acid group or a sulfonic acid group with a pKa of -3.0 to 3.5 as an acid generator that generates an acid. In addition, the definition of the acid dissociation constant pKa is as described above.

From the viewpoint of more excellent LWR, the acid generator C preferably has an acid-generating pKa of 2.0 to 3.5.

The acid generator C is preferably a low molecule, and its molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and further preferably 1,000 or less.

As the acid generator C, an onium salt structure is preferable, and a compound represented by the following general formula (ZV) or a compound represented by the following general formula (ZVI) is preferable.

[Chemical Formula 18]

In the general formula (ZV), R ^f represents a hydrocarbon group having at least one electron-withdrawing group as a substituent. In the general formula (ZVI), R ^g represents a hydrocarbon group which may have a substituent. In the general formula (of ZVs) and formula (ZVI), M _C ⁺ represents a cation.

The hydrocarbon group represented by R ^f may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group is not particularly limited, and an alkyl group (which may be linear, branched, or cyclic.) Is preferred. The carbon number of the aliphatic hydrocarbon group is not particularly limited. For example, 1 to 15, 1 to 10 are preferred, and 1 to 6 are further preferred. The aromatic hydrocarbon group is not particularly limited, and its carbon number is, for example, 1 to 20, and phenyl is preferred.

From the viewpoint of adjusting pKa to a predetermined range, the hydrocarbon group represented by R ^f has at least one electron-withdrawing group as a substituent. The electron-withdrawing group is not particularly limited, and examples thereof include halogen atoms (preferably fluorine atoms, iodine atoms, or chlorine atoms, more preferably fluorine atoms.), And alkyl groups substituted with halogen atoms such as fluorine atoms ( Preferably, the carbon number is 1 to 10, and more preferably the carbon number is 1 to 6. Furthermore, perfluoroalkyl groups are preferred.), Cyano, nitro, and carbonyl groups. As the above electron-withdrawing group, among them, a halogen atom (preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom.) Or an alkyl group substituted with a halogen atom such as a fluorine atom (preferably the carbon number is 1-10, More preferably, the carbon number is 1 to 6. Furthermore, perfluoroalkyl groups are preferred.) Is preferred. In addition, the hydrocarbon group represented by R ^f may have a substituent other than the above electron-withdrawing group. Examples of the substituent include a hydroxyl group, an alkoxy group, and an amine group.

The hydrocarbon group represented by R ^g may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group is not particularly limited, and an alkyl group (which may be linear, branched, or cyclic.) Is preferred. The carbon number of the aliphatic hydrocarbon group is not particularly limited, but it is, for example, 1 to 15, preferably 1 to 10. In addition, the carbon number of the aliphatic hydrocarbon group may be substituted with carbonyl carbon. The aromatic hydrocarbon group is not particularly limited, and its carbon number is, for example, 1 to 20, and phenyl is preferred.

The hydrocarbon group represented by R ^g may have a substituent. The substituent is not particularly limited, and examples thereof include the groups exemplified in the above substituent group T.

M _C ⁺ represents a cation. As M _C ⁺ , it has the same meaning as the above M _B ⁺ , and the preferred aspects are also the same.

As the acid generator C, a compound represented by the following general formula (ZV-1) is more preferable from the viewpoint that the LWR of the formed pattern is more excellent.

[Chemical Formula 19]

In the general formula (ZV-1), R ^h represents a substituent. r represents an integer of 1 to 5. When r is 2 or more, a plurality of R ^h may be the same as or different from each other, and at least two R ^h may be bonded to each other to form a ring. Among them, at least one of R ^h is an electron-withdrawing group.

The substituent represented by R ^h has the same meaning as the substituent that may have the above R ^f , and the preferred aspects are also the same. In addition, at least one of R ^h is an electron-withdrawing group. r represents an integer of 1 to 5, preferably 1 to 3. In addition, when r is 2 or more, a plurality of R ^h may be the same as or different from each other. In addition, M _C ⁺ are as described above.

One type of acid generator C may be used alone, or two or more types may be used simultaneously.

Hereinafter, specific examples of the acid generator C will be illustrated, but the present invention is not limited thereto.

[Chemical Formula 20]

(Contents of the acid generator B and the acid generator C) In the composition of the present invention, the content of the acid generator selected from the acid generator B and the acid generator C (in the case of plural kinds, the total amount is relative) The total solid content in the composition is preferably 0.5 to 20% by mass, more preferably 1.0 to 15% by mass, and further preferably 2.0 to 10% by mass.

<Resin> The composition of the present invention includes a resin whose polarity increases by the action of an acid (hereinafter, also referred to as "resin (X)"). In addition, as described above, the resin (X) is a resin whose polarity is increased by the action of an acid. Therefore, in the pattern forming method of the present invention described later, typically, when an alkaline developer is used as the developer, a positive pattern is appropriately formed, and when an organic developer is used as the developer, it is appropriate To form a negative pattern.

Hereinafter, preferred aspects of the repeating unit having the resin (X) will be described in detail.

(Repeating unit having an acid-decomposable group) The resin (X) includes a repeating unit having a structure in which a polar group is protected by a release group that is detached by the action of an acid (hereinafter, also referred to as "acid-decomposable repeating unit"). ) Is better. That is, it is preferable that the resin (X) includes a repeating unit having a group that decomposes by the action of an acid to generate a polar group (hereinafter, also referred to as "acid-decomposable group"). The resin having this repeating unit increases the solubility with respect to the alkali developer by the polarity of the acid and increases the solubility to the organic solvent. As the polar group in the repeating unit having a structure (acid-decomposable group) in which the polar group is protected by an escaping group detached by the action of an acid, an alkali-soluble group is preferred, and examples thereof include carboxyl groups and phenolic hydroxyl groups , Fluorinated alcohol group, sulfonate group, sulfonamide group, sulfonimide group, (alkylsulfonyl group) (alkylcarbonyl) methylene group, (alkylsulfonyl group) (alkylcarbonyl group) amide Imino, bis (alkylcarbonyl) methylene, bis (alkylcarbonyl) imino, bis (alkylsulfonyl) methylene, bis (alkylsulfonyl) imide, Acid groups such as tri (alkylcarbonyl) methylene and tri (alkylsulfonyl) methylene, and alcoholic hydroxyl groups. 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 that is released by the action of an acid include groups represented by formulae (Y1) to (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 formula (Y1) and formula (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (straight chain or branched chain) or cycloalkyl group (monocyclic or polycyclic). In addition, when all of Rx ₁ to Rx ₃ are alkyl groups, it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups. Wherein, Rx ₁ ~ Rx ₃ each independently represents a linear or branched alkyl group is preferred, Rx ₁ ~ Rx ₃ each independently represent a linear alkyl group is more preferred. Two of Rx ₁ to Rx ₃ may be bonded to form a single ring or multiple rings. As the alkyl group of Rx ₁ to Rx _3, a C _1-4 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tertiary butyl groups is preferred. As cycloalkyl groups of Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic groups such as norbornyl, tetracyclodecyl group, tetracyclododecyl group and adamantyl group Is preferred. Cycloalkyl formed as two bonds of Rx ₁ to Rx ₃ , monocyclic cycloalkyl such as cyclopentyl and cyclohexyl, and norbornyl, tetracyclodecyl, tetracyclododecyl Polycyclic cycloalkyl groups such as adamantyl and the like are preferred, and monocyclic cycloalkyl groups having 5 to 6 carbon atoms are more preferred. The cycloalkyl group formed by bonding two Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. Among the groups represented by formula (Y1) or formula (Y2), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the above-mentioned cycloalkyl group.

In formula (Y3), R ₃₆ and R ₃₇ each independently represent a hydrogen atom or a monovalent organic group. R ₃₈ represents a monovalent organic group. R ₃₇ and R ₃₈ may be bonded to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. R ₃₆ is also preferably a hydrogen atom.

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

[Chemical Formula 21]

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group 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 contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group, an amine group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination of these groups (for example , Combining alkyl and cycloalkyl groups). In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be substituted with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. In addition, 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 in which an alkylene group and an aryl group are combined. 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). From the viewpoint of miniaturization of the resist pattern, L ₂ is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl group, cyclohexyl group and norbornyl group, and examples of the tertiary alkyl group include tertiary butyl group and adamantyl group. In these aspects, since Tg (glass transition temperature) and activation energy become higher, blurring can be suppressed while ensuring film strength.

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

The content of the acid-decomposable repeating unit in the resin (X) (when there are a plurality of acid-decomposable repeating units, the total) is, for example, 10% by mass or more and 20% by mass of all repeating units of the resin (X) % Or more is preferable, and 30% by mass or more is more preferable. The upper limit value is, for example, 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less. The content of the acid-decomposable repeating unit (total number of acid-decomposable repeating units is the total) is, for example, 10 to 90% by mass, and 20 to 70% by mass relative to all repeating units of the resin (X). Preferably, 20 to 60% by mass is more preferable, and 30 to 60% by mass is even more preferable.

Hereinafter, preferred aspects of the acid-decomposable repeating unit will be described in detail. In the resin (X), as the acid-decomposable repeating unit, it is preferable to include a repeating unit X1 described later, a repeating unit X2 described later, and / or a repeating unit X3 described later.

"Phenolic hydroxyl group has a repeating unit protected by an acid-decomposable group (acid-decomposable group) which is decomposed by the action of an acid" As the resin (X), there is no particular limitation, and the acid-decomposable repeating unit includes The repeating unit (hereinafter, also referred to as "repeating unit X1") of a structure (acid-decomposable group) protected by a detached group decomposed and decomposed by the action of an acid is preferred. In addition, in the present specification, the phenolic hydroxyl group refers to a group in which a hydrogen atom of an aromatic hydrocarbon group is substituted with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group may be a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

Examples of the leaving group that is decomposed and decomposed by the action of an acid include groups represented by the above formulas (Y1) to (Y4).

As the repeating unit X1, a structure having a hydrogen atom in a phenolic hydroxyl group protected by groups represented by formulae (Y1) to (Y4) is preferred.

As the repeating unit X1, a repeating unit represented by the following general formula (AII) is preferred.

[Chemical Formula 22]

In the general formula (AII), R ₆₁ , R ₆₂ and R ₆₃ 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 ₆₂ may bond with Ar ₆ to form a ring, and R ₆₂ at this time represents a single bond or an alkylene group. X ₆ represents a single bond, -COO-, or -CONR _64- . R ₆₄ represents a hydrogen atom or an alkyl group. L ₆ represents a single bond or an alkylene group. Ar ₆ represents an (n + 1) -valent aromatic hydrocarbon group, and when bonded to R ₆₂ to form a ring, represents an (n + 2) -valent aromatic hydrocarbon group. In the case of n ≧ 2, Y ₂ each independently represents a hydrogen atom or a group detached by the action of an acid. Among them, at least one of Y ₂ represents a group detached by the action of an acid. The group that Y ₂ is detached by the action of an acid is preferably a group represented by formulae (Y1) to (Y4). n represents an integer of 1-4.

The alkyl group represented by R ₆₁ , R ₆₂ and R ₆₃ in the general formula (AII) is an alkyl group which may have a substituent, methyl, ethyl, propyl, isopropyl, n-butyl, and second butyl , Hexyl, 2-ethylhexyl, octyl, dodecyl and other alkyl groups with a carbon number of 20 or less are preferred, alkyl groups with a carbon number of 8 or less are more preferred, and alkyl groups with a carbon number of 3 or less are Further preferred.

The cycloalkyl represented by R ₆₁ , R ₆₂ and R ₆₃ in the general formula (AII) may be monocyclic or polycyclic. The optionally substituted cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl group, cyclopentyl group, and cyclohexyl group, which is monocyclic, is preferred. Examples of the halogen atom represented by R ₆₁ , R ₆₂ and R ₆₃ in the general formula (AII) 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 represented by R ₆₁ , R ₆₂ and R ₆₃ in the general formula (AII) is preferably the same as the alkyl group in the aforementioned R ₆₁ , R ₆₂ and R ₆₃ .

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, and an alkoxy group It is preferably a carbonyl group (carbon number 2 to 6) and the like, and a carbon number of 8 or less.

Ar ₆ represents an (n + 1) -valent aromatic hydrocarbon group. When n is 1, the divalent aromatic hydrocarbon group may have a substituent, for example, a phenylene group, a tolylene group (tolylene group), a naphthyl group, a anthracenyl group and the like having a carbon number of 6 to 18 Aryl, or, for example, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, Mitsui, imidazole, benzimidazole, triazole, thiadiazole, and thiazole, etc. Is better.

As a specific example of the (n + 1) -valent aromatic hydrocarbon group when n is an integer of 2 or more, (n-1) arbitrary removal from the above-mentioned specific examples of the divalent aromatic hydrocarbon group can be given as appropriate. A group made of hydrogen atoms. The (n + 1) -valent aromatic hydrocarbon group may further have a substituent.

Examples of the substituents that the aforementioned alkyl group, cycloalkyl group, alkoxycarbonyl group and (n + 1) -valent aromatic hydrocarbon group may have include, for example, R ₆₁ , R ₆₂ and R in the general formula (AII) The alkyl groups mentioned in ₆₃ ; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl. The alkyl group of R ₆₄ in -CONR _64- (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₆ may have a substituent, methyl, ethyl, propyl, isopropyl, n-butyl , A second butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group, and the like, an alkyl group having a carbon number of 20 or less is preferable, and an alkyl group having a carbon number of 8 or less is more preferable. As X ₆ , a single bond, -COO- or -CONH- is preferred, and a single bond or -COO- is more preferred.

As the alkylene group of L ₆ , alkyl groups having 1 to 8 carbon atoms, such as methylene, ethylidene, propyl, butyl, hexyl, and octyl groups, which may have substituents are preferred . As Ar ₆ , an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent is preferred, and a benzene ring group, a naphthalene ring group or a biphenylene ring group is more preferred. Among them, among the repeating units represented by the general formula (AII), repeating units derived from hydroxystyrene are preferred. That is, Ar ₆ is preferably a benzene ring group.

Hereinafter, specific examples of the repeating unit corresponding to the repeating unit X1 are listed, but the present invention is not limited to these specific examples.

[Chemical Formula 23]

[Chemical Formula 24]

[Chemical Formula 25]

The resin (X) may contain one kind of repeating unit X1 alone, or two or more kinds at the same time.

The content of the repeating unit X1 in the resin (X) (when there are a plurality of repeating units X1, the total) is, for example, 10% by mass or more and 20% by mass or more with respect to all repeating units of the resin (X) Good, more than 30% by mass. The upper limit value is, for example, 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less. The content of the repeating unit X1 (when there are multiple repeating units X1, the total) is, for example, 10 to 90% by mass, preferably 20 to 70% by mass, with respect to all the repeating units of the resin (X). 60% by mass is more preferable, and 30 to 60% by mass is even more preferable.

"Repeat Unit with Structure (Acid Decomposable Group) Protected by a -COOH Group by a Breaking Group" The resin (X) may include a structure protected by a break group (acid decomposability) as an acid decomposable repeating unit Radical) of repeating unit X2. As the repeating unit X2, a repeating unit represented by the following general formula (AI) is preferred.

[Chemical Formula 26]

In the general formula (AI), Xa ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group. T represents a single bond or a divalent linking group. Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group. Any two of Rx ₁ to Rx ₃ may be bonded to form a ring structure, or may not be formed.

Examples of the divalent linking group of T include alkylene group, aryl group, -COO-Rt-, -O-Rt- and the like. In the formula, Rt represents an alkylene group, a cycloalkylene group or an aryl group. T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and -CH ₂ -,-(CH ₂ ) _2- , or-(CH ₂ ) ₃ -is more preferable. T is a single bond is better.

Xa ₁ is preferably a hydrogen atom or an alkyl group. The alkyl group of Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom). The alkyl group of Xa ₁ preferably has 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, hydroxymethyl, and trifluoromethyl. The alkyl group of Xa ₁ is preferably a methyl group.

The alkyl groups as Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tertiary Butyl and the like are preferred. The carbon number of the alkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3. In the alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ , a part of the carbon-carbon bond may be a double bond. As the cycloalkyl groups of Rx ₁ , Rx ₂ and Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl groups, etc. Polycyclic cycloalkyl is preferred.

As a ring structure formed by two bonds of Rx ₁ , Rx ₂ and Rx ₃ , a monocyclic cycloalkane ring such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring and cyclooctane ring, or norbornane Polycyclic cycloalkyl rings such as ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring are preferred. Among them, cyclopentyl ring, cyclohexyl ring or adamantane ring is more preferable. As the ring structure formed by the two bonds of Rx ₁ , Rx ₂ and Rx ₃ , the structure shown below is also preferable.

[Chemical Formula 27]

Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (AI) are given, but the present invention is not limited to these specific examples. The following specific examples correspond to the case where Xa ₁ in the general formula (AI) is a methyl group, but Xa ₁ can be arbitrarily substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

[Chemical Formula 28]

In the resin (X), as the repeating unit X2, it is also preferable to have the repeating units described in paragraphs <0336> to <0369> of US Patent Application Publication No. 2016 / 0070167A1.

The resin (X) may have one kind of repeating unit X2 alone, or may have two or more kinds at the same time.

When the resin (X) contains the repeating unit X2, the content of the repeating unit X2 (when there are a plurality of repeating units X2, the total) is, for example, 5 mass% or more relative to all the repeating units in the resin (X) , 10% by mass or more is preferable. The upper limit value is, for example, 90% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less. The content of the repeating unit X2 (when there are multiple repeating units X2, the total) is, for example, 5 to 90% by mass, preferably 5 to 60% by mass relative to all repeating units in the resin (X), 10 ~ 40% by mass is better.

<< Acid-decomposable repeating unit represented by the following general formula (A) >> The resin (X) may contain an acid-decomposable repeating unit represented by the following general formula (A) (hereinafter, also referred to as "repeating unit" X3 ".) As an acid-decomposable repeating unit. In addition, the repeating unit X3 does not include the repeating unit X1 and the repeating unit X2 described above.

[Chemical Formula 29]

L ₁ represents a divalent linking group which may have a fluorine atom or an iodine atom, R ₁ represents an alkyl group which may have a hydrogen atom, a fluorine atom, an iodine atom, or a fluorine atom or an iodine atom, and R _{2 is} activated by an acid Detachment means a leaving group which 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 which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO _2- , and a hydrocarbon group which may have a fluorine atom or an iodine atom (for example , Alkylene, cycloalkylene, alkenyl, aryl, etc.), and a plurality of linking groups connecting these. Among them, L ₁ , -CO-, or -arylene-alkylene group having a fluorine atom or an iodine atom- is preferred. As the arylene group, phenylene group is preferred. The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. 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, preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

R ₁ represents a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl 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 1-10 is more preferable, and 1-3 is more preferable. 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, preferably 1 or more, more preferably 1 to 5, and further preferably 1 to 3.

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, examples of the leaving group include groups represented by formulae (Z1) to (Z4). 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 the formulas (Z1) and (Z2), Rx ₁₁ to Rx ₁₃ each independently represent an alkyl group (linear or branched) which may have a fluorine atom or an iodine atom, or a ring which may have a fluorine atom or an iodine atom Alkyl (monocyclic or polycyclic). In addition, 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. It may have a fluorine atom or an iodine atom. Except for this point, Rx ₁₁ to Rx ₁₃ are the same as Rx ₁ to Rx _{3 in} (Y1) and (Y2) above, and have the same definitions and appropriate ranges as alkyl groups and cycloalkyl groups.

In formula (Z3), R ₁₃₆ to R ₁₃₇ each independently represent a hydrogen atom or a monovalent organic group that may have a fluorine atom or an iodine atom. R ₁₃₈ represents a monovalent organic group 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 organic group 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 aromatic group which may have a fluorine atom or an iodine atom Group, an aralkyl group which may have a fluorine atom or an iodine atom, and a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). In addition, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a hetero atom such as an oxygen atom in addition to a fluorine atom and an iodine atom. 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 group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group.

As the formula (Z3), a group represented by the following formula (Z3-1) is preferred.

[Chemical Formula 30]

Among them, L ₁₁ and L ₁₂ each independently represent a hydrogen atom; an alkyl group having a hetero atom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; Cycloalkyl of a heteroatom in the group of oxygen atoms; may have an aryl group selected from a heteroatom in the group containing a fluorine atom, an iodine atom, and an oxygen atom; or a group combining these (for example, may have (A group selected from a group consisting of a fluorine atom, an iodine atom, and an oxygen atom, a combination of an alkyl group and a cycloalkyl group). M ₁ represents a single bond or a divalent linking group. Q ₁ represents that it may have an alkyl group having a hetero atom selected from the group consisting of fluorine atom, iodine atom and oxygen atom; it may have a ring having a hetero atom selected from the group containing fluorine atom, iodine atom and oxygen atom An alkyl group; may have an aryl group selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; an amine group; an ammonium group; a mercapto group; a cyano group; an aldehyde group; or a group combining these (for example, may have (A group selected from a group consisting of a fluorine atom, an iodine atom, and an oxygen atom, a combination of an alkyl group and a cycloalkyl group).

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.

Examples of the repeating unit represented by the general formula (A) include the following.

[Chemical Formula 31]

When the resin (X) contains the repeating unit X3, the content of the repeating unit X3 (when there are a plurality of repeating units X3, the total) is, for example, 5 mass% or more relative to all the repeating units in the resin (X) , 10% by mass or more is preferable. The upper limit value is, for example, 90% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less. The content of the repeating unit X3 (when there are multiple repeating units X3, the total) is, for example, 5 to 90% by mass, preferably 5 to 60% by mass relative to all repeating units in the resin (X), 10 ~ 40% by mass is better.

(Repeating Unit with Phenolic Hydroxyl Group) The resin (X) preferably contains a repeating unit X4 having a phenolic hydroxyl group in addition to the above acid-decomposable repeating unit (repeating unit X1, repeating unit X2 or repeating unit X3). In addition, the repeating unit X4 does not have an acid-decomposable group. By including the repeating unit X4, the resin (X) has a better dissolution rate during alkaline development. Examples of the repeating unit X4 include hydroxystyrene repeating units or acrylate repeating units. As the repeating unit X4, the repeating unit represented by the following general formula (I) is preferred.

[Chemical Formula 32]

In the formula, 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, and R ₄₂ at this time 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 a divalent linking group. Ar ₄ represents an (n + 1) -valent aromatic hydrocarbon group, and when bonded to R ₄₂ to form a ring, represents an (n + 2) -valent aromatic hydrocarbon group. n represents an integer of 1-5. In order to make the repeating unit represented by the general formula (I) highly polar, it is also preferable that n is an integer of 2 or more, or X ₄ is -COO- or -CONR _64- .

As the alkyl group represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I), it may have a substituent, methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, Alkyl groups such as hexyl, 2-ethylhexyl, octyl, and dodecyl have a carbon number of 20 or less, alkyl groups having a carbon number of 8 or less are more preferable, and alkyl groups having a carbon number of 3 or less are further Better.

The cycloalkyl groups represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) may be monocyclic or polycyclic. The optionally substituted cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl group, cyclopentyl group, and cyclohexyl group, which is monocyclic, is preferred. _Examples of the halogen atom represented by 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 represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) is preferably the same as the alkyl group in the aforementioned R ₄₁ , R ₄₂ and R ₄₃ .

Preferred substituents in the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amine groups, amide groups, ureido groups, carbamate groups, hydroxyl groups, carboxyl groups, and halogens. Atom, alkoxy, thioether, acetyl, alkoxy, alkoxycarbonyl, cyano, nitro and the like, and the carbon number of the substituent is preferably 8 or less.

Ar ₄ represents a (n + 1) -valent aromatic hydrocarbon group. When n is 1, the divalent aromatic hydrocarbon group may have a substituent, for example, a phenylene group, a methylene group, a naphthyl group, a anthracenyl group, etc., having 6 to 18 carbon atoms, or for example Aromatic hydrocarbon groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, three wells, imidazole, benzimidazole, triazole, thiadiazole, and thiazole are preferred.

As a specific example of the (n + 1) -valent aromatic hydrocarbon group when n is an integer of 2 or more, (n-1) arbitrary hydrogens can be appropriately removed from the above specific example of the divalent aromatic hydrocarbon group Atom group. The (n + 1) -valent aromatic hydrocarbon group may further have a substituent.

Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n + 1) -valent aromatic hydrocarbon group may have include, for example, R ₄₁ , R _42, and R ₄₃ in the general formula (I) Alkyl groups mentioned in the above; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl. The alkyl group of R ₆₄ in -CONR _64- (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ may have a substituent, methyl, ethyl, propyl, isopropyl, n-butyl Alkyl groups, a second butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group are preferably an alkyl group having a carbon number of 20 or less, and an alkyl group having a carbon number of 8 or less is more preferable. As X ₄ , a single bond, -COO- or -CONH- is preferred, and a single bond or -COO- is more preferred.

The divalent linking group of L ₄ is preferably an alkylene group. The alkylene group may have a substituent, methylene group, ethyl group, propyl group, butyl group, hexyl group and octyl group. Alkyl groups having an equal carbon number of 1 to 8 are preferred. As Ar ₄ , an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent is preferred, and a benzene ring group, a naphthalene ring group or a biphenylene ring group is more preferred. Among them, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar ₄ is preferably a benzene ring group.

Hereinafter, specific examples of the repeating unit X4 are shown, but the present invention is not limited to this. In the formula, a represents 1 or 2.

[Chemical Formula 33]

The resin (X) may use one kind of repeating unit X4 alone, or may have two or more kinds at the same time.

When the resin (X) contains the repeating unit X4, the content of the repeating unit X4 relative to all the repeating units in the resin (X) is, for example, 5% by mass or more, preferably 10% by mass or more. The upper limit value is, for example, 90% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less. The content of the repeating unit X4 (when there are multiple repeating units X4, the total) is, for all repeating units in the resin (X), for example, 5 to 90% by mass is preferable, and 5 to 60% by mass is more Preferably, 10 to 40% by mass is more preferable, and 10 to 30% by mass or less is particularly preferable.

(The repeating unit having an internal fat structure in the side chain) In addition, the resin (X) is preferably contained in the repeating unit having an internal fat structure in the side chain (hereinafter, also referred to as "repeat unit X5"). In addition, the repeating unit X5 does not include the repeating unit X1, the repeating unit X2, the repeating unit X3, and the repeating unit X4.

As the lipid structure, a 5 to 7-membered ring lipid structure is preferred. Among them, other ring structures in the form of a double ring structure or a spiro ring structure are condensed into a 5 to 7-membered ring lipid structure is better. It is more preferable that the resin (X) includes a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21). Preferred structures include general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), Or the internal fat structure represented by the general formula (LC1-21).

[Chemical Formula 34]

The internal fat structural part may have a substituent (Rb ₂ ) or may not. Examples of preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and 2 carbon atoms. ~ 8 alkoxycarbonyl group, carboxyl group, halogen atom, hydroxyl group, cyano group, etc. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. In addition, there are a plurality of substituents (Rb ₂ ) that can be bonded to each other to form a ring.

As the repeating unit having a lactone structure, a repeating unit represented by the following general formula (III) is preferred.

[Chemical Formula 35]

In the above general formula (III), A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-). N is the number of repetitions of the structure represented by -R ₀ -Z- and represents an integer of 0 to 5, 0 or 1 is preferred, and 0 is more preferred. When n is 0, -R ₀ -Z- does not exist and becomes a single bond. R ₀ represents alkylene, cycloalkylene, or a combination thereof. When there are a plurality of R ₀ , each R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination thereof. Z represents a single bond, ether bond, ester bond, amide bond, urethane bond or urea bond. When there are plural Z, each Z independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. R ₈ represents a monovalent organic group having a lactone structure. R ₇ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

The alkylene group or cycloalkylene group of R ₀ may have a substituent. As Z, an ether bond or an ester bond is preferable, and an ester bond is more preferable.

Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) will be given, but the present invention is not limited to these specific examples. The following specific examples correspond to the case where R ₇ in the general formula (III) is a methyl group, but R ₇ can be arbitrarily substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

[Chemical Formula 36]

The content of the repeating unit X5 contained in the resin (X) (when there are a plurality of repeating units X5, the total) is, for example, 5% by mass or more and 10% by mass relative to all the repeating units in the resin (X) The above is better. For example, the upper limit value is preferably 60% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. The content of the repeating unit X5 (when there are plural repeating units X5, the total) is preferably 5 to 60% by mass relative to all repeating units in the resin (X).

(Other Repeating Units with Acid Groups) The resin (X) preferably contains other repeating units with acid groups (hereinafter, also referred to as "repeating unit X6"). In addition, the repeating unit X6 does not include the repeating unit X1, the repeating unit X2, the repeating unit X3, the repeating unit X4, and the repeating unit X5. Examples of the acid group included in the repeating unit X6 include a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl group) (alkylcarbonyl) group Methyl, (alkylsulfonyl) (alkylcarbonyl) amide imino, bis (alkylcarbonyl) methylene, bis (alkylcarbonyl) amide imino, bis (alkylsulfonyl) imide Methyl, bis (alkylsulfonyl) imide, tri (alkylcarbonyl) methylene and tri (alkylsulfonyl) methylene, etc. As an acid group, a fluorinated alcohol group (hexafluoroisopropanol is preferred.), A sulfonylimide group or a bis (alkylcarbonyl) methylene group is preferred, and a fluorinated alcohol group (hexafluoroisopropanol is Better.) Better.

The skeleton of the repeating unit X6 is not particularly limited, and (meth) acrylate-based repeating units or styrene-based repeating units are preferred.

Hereinafter, specific examples of the repeating unit X6 will be given, but the present invention is not limited to these specific examples. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

[Chemical Formula 37]

When the resin (X) contains the repeating unit X6, the content of the repeating unit X6 relative to all the repeating units in the resin (X) is, for example, 5% by mass or more, preferably 10% by mass or more. The upper limit value is, for example, 90% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less. The content of the repeating unit X6 (when there are multiple repeating units X6, the total) is, for example, 5 to 90% by mass, preferably 20 to 80% by mass, relative to all the repeating units in the resin (X), 20 ~ 60% by mass is better.

(Other Repeating Units) Furthermore, the resin (X) may further contain other repeating units than the above repeating units.

From the viewpoint of being able to suppress the excessive diffusion of acid or the collapse of the resist pattern during development, it is preferable that the resin (X) has a high glass transition temperature (Tg). Tg greater than 90 ° C is preferred, greater than 100 ° C is more preferred, greater than 110 ° C is further preferred, and greater than 125 ° C is particularly preferred. In addition, from the viewpoint of good dissolution rate in the developer, Tg is preferably 400 ° C or lower, and more preferably 350 ° C or lower. In addition, in this specification, the glass transition temperature (Tg) of the resin (X) is calculated by the following method. First, using the Bicerano method, the Tg of a homopolymer composed only of each repeating unit contained in the resin (X) was calculated. Then, the calculated Tg is referred to as "Tg of the repeating unit". Next, the mass ratio (%) of each repeating unit to all repeating units in the resin (X) is calculated. Next, the product of the Tg of each repeating unit and the mass ratio of the repeating units is calculated separately, and these are added to make the Tg (° C) of the resin (X). The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993), etc. In addition, calculation of Tg based on the Bicerano method can be performed using the polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).

In order to make the Tg of the resin (X) greater than 90 ° C, it is preferable to reduce the mobility of the main chain of the resin (X). As a method of reducing the mobility of the main chain of the resin (X), the following methods (a) to (e) may be mentioned. (A) Introduce bulky substituents into the main chain (b) Introduce multiple substituents into the main chain (c) Introduce substituents that cause interactions between resins (X) near the main chain (d) Ring structure The formation of the main chain (e) on the main chain (e) connects the cyclic structure to the main chain. In addition, it is preferable that the resin (X) has a repeating unit having a Tg of 130 ° C. or higher. In addition, the Tg of the homopolymer shows that the type of the repeating unit at 130 ° C or higher is not particularly limited, as long as the Tg of the homopolymer calculated by the Bicerano method is a repeating unit at 130 ° C or higher. In addition, depending on the type of the functional group in the repeating unit represented by the general formula (A) to the general formula (E) described later, the repeating unit corresponding to the Tg of the homopolymer exhibits 130 ° C. or higher.

As an example of the specific implementation of the above (a), a method of introducing a repeating unit represented by the following general formula (A) into the resin (X) may be mentioned.

[Chemical Formula 38]

In the general formula (A), R _A represents a group having a polycyclic structure. R _x represents a hydrogen atom, methyl or ethyl. A group having a multi-ring structure refers to a group having a plurality of ring structures, which may or may not be fused. As specific examples of the repeating unit represented by the general formula (A), the following repeating units may be mentioned.

[Chemical Formula 39]

[Chemical Formula 40]

In the above formula, R represents a hydrogen atom, a methyl group or an ethyl group. Ra represents hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxy group, alkoxy group, acetyl group, cyano group, nitro group, amine group, halogen atom, ester group (-OCOR ''' Or -COOR ''':R''' is an alkyl or fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by Ra may be replaced by a fluorine atom or an iodine atom. Moreover, R 'and R''each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an oxy group, a cyano group, a nitro group, an amine group, a halogen atom , An ester group (-OCOR '''or-COOR''': R '''is an alkyl or fluorinated alkyl group having 1 to 20 carbon atoms or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R ′ and R ″ may be substituted with a fluorine atom or an iodine atom. L represents a single bond or a divalent linking group. Examples of the divalent linking group include -COO-, -CO-, -O-, -S-, -SO-, -SO _2- , alkylene, cycloalkylene, alkenyl, and Connect these plural link bases, etc. m and n each independently represent an integer of 0 or more. The upper limit of m and n is not particularly limited, and there are many cases of 2 or less, and more cases of 1 or less.

As an example of the specific implementation of the above (b), a method of introducing a repeating unit represented by the general formula (B) into the resin (X) may be mentioned.

[Chemical Formula 41]

In the general formula (B), R _b1 to R _b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R _b1 to R _b4 represent an organic group. In addition, when at least one of the organic groups is a group in which the ring structure is directly connected to the main chain in the repeating unit, the type of other organic groups is not particularly limited. In addition, in the case where none of the organic groups is directly connected to the main chain of the repeating unit with a ring structure, at least two or more of the organic groups are substituents having at least three constituent atoms other than hydrogen atoms.

As specific examples of the repeating unit represented by the general formula (B), the following repeating units may be mentioned.

[Chemical Formula 42]

In the above formula, R independently represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups which may have substituents. R 'independently represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxyl group, alkoxy group, acetyl group, cyano group, nitro group, amine group, halogen atom, ester group (-OCOR '' Or -COOR '': R '' is an alkyl or fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R 'may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and there are many cases below 2 and many cases below 1.

As an example of the specific implementation of the above (c), a method of introducing a repeating unit represented by the general formula (C) into the resin (X) may be mentioned.

[Chemical Formula 43]

In the general formula (C), R _c1 to R _c4 independently represent a hydrogen atom or an organic group, and at least one of R _c1 to R _c4 is a hydrogen bondable hydrogen atom within 3 atoms from the main chain carbon Group. Among them, it is preferable to cause interaction between the main chains of the resin (X) and have hydrogen bonding hydrogen atoms within 2 atoms (closer to the main chain side).

As specific examples of the repeating unit represented by the general formula (C), the following repeating units may be mentioned.

[Chemical Formula 44]

In the above formula, R represents an organic group. Examples of the organic group include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, and ester groups (-OCOR or -COOR: R is an alkyl group having 1 to 20 carbon atoms. Or fluorinated alkyl). R 'represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. In addition, the hydrogen atom in the organic group may be replaced by a fluorine atom or an iodine atom.

As an example of the specific implementation of the above (d), a method of introducing a repeating unit represented by the general formula (D) into the resin (X) may be mentioned.

[Chemical Formula 45]

In the general formula (D), "Cyclic" means a group that forms a main chain with a cyclic structure. The number of constituent atoms of the ring is not particularly limited.

As specific examples of the repeating unit represented by the general formula (D), the following repeating units may be mentioned.

[Chemical Formula 46]

In the above formula, R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an oxy group, a cyano group, a nitro group, an amine group, a halogen atom , An ester group (-OCOR '' or -COOR '': R '' is an alkyl or fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be replaced by a fluorine atom or an iodine atom. In the above formula, R ′ independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an oxy group, a cyano group, a nitro group, an amine group, a halogen atom, an ester Group (-OCOR '' or -COOR '': R '' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R 'may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and there are many cases below 2 and many cases below 1.

As an example of the specific implementation of the above (e), a method of introducing a repeating unit represented by the general formula (E) into the resin (X) may be mentioned.

[Chemical Formula 47]

In the general formula (E), Re independently represents a hydrogen atom or an organic group. Examples of the organic group include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups which may have substituents. "Cyclic" is a cyclic group containing main chain carbon atoms. The number of atoms contained in the cyclic group is not particularly limited.

As specific examples of the repeating unit represented by the general formula (E), the following repeating units may be mentioned.

[Chemical Formula 48]

In the above formula, R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an oxy group, a cyano group, a nitro group, an amine group, a halogen atom , An ester group (-OCOR '' or -COOR '': R '' is an alkyl or fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be replaced by a fluorine atom or an iodine atom. R 'independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an oxy group, a cyano group, a nitro group, an amine group, a halogen atom, an ester group (-OCOR '' or -COOR '': R '' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R 'may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and there are many cases of 2 or less, and more cases of 1 or less. In addition, in the general formula (E-2), the general formula (E-4), the general formula (E-6), and the general formula (E-8), two Rs may be bonded to each other to form a ring.

The resin (X) can be synthesized according to a conventional method (for example, radical polymerization).

The weight average molecular weight of the resin (X) is preferably 2,500 to 30,000, more preferably 3,500 to 25,000, further preferably 4,000 to 10,000, and particularly preferably 4,000 to 8,000. The degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.5, more preferably 1.0 to 2.0, and further preferably 1.0 to 1.8. In addition, the weight average molecular weight of resin (X) means the polystyrene conversion value measured by GPC (Gel Permeation Chromatography, gel permeation chromatography) measurement.

One type of resin (X) may be used alone, or two or more types may be used simultaneously. In the composition of the present invention, in the total solid content, the content of the resin (X) is generally more than 30% by mass, preferably 40% by mass or more, more preferably 50% by mass or more, and more than 60% by mass Is further preferred. The upper limit is not particularly limited, but 95% by mass or less is preferable. In addition, from the viewpoint that the sensitivity is more excellent and the LWR is more excellent, it is preferable that the resin (X) contains a halogen atom. That is, in the resin (X), the repeating units X1 to X6 may contain a halogen atom, and in addition to the repeating units, further, may contain a repeating unit containing a halogen atom. The halogen atom is preferably a fluorine atom or an iodine atom.

<Solvent> The composition of the present invention contains a solvent. As the solvent, it is preferable to contain at least one of the following component (M1) and the following component (M2), and it is more preferable to include the following component (M1). When the solvent contains the following component (M1), the solvent consists essentially of the component (M1), or a mixed solvent containing at least the component (M1) and the component (M2) is preferable.

Hereinafter, the component (M1) and the component (M2) are shown. Component (M1): propylene glycol monoalkyl ether carboxylate component (M2): solvent selected from the following component (M2-1) or solvent component (M2-1) selected from the following component (M2-2) : Propylene glycol monoalkyl ether, lactate, acetate, butyl butyrate, alkoxy propionate, chain ketone, cyclic ketone, lactone or alkylene carbonate component (M2-2): Solvents with a flash point (hereinafter also referred to as fp) of 37 ° C or higher

When the above-mentioned solvent and the above-mentioned resin (X) are used in combination, it is possible to obtain a pattern with improved coatability of the composition and a small number of development defects. Although the reason is not clear, it is considered that the reason is that the above-mentioned solvent (X) of the solvent has excellent balance of solubility, boiling point, and viscosity, so that it is possible to suppress unevenness in the thickness of the resist film and during the spin coating process Generation of precipitates, etc.

As the above component (M1), at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferred. Propylene glycol monomethyl ether Ether acetate (PGMEA) is preferred.

As the above component (M2-1), the following is preferred. As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether is preferred. As the lactate, ethyl lactate, butyl lactate, or propyl lactate is preferred. As the acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or acetate 3- Methoxybutyl ester is preferred. As the alkoxy propionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferred. As chain ketones, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl Ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone acetone, acetone acetone, ionone, diacetone alcohol (diacetonyl alcohol), acetone methanol, acetophenone, Methylnaphthyl ketone or methyl amyl ketone are preferred. As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferred. As the lactone, γ-butyrolactone is preferred. As the alkylene carbonate, propylene carbonate is preferred.

As the above component (M2-1), propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate (pentyl acetate) acetate), γ-butyrolactone or propylene carbonate is more preferred.

Specific examples of the above component (M2-2) include propylene glycol monomethyl ether (fp: 47 ° C), ethyl lactate (fp: 53 ° C), and ethyl 3-ethoxypropionate (fp: 49 ° C) , Methyl amyl ketone (fp: 42 ° C), cyclohexanone (fp: 44 ° C), amyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), γ- Butyrolactone (fp: 101 ° C) or propylene carbonate (fp: 132 ° C). Among these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate or cyclohexanone is preferred, and propylene glycol monoethyl ether or ethyl lactate is more preferred. In addition, "flash point" means the value described in the reagent product catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich company.

From the viewpoint of further reducing the number of development defects, the mixing ratio (mass ratio: M1 / M2) of component (M1) and component (M2) is preferably 100/0 to 15/85, and 100/0 to 40/60 is More preferably, 100/0 to 60/40 is more preferable.

In addition, the solvent may contain other solvents in addition to the above-mentioned component (M1) and component (M2). In this case, the content of other solvents than the components (M1) and (M2) is preferably 5 to 30% by mass relative to the total mass of the solvent.

As another solvent, for example, an ester-based solvent having a carbon number of 7 or more (preferably 7 to 14, preferably 7 to 12, more preferably 7 to 10) and a heteroatom number of 2 or less is mentioned. In addition, the ester-based solvent referred to herein with a carbon number of 7 or more and a heteroatom number of 2 or less does not include a solvent corresponding to the aforementioned component (M2).

As an ester solvent having a carbon number of 7 or more and a hetero atom number of 2 or less, amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, and amyl propionate , Hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, or butyl butyrate are preferred, and isoamyl acetate is preferred.

<Other additives> The composition of the present invention may further include an acid generator other than the acid generator A, a hydrophobic resin, an acid diffusion control agent other than the acid generator B and the acid generator C, a surfactant, and a dissolution inhibitor Compounds (compounds that are decomposed by the action of acid to reduce the solubility in organic developing solutions, preferably molecular weights below 3000), dyes, plasticizers, photosensitizers, light absorbers, and / or promote development Liquid-soluble compounds (for example, phenol compounds with a molecular weight of 1000 or less, or alicyclic or aliphatic compounds containing carboxyl groups).

<Preparation method> In the composition of the present invention, from the viewpoint of more excellent coatability, the solid content concentration is preferably 0.5 to 5.0% by mass, and more preferably 0.5 to 2.0% by mass. The solid content concentration refers to the mass percentage of the mass of the resist component other than the solvent relative to the total mass of the composition.

In addition, from the viewpoint of improving the analytical power, the film thickness of the resist film (sensitized radiation or radiation-sensitive film) formed from the composition of the present invention is usually 200 nm or less, preferably 100 nm or less. For example, in order to analyze a 1: 1 line and line-space pattern with a line width of 20 nm or less, the thickness of the resist film formed is preferably 80 nm or less. If the film thickness is 80 nm or less, when the development process described later is applied, pattern collapse is less likely to occur, and more excellent resolution performance can be obtained. As the range of the film thickness, 15 to 60 nm is more preferable. This kind of film thickness can be formed by setting the solid content concentration in the composition within an appropriate range and giving it an appropriate viscosity, and improving the coating properties or film forming properties.

The composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering it through a filter, and applying it to a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-062667 (Japanese Unexamined Patent Publication No. 2002-062667), it is possible to perform circulating filtration, and it is also possible to connect a plurality of filters in series or parallel And filter. In addition, the composition can be filtered a plurality of times. Furthermore, before and after filtration by the filter, degassing treatment of the composition may be performed.

<Usage> The composition of the present invention relates to a sensitizing ray or radiation sensitive resin composition whose properties are changed by reacting with actinic rays or radiation. More specifically, the composition of the present invention relates to a semiconductor manufacturing process such as IC (Integrated Circuit), a circuit board manufacturing such as a liquid crystal or a thermal head, and a mold structure for imprinting. , Other photosensitive etching process, or sensitized ray or radiation sensitive resin composition used in the manufacture of lithographic printing plate or acid hardening composition. The pattern formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring formation processes, MEMS (Micro Electro Mechanical Systems), and the like.

[Pattern Forming Method] The present invention also relates to a pattern forming method using the above-mentioned sensitized radiation or radiation sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. In addition, the resist film of the present invention will be described together with the description of the pattern forming method.

The pattern forming method of the present invention has: (i) a process (resistance) of forming a resist film (sensitized radiation or radiation-sensitive film) on a support using the above-mentioned sensitized radiation or radiation-sensitive resin composition (Film formation process); (ii) a process (exposure process) for exposing (irradiating actinic rays or radiation) the above resist film; and (iii) using a developing solution for the above exposed resist film The development process (development process).

The pattern forming method of the present invention is not particularly limited as long as it includes the processes of (i) to (iii) above, and may further have the following processes. In the pattern forming method of the present invention, (ii) the exposure method in the exposure process may be immersion exposure. In the pattern forming method of the present invention, the process of (ii) heating (pre-bake (PB: PreBake)) before (ii) exposure process includes (iv) pre-baking process. In the pattern forming method of the present invention, it is preferable to include (v) post-exposure heating (post-exposure baking (PEB: Post Exposure Bake)) process after (ii) exposure process and (iii) development process. The pattern forming method may include a plurality of (ii) exposure processes. The pattern forming method of the present invention may include a plurality of (iv) preheating processes. The pattern forming method of the present invention may include a plurality of (v) exposures After heating process.

In the pattern forming method of the present invention, the above (i) film-forming process, (ii) exposure process, and (iii) development process can be performed by a generally known method. Furthermore, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon) and anti-reflection film can be formed between the resist film and the support ). As a material constituting the resist underlayer film, a known organic or inorganic material can be used as appropriate. A protective film (top coat) may be formed on the upper layer of the resist film. As the protective film, well-known materials can be appropriately used. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, and US Patent Application Publication No. 2016/0299432 can be preferably used. , The composition for forming a protective film disclosed in the specification of US Patent Application Publication No. 2013/0244438 and the specification of International Patent Application Publication No. 2016 / 157988A. The thickness of the protective film is preferably from 10 to 200 nm, more preferably from 20 to 100 nm, and even more preferably from 40 to 80 nm.

The support is not particularly limited, and substrates commonly used in photolithography processes other than photolithographic processes other than the manufacturing processes of semiconductors such as ICs or the manufacturing processes of circuit boards such as liquid crystals or thermal heads can be used. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ and SiN.

The heating temperature in any of (iv) the preheating process and (v) the post-exposure heating process is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and further preferably 80 to 130 ° C. The heating time is preferably in the range of (iv) preheating process and (v) post-exposure heating process, 30 to 1000 seconds, more preferably 60 to 800 seconds, and further 60 to 600 seconds. Better. The heating can be performed using a mechanism provided in the exposure device and the developing device, or it can be performed using a baking sheet or the like.

The wavelength of the light source used in the exposure process is not limited, and examples include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among these, far ultraviolet light is preferable, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and further preferably 1 to 200 nm. Specifically, KrF excimer laser (248nm), ArF excimer laser (193nm), F ₂ excimer laser (157nm), X-ray, EUV (13nm) or electron beam, etc., KrF excimer laser , ArF excimer laser, EUV or electron beam is preferred.

(Iii) The developer used in the development process may be an alkali developer, or a developer containing an organic solvent (hereinafter, also referred to as an organic developer), and an alkali developer is preferred.

As the alkali component contained in the alkali developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide is generally used. In addition to this, an alkaline aqueous solution containing an alkaline component such as an inorganic base, primary to tertiary amines, alcohol amines, and cyclic amines can also be used. Furthermore, the alkali developer may contain alcohols and / or surfactants in appropriate amounts. The alkali concentration of the alkali developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15. The development time using an alkaline developer is usually 10 to 300 seconds. The alkali concentration, pH, and development time of the alkali developing solution can be appropriately adjusted according to the formed pattern.

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

Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1- Hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone acetone, acetone acetone, violet Ketone, diacetone alcohol, acetone methanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, etc.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, and propylene glycol monomethyl ester. Ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methyl Oxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Ester, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate and butyl propionate.

As the alcohol-based solvent, amide-based solvent, ether-based solvent, and hydrocarbon-based solvent, the solvents disclosed in paragraphs <0715> to <0718> of US Patent Application Publication No. 2016 / 0070167A1 can be used.

The above-mentioned solvents may be mixed in plural or may be mixed with solvents other than the above or water. The water content of the entire developing solution is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and it is particularly preferable that it contains substantially no moisture. The content of the organic solvent relative to the organic developing solution is preferably 50 to 100% by mass relative to the total amount of the developing solution, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, 95 to 100% % Is excellent.

The organic developer may contain a known surfactant in an appropriate amount as needed.

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

As a developing method, for example, a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method); by surface tension, the developer is raised on the surface of the substrate and allowed to stand for a certain period of time The method of time (puddle method); the method of spraying the developer onto the surface of the substrate (spray method); or on the substrate rotating at a constant speed, the developer is sprayed out of the nozzle at a constant speed Scanning, a method of continuously ejecting the developer solution (dynamic dispense method), etc.

It is also possible to combine the development process using an alkaline aqueous solution (alkaline development process) and the development process using an organic solvent-containing developing solution (organic solvent development process). With this, it is possible to form a pattern without dissolving only the region of intermediate exposure intensity, and therefore it is possible to form a finer pattern.

(Iii) After the development process, a process (rinsing process) including washing with a rinse solution is preferred.

Pure water can be used as the rinsing solution used in the rinsing process after the development process using the alkali developer. Pure water may contain an appropriate amount of surfactant. In this case, after the development process or the rinsing process, a process of removing the developing solution or the rinsing liquid attached to the pattern by supercritical fluid may also be added. Furthermore, after rinsing or supercritical fluid treatment, heat treatment may be performed to remove moisture remaining in the pattern.

The developing solution used in the developing process after using the developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common organic solvent can be used. As the rinsing liquid, it is preferable to use a rinsing liquid 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. Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent are the same as those described in the developer containing an organic solvent. As the rinsing liquid used in the rinsing process at this time, a rinsing liquid containing monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the washing process include linear, branched or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, third butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl alcohol 2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol , 4-octanol and methyl isobutyl methanol. Examples of monohydric alcohols having a carbon number of 5 or more include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and methyl alcohol Base isobutyl methanol and so on.

Each component may be mixed in plural or may be mixed with organic solvents other than the above. The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The rinse solution may contain an appropriate amount of surfactant. In the rinsing process, the rinsing solution containing the organic solvent is used to clean the substrate developed with the organic developer. The method of cleaning treatment is not particularly limited. For example, the following methods may be mentioned: a method of continuously spraying a rinsing liquid on a substrate rotating at a constant speed (spin coating method); immersing the substrate in a tank filled with the rinsing liquid for a certain period of time The method of time (dipping method); and the method of spraying rinsing liquid onto the surface of the substrate (spray method), etc. Among them, it is preferable to perform a cleaning process by a spin coating method, and after cleaning, rotate the substrate at a rotation speed of 2,000 to 4,000 rpm, and remove the rinse liquid from the substrate. Furthermore, it is also preferable to include a heating process (Post Bake) after the rinsing process. Through the heating process, the developer and rinse liquid remaining between the patterns and inside the patterns are removed. In the heating process after the rinsing process, the heating temperature is usually 40 to 160 ° C, preferably 70 to 95 ° C, and the heating time is usually 10 seconds to 3 minutes, preferably 30 to 90 seconds.

The sensitized radiation or radiation-sensitive resin composition of the present invention and various materials used in the pattern forming method of the present invention (for example, resist solvent, developer, rinse solution, anti-reflection film forming composition or top The composition for forming the coating layer, etc.) preferably does not contain impurities such as metal components, isomers and residual monomers. As the content of the impurities contained in the above-mentioned various materials, 1 mass ppm or less is preferable, 100 mass ppt or less is more preferable, and 10 mass ppt or less is even more preferable, which is not substantially included (is the detection limit of the measuring device (Below) is particularly good.

As a method of removing impurities such as metals from the above-mentioned various materials, for example, filtration using a filter may be mentioned. As the filter pore size, the pore size is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter can be washed with an organic solvent in advance. In the filter filtration process, a plurality of filters can be connected in series or in parallel and used. When using multiple filters, filters with different pore sizes and / or materials can be used in combination. In addition, various materials may be filtered a plurality of times, and the process of performing the plurality of times of filtration may be a circulating filtration process. As a filter, it is preferable to reduce the eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426). In addition to filter filtration, the adsorbent can also be used to remove impurities, or the filter can be used in combination with the adsorbent. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500). In addition, as a method of reducing impurities such as metals contained in the above-mentioned various materials, the following methods may be mentioned: a method of selecting a raw material with a small metal content as a raw material constituting various materials, and a method of filtering a raw material constituting various materials Or, by using Teflon (registered trademark) in the device for lining, etc. to minimize pollution as much as possible, distillation and other methods. The preferable conditions for the filtration of the raw materials constituting various materials are the same as the above-mentioned conditions.

In order to prevent the mixing of impurities, the above materials are stored in the containers described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351), etc. good.

The method of improving the surface roughness of the pattern can also be applied to the pattern formed by the pattern forming method of the present invention. As a method for improving the surface roughness of the pattern, for example, a method for processing the pattern by plasma containing hydrogen gas disclosed in US Patent Application Publication No. 2015/0104957 can be mentioned. In addition, for example, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. Of SPIE Vol. 8328 83280N-1 A well-known method described in "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement". Furthermore, the pattern formed by the above method can be used, for example, as disclosed in Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/0209941 The core material of Spacer Process.

[Manufacturing method of electronic component] In addition, the present invention also relates to a manufacturing method of electronic component including the above pattern forming method. Electronic components manufactured by the method for manufacturing electronic components of the present invention are suitably mounted on electrical and electronic equipment (eg, home appliances, office appliances (Office Automation, Office Automation, Office Automation), media-related equipment, optical equipment, and communications Equipment, etc.). [Example]

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

First, the various components contained in the sensitized radiation or radiation sensitive resin composition shown in Table 5 will be described.

[Resin] The repeating units in Resins P-1 to P-24 shown in Table 5 are shown below. In addition, the following Table 1 shows the composition ratio (mass%), weight average molecular weight (Mw), and degree of dispersion (Mw / Mn) of each resin. In addition, the weight average molecular weight (Mw) and dispersion degree (Mw / Mn) of the resins P-1 to P-24 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). In addition, the composition ratio of the resins P-1 to P-24 was measured by ¹³ C-NMR (nuclear magnetic resonance).

[Chemical Formula 49]

[Chemical Formula 50]

[Table 1] (Table 1)

[Acid generator A] The structure of the acid generator A (A-1 to A-10) shown in Table 5 is shown in Table 2 below. In addition, Table 2 shows the LUMO (eV) of the cationic part of the acid generator A (A-1 to A-10) and the acid (generated acid) generated from the acid generator A (A-1 to A-10) ) Of pKa. In addition, the respective values of the LUMO (eV) of the cation portion of the acid generator A (A-1 to A-10) and the pKa of the acid generated were determined by the measurement method described below.

[Chemical Formula 51]

[Chemical Formula 52]

[Table 2] (Table 2)

[Acid generator B] The structure of the acid generator B (B-1 to B-5) shown in Table 5 is shown in Table 3 below. In addition, Table 3 shows the pKa of the acid (generated acid) generated from the acid generator B (B-1 to B-5). In addition, the acid-generating pKa is determined by the measurement method described later.

[Chemical Formula 53]

[Table 3] (Table 3)

[Acid generator C] The structure of the acid generator C (C-1 to C-6) shown in Table 5 is shown in Table 4 below. In addition, Table 4 shows the pKa of the acid (generated acid) generated from the acid generator C (C-1 to C-6). In addition, the acid-generating pKa is determined by the measurement method described later.

[Chemical Formula 54]

[Table 4] (Table 4)

[Solvent] PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether

<Preparation of sensitized radiation-sensitive or radiation-sensitive resin composition> Each component shown in the following Table 5 was dissolved in the solvent shown in Table 5 to prepare a solution having a solid content concentration of 1.2% by mass, respectively , Using a polyethylene filter with a pore size of 0.03 μm to filter, thereby preparing a photosensitive radiation or radiation-sensitive resin composition (hereinafter, also referred to as “resist composition”.) (E-1 ) ~ (E-44). In the resist composition, the solid content means all components except the solvent. The obtained resist composition was used in Examples and Comparative Examples. In addition, the content (mass%) of each component described in the "Resin" column, "Acid generator A" column, and "Acid generator B or Acid generator C" column below indicates the ratio of each component relative to the total solid content .

[Various measurements and evaluations] <Measurement of the lowest unoccupied molecular orbital area (LUMO) of acid generator A> The quantum chemical calculation program Gaussian09 (made by Gaussian Corporation, USA) was used to measure the minimum unused acid generator A under the following conditions Occupy the molecular orbital area (LUMO). · Density functional method · Generic function: B3LYP · Base function: TZVP

<Measurement of acid-generated pKa of acid generator A, acid generator B, and acid generator C> The pKa of the acid generator of acid generator A, acid generator B, and acid generator C was determined by the following software. Advanced Chemistry Development (ACD / Labs) pKa Database V8.0

<Residual rate of acid generator A after 9 months storage at 4 ° C> (heating time-lapse test) For resist compositions (E-1) to (E-44) immediately after preparation, use HPLC (High performance liquid chromatography) The initial content of each acid generator A at 45 ° C, 60 ° C and 75 ° C was measured. Next, the resist compositions (E-1) to (E-44) after storage at 45 ° C, 60 ° C and 75 ° C for 7 days were measured by HPLC for each residue of the acid generator A at each temperature Rate (hereinafter, also referred to as "PAG residual rate"). In addition, the resist compositions (E-1) to (E-44) after storage at 45 ° C, 60 ° C, and 75 ° C for 14 days were also measured in the same manner for each PAG residual rate at each temperature. In addition, the PAG residual rate was obtained from the following formula based on the peak area value obtained by HPLC. PAG residual rate (%) = (residual amount of acid generator A in the resist composition after storage for a predetermined time) / (initial content of acid generator A in the resist composition) × 100

(Preparation of Arrhenius plot) The Arrhenius plot was prepared using each PAG residual rate obtained by the above-mentioned heating time-lapse test, and the acid generator after 9 months storage at 4 ° C was obtained The residual rate of A was evaluated by the following evaluation criteria. The results are shown in Table 5.

(Evaluation criteria) "A": The residual rate of the acid generator A is 80% or more. "B": The residual rate of the acid generator A is 40% or more and less than 80%. "C": The residual rate of the acid generator A is less than 40%.

[Pattern formation and evaluation] (Formation of a resist pattern) "Formation of a resist film" AL412 (manufactured by Brewer Science, Inc.) was coated on a silicon wafer and performed at 200 ° C for 60 seconds After baking, a resist underlayer film with a thickness of 20 nm was formed. The resist compositions (E-1) to (E-44) just prepared were coated thereon, and baked at 100 ° C for 60 seconds (PB: Prebake) to form a film thickness of 30 nm Of resist film.

"Exposure Process (EUV Exposure)" Use an EUV exposure machine (manufactured by ASML; NXE3350, NA0.33, Dipole 90 °, Outer sigma 0.87, inner sigma 0.35), and reflect via a pitch of 44 nm and a line width of 22 nm A type mask exposed the resist film. Then, it heated at 85 degreeC for 60 second (PEB: Post Exposure Bake). Next, it was developed in a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution for 30 seconds, and rinsed with water for 20 seconds. Next, the wafer was rotated at 2000 rpm for 40 seconds to form a pattern of lines and spaces with a pitch of 44 nm and a line width of 22 nm.

(1) Sensitivity evaluation While changing the exposure amount, the line width of the line and the space pattern was measured, and the exposure amount (optimal exposure amount) when the line width became 22 nm was obtained, and this was taken as the sensitivity (mJ / cm ² ). The smaller the value, the higher the sensitivity of the resist composition. The results are shown in Table 5.

(2) LWR (Line Width Roughness) evaluation In the above sensitivity evaluation, the critical size-scan type is used in the observation process of the line and space resist patterns analyzed at the optimal exposure amount An electron microscope (SEM: Scanning Electron Microscope (CG-4100 manufactured by Hitachi High-Technologies Corporation)) was observed at any point in the distance from the center of the pattern to the edge of the pattern, and its measurement fluctuation was evaluated with 3σ. The smaller the value, the better the performance. The results are shown in Table 5.

[table 5]

[Table 6]

It is clear from Table 5 that the photosensitizing radiation or radiation-sensitive resin compositions of Examples have excellent storage stability, high sensitivity, and excellent LWR of the formed pattern. In addition, as is clear from the results of Example 4, Example 8, and Example 9, a carboxyl group-containing compound having a pKa of 2.0 to 3.5 is used as the acid generator (acid generator C: equivalent to the implementation) In the case of Examples 8 and 9), LWR is more excellent. Furthermore, it is clear from the results of Example 4, Example 8, and Example 9 that the compound represented by the general formula (ZV-1) is used as the acid generator (acid generator C: In the case of equivalent to Examples 8 and 9), LWR is more excellent. In addition, from the results of Example 4 and Examples 10 to 16, it can be seen that when the acid generator A contains an acid generator containing a cation represented by the general formula (ZII) (equivalent to Example 4, Example 10, In Examples 14 to 16), the sensitivity is more excellent, or the LWR is more excellent. In addition, it is clear from the results of Example 4, Examples 17 to 19, and Examples 22 to 39 that when the resin contains a repeating unit having a halogen atom, the sensitivity is more excellent and the LWR is more excellent.

no

Claims (11)

A sensitized radiation or radiation sensitive resin composition, comprising: an acid generator that generates an acid by irradiation with actinic rays or radiation, a resin and a solvent whose polarity increases by the action of an acid, and a solvent, the acid is generated The agent includes: an acid generator A containing a cation with a minimum unoccupied molecular orbital energy level of -7.0 eV or more and less than -5.0 eV; and selected from those containing an amide imide compound having a pKa of -3.0 to 5.0 as an acid generator One or more types of acid generator B and a compound containing a carboxylic acid group or a sulfonic acid group having a pKa of -3.0 to 3.5 as an acid generator C that generates an acid. The sensitized radiation or radiation-sensitive resin composition as described in item 1 of the patent application scope, wherein the acid generator A contains a cation represented by the following general formula (ZI), In the general formula (ZI), R ^a , R ^b and R ^c each independently represent a substituent; o and p each independently represent an integer of 0 to 5; q represents an integer of 1 to 5; o is 2 or more , Plural ^Ra may be the same as each other or different, and at least two ^Ras may be bonded to each other to form a ring; when p is 2 or more, plural R ^b may be the same as each other, or different, and, At least 2 R ^b may be bonded to each other to form a ring; when q is 2 or more, a plurality of R ^c may be the same as or different from each other, and at least 2 R ^c may be bonded to each other to form a ring; and, R ^a and R ^b , R ^b and R ^c, and R ^a and R ^c may each be bonded to each other to form a ring. The sensitized radiation- or radiation-sensitive resin composition as described in item 2 of the scope of the patent application, wherein at least one of the R ^c is a substituent containing a fluorine atom. The sensitized radiation or radiation sensitive resin composition as described in item 2 of the patent application scope, wherein the cation represented by the general formula (ZI) is a cation represented by the following general formula (ZII) In the general formula (ZII), R ^a represents a substituent; R ^b1 , R ^b2 , R ^c1 and R ^c2 each independently represent a substituent containing a fluorine atom; o represents an integer of 1 to 3. The sensitized radioactive or radiation-sensitive resin composition as described in any one of claims 1 to 4 in which the acid generating agent B generates acid and the acid generating agent C generates acid pKa It is greater than the pKa of the acid generated from the acid generator A. The sensitized radioactive or radiation-sensitive resin composition as described in any one of claims 1 to 4, wherein the acid generator B and the acid generator C are onium salts. The sensitized radioactive or radiation-sensitive resin composition as described in any one of claims 1 to 4, wherein the resin contains halogen atoms. The photosensitive ray-sensitive or radiation-sensitive resin composition as described in Item 7 of the patent application, wherein the halogen atom is a fluorine atom or an iodine atom. A resist film formed by the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of the first to eighth patent applications. A pattern forming method, comprising: a resist film forming process, using the sensitized radiation or radiation-sensitive resin composition described in any one of claims 1 to 8 to form a resist film; In the exposure process, the resist film is exposed; and in the development process, the exposed resist film is developed using a developing solution. An electronic component manufacturing method, including the pattern forming method described in item 10 of the patent application scope.