TWI787469B - Actinic radiation-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and manufacturing method of electronic component - Google Patents

Abstract

The present invention provides an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming patterns with high aspect ratio and narrow pitch. Furthermore, there are provided a resist film, a method for forming a pattern, and a method for manufacturing an electronic element. The actinic radiation-sensitive or radiation-sensitive resin composition includes: an ether compound; a resin comprising repeating units having phenolic polar groups and repeating units having acid-decomposable groups; a photoacid generator; an acid diffusion control agent, which is compatible with A compound different from the ether compound; and a solvent, wherein the mass ratio of the content of the ether compound to the content of the acid diffusion control agent is 0.2 or more, the mass ratio of the content of the ether compound to the content of the resin B is 0.1 or less, and the solid content concentration is greater than 20 quality%.

Description

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

The present invention relates to an actinic radiation-sensitive or radiation-sensitive resin composition, a resist film, a method for forming a pattern, and a method for manufacturing electronic components.

In order to compensate for the decrease in sensitivity caused by light absorption after using a resist for KrF excimer laser (248 nm), an image forming method such as chemical amplification is used as an image forming method of a resist. For example, as an image forming method of positive-type chemical amplification, an image forming method in which a photoacid generator in an exposed portion is decomposed by exposure to excimer laser, electron beam, extreme ultraviolet light, etc. to generate Acid, and in post-exposure baking (PEB: Post Exposure Bake), use it to generate acid as a reaction catalyst to change the alkali-insoluble group into alkali-soluble group, and remove the exposed part by alkali developer.

For example, Patent Document 1 discloses a pattern forming method having a step of forming a film with a thickness T on a substrate using a predetermined actinic radiation-sensitive or radiation-sensitive resin composition. As the thickness T, for example, assume Above 800nm. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication WO2017/057226

Conventionally, in the manufacturing process of image sensors and the like, ion implantation is performed in semiconductors. In recent years, considering the demand for high-resolution ion implantation, etc., even when the high aspect ratio (the height of the formed line with respect to the width) of the obtained pattern is promoted by making the resist film thick, In the case of increasing the ratio), it is also required that the pattern can be made into a narrow pitch (interval). As a result of studying the actinic radiation-sensitive or radiation-sensitive resin composition described in Patent Document 1, the present inventors found that there is room for improvement in the pitch of patterns when increasing the aspect ratio of patterns.

Therefore, an object of the present invention is to provide an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern with a high aspect ratio and a narrow pitch. Moreover, the subject of this invention is providing the manufacturing method of a resist film, a pattern formation method, and an electronic component.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors found that the above-mentioned problems can be solved by a predetermined actinic radiation-sensitive or radiation-sensitive resin composition containing an ether compound, and completed the present invention. That is, it discovered that the above object can be achieved by the following constitution.

[1] An actinic radiation-sensitive or radiation-sensitive resin composition comprising: an ether compound; a resin comprising a repeating unit having a phenolic polar group and a repeating unit having an acid-decomposable group; a photoacid generator; an acid diffusion A control agent, which is a compound different from the above-mentioned ether compound; and a solvent, wherein the mass ratio of the content of the above-mentioned ether compound to the content of the above-mentioned acid diffusion control agent in the actinic radiation-sensitive or radiation-sensitive resin composition is 0.2 or more , the mass ratio of the content of the above-mentioned ether compound to the content of the above-mentioned resin is 0.1 or less, and the solid content concentration is greater than 20% by mass. [2] The actinic radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the ether compound contains a nitrogen atom. [3] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [1] or [2], wherein the ether compound is a compound represented by general formula (X1) described below. [4] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [3], wherein in the general formula (X1) described later, at least one R ^q1 is a phenyl ring group. [5] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [4], wherein the content of the repeating unit having a benzene ring group in all the repeating units of the resin is less than 65% mole %. [6] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the resin further has a repeating unit represented by the general formula (VW) described below. [7] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [6], wherein the above-mentioned photoacid generator is selected from the group consisting of the following general formula (ZI-3). One or more compounds in the group of the compound represented and the compound represented by the general formula (ZI-4) described later. [8] A resist film formed using the actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [7]. [9] A method for forming a pattern, comprising: a step of forming a resist film using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of [1] to [7]; a step of exposing the resist film; and a step of developing the exposed resist film using a developer. [10] A method of manufacturing an electronic device, including the pattern forming method described in [9]. [Invention effect]

According to the present invention, it is possible to provide an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern with a high aspect ratio and a narrow pitch. Also, according to the present invention, it is possible to provide a resist film, a method for forming a pattern, and a method for manufacturing an electronic component.

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

In this specification, (meth)acrylate means acrylate and methacrylate. Moreover, (meth)acrylic acid means acrylic acid and methacrylic acid. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn) and dispersion (also called molecular weight distribution) (Mw/Mn) of the resin are defined by GPC (Gel Permeation Chromatography (Gel Permeation Chromatography) )) GPC measurement of device (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40°C , Flow rate: 1.0 mL/min, Detector: Refractive Index Detector (Refractive Index Detector)) polystyrene conversion value.

The pKa (acid dissociation constant pKa) in this specification refers to the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Chem. The lower the value of the acid dissociation constant pKa, the stronger the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be actually measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can also be used to calculate the value based on the database of Hammett's substituent constants and known literature values. All the values of pKa described in this specification represent values obtained by calculation using this software package.

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

In the notation of a group (atomic group) in this specification, the notation of substitution and unsubstituted notation includes a group not having a substituent and also a group having a substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Moreover, the "organic group" in this specification means a group containing at least 1 carbon atom.

In addition, in this specification, the kind of substituent, the position of a substituent, and the number of a substituent, such as "may have a substituent", are not particularly limited. The number of substituents may be, for example, 1, 2, 3 or more. Examples of substituents include monovalent non-metallic atomic groups other than hydrogen atoms, and can be selected from the following substituent group group T, for example. (substituent T) Examples of substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; phenoxy and p-toluene Aryloxy groups such as oxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetyloxy, propionyloxy, and benzoyloxy; Acyl group, benzoyl group, isobutyryl group, acryl group, methacryl group, and acyl group such as acyl group; methylsulfanyl group (methylsulfanyl) and tertiary butylsulfanyl group, etc. Alkyl sulfanyl; aryl sulfanyl such as phenyl sulfanyl and p-toluene sulfanyl; alkyl; cycloalkyl; aryl; heteroaryl ; Hydroxy; Carboxyl; Formyl; Sulfonyl; Cyano; Alkylaminocarbonyl; Arylaminocarbonyl; basis; and such combinations.

[Actinic radiation-sensitive or radiation-sensitive resin composition] The actinic radiation-sensitive or radiation-sensitive resin composition (hereinafter also referred to simply as "resist composition") of the present invention includes: an ether compound; a resin containing repeating units having phenolic polar groups and acid-decomposable groups A repeating unit of ; a photoacid generator; an acid diffusion controller, which is a compound different from the aforementioned ether compound; and a solvent. In addition, in the resist composition, the mass ratio of the content of the ether compound to the content of the acid diffusion controller is 0.2 or more. Likewise, in the resist composition, the mass ratio of the content of the ether compound to the content of the resin is 0.1 or less. In addition, the solid content concentration is greater than 20% by mass.

The mechanism by which the subject of the present invention can be solved by employing such a constitution in the resist composition is not clear, but the inventors of the present invention think as follows. It is considered that the following content contributes to solving the problem of the present invention, that is, the ether compound exists in a certain ratio in the resist composition, thereby improving the adhesion of the resist film to the substrate, etc., even when a high aspect ratio is formed. When forming a pattern, pattern collapse can also be suppressed, thereby improving the contrast of the pattern analyzed in the process from exposure to development. Also, it is considered that the resist composition of the present invention is used to form a thick resist for obtaining a pattern with a high aspect ratio by having a solid content concentration of more than 20% by mass, and the resin contains a repeating unit having a phenolic polar group. The applicability of the etch film is improved. Moreover, the pattern obtained by using the resist composition of this invention is also excellent in the cross-sectional shape (rectangularity) of a pattern.

Hereinafter, components contained in the resist composition of the present invention will be described in detail. In addition, the resist composition of the present invention may be a positive resist composition or a negative resist composition. In addition, it may be a resist composition for alkali development, or may be a resist composition for organic solvent development. Among them, a positive type resist composition and a resist composition for alkali development are preferable. The resist composition of the present invention is typically a chemically amplified resist composition.

＜Ether compound＞ The resist composition of the present invention contains an ether compound. The molecular weight of the ether compound is preferably from 100 to 2000, more preferably from 150 to 1000, and still more preferably from 200 to 600. The ether compound is a compound having an ether group (-O-). The ether group is bonded to a carbon atom at two bonding positions, respectively. Here, the ether group possessed by the ether compound does not mean a group that is directly bonded to a carbonyl carbon (a carbon atom that forms -C(=O)-) to form an ester group.

The ether compound is preferably, for example, a compound having a group represented by the following general formula (O1). *x-(-O-AL-) _a -*y (O1)

In the general formula (O1), *x and *y represent the bonding positions with groups other than the groups represented by the general formula (O1).

AL represents alkylene. The above-mentioned alkylene group may be branched or linear. Moreover, it may have a ring structure, and may not have it. The number of carbon atoms in the alkylene group is preferably 1-10, more preferably 1-5, and still more preferably 2-3. The substituents that the above-mentioned alkylene group may have are not particularly limited, and are preferably unsubstituted. In addition, the above-mentioned preferable carbon number is a number not including the number of carbon atoms contained in the substituent. Among them, -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ - is preferable as the alkylene group. When there are plural ALs, the plural ALs may be the same or different.

a represents an integer of 1 or more. It is preferable that a is 1-10, it is more preferable that it is 1-6, and it is still more preferable that it is 1-4.

The group bonded to the group represented by the general formula (O1) at *x is not particularly limited, for example, a hydrogen atom, an alkylene group, and an aromatic ring group (preferably having 6 to 15 carbon atoms are mentioned. For example, a phenyl ring group) or an alkyl group (preferably having 1 to 5 carbon atoms). Also, when a is 1, the atom bonded to the group represented by the general formula (O1) at *x is a carbon atom other than the carbonyl carbon. As the carbon atom other than the above-mentioned carbonyl carbon, for example, it is a carbon atom constituting an aromatic ring group (preferably having 6 to 15 carbon atoms. An aromatic hydrocarbon group is more preferable, and a benzene ring group is more preferable), constituting an alkyl group (preferably It is preferably a carbon atom having 1 to 5 carbon atoms or a carbon atom constituting an alkylene group.

The group bonded to the group represented by the general formula (O1) at *y is not particularly limited, for example, a hydrogen atom, a hydroxyl group, an ether group, an aryloxy group (preferably having 6 to 15 carbon atoms) .eg, phenoxy) and -NR _p R _q . R _p and R _q each independently represent a hydrogen atom or a substituent. R _p and R _q may be bonded to each other to form a ring. R _p or R _q can become a divalent linking group (for example, an alkylene group (preferably having 1 to 5 carbons)) and a group represented by the general formula (O1) at *x to form a bond containing the general A ring of the group represented by the formula (O1). R _p , R _q , and a ring formed by bonding R _p and R _q to each other may each have a group represented by the general formula (O1). In addition, R _p or R _q which is the above-mentioned divalent linking group may have a group represented by the general formula (O1).

Also, the group represented by the general formula (O1) satisfies at least one of the group bonded at *x being a group other than a hydrogen atom and the group bonded at *y being a group other than a hydroxyl group Necessary conditions are better.

The number of groups represented by the general formula (O1) contained in the ether compound is preferably 1 or more, more preferably 1-5, and still more preferably 1-3. When a plurality of groups represented by the general formula (O1) exist in the ether compound, these may be respectively the same or different. In addition, the number of groups represented by the general formula (O1) in the ether compound is a number obtained by counting the number of groups represented by the general formula (O1) present in each compound as little as possible. . For example, the ether compound represented by "phenyl-O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-phenyl" has a general formula of a=3 ( The group represented by O1).

The ether compound is preferably a nitrogen-containing compound. That is, the ether compound is preferably a compound containing an ether group and a nitrogen atom. The number of nitrogen atoms which the ether compound which is a nitrogen-containing compound has is not limited, For example, 1-5 are preferable.

Among them, the ether compound is preferably a compound represented by the general formula (X1). [R ^q1 -(-O-AL-) _m ] _n -NR ^q2 _3-n (X1)

In general formula (X1), m represents the integer of 1-10. m is preferably 1-6, more preferably 1-4. When there are plural m, that is, when n is an integer of 2 or more, the plural m may be the same or different.

n represents the integer of 1-3.

AL represents alkylene. The form that AL in general formula (X1) can take is the same as the form that AL in general formula (O1) can take. When there are plural ALs, the plural ALs may be the same or different.

R ^q1 represents a hydrogen atom or a substituent. As a substituent for R ^q1 , for example, an organic group is preferred, an aromatic ring group (preferably having 6 to 15 carbon atoms. Aryl is preferred, phenyl ring is more preferred) or an alkyl group (preferably carbon Number 1 to 5) is better. Moreover, as a substituent which the aromatic ring group in ^Rq1 has, for example, an alkoxy group (preferably having 1-5 carbon atoms) is preferable. When there are plural R ^q1s , the plural R ^q1s may be the same or different. ^{Among the R q1s that may exist in plural, at least one R q1 is} preferably a phenyl ring group.

In addition, when a group represented by [R ^q1 -(-O-AL-)] exists in the general formula (X1) because one or more of the m that may exist in plural is 1, among such groups R ^q1 is more preferably an organic group, an aromatic ring group (preferably having 6 to 15 carbon atoms. An aryl group is more preferred, and a phenyl ring group is more preferred) or an alkyl group (preferably having 1 to 5 carbon atoms) for further improvement. Also, in this kind of [R ^q1 -(-O-AL-)], the atom directly bonded to (-O-AL-) in R ^q1 is an atom other than a hydrogen atom and a carbonyl carbon atom. Preferably, carbon atoms other than carbonyl carbon are more preferred. As a carbon atom other than the above-mentioned carbonyl carbon, for example, a carbon atom constituting an aromatic ring group (preferably having 6 to 15 carbon atoms. An aromatic hydrocarbon ring group is preferred, and a benzene ring group is more preferred) or an alkyl group (more preferably Preferably it is a carbon atom with a carbon number of 1 to 5).

R ^q2 represents a hydrogen atom or a substituent. The substituent for R ^q2 is not particularly limited, for example, an organic group having 1 to 20 carbons is preferred, and an alkyl ester alkyl group having 1 to 17 carbons is more preferred. When there are plural R ^q2s , the plural R ^q2s may be the same or different.

When n is 1 or 2, R ^q1 and R ^q2 may be bonded to each other to form a ring. The group formed by the mutual bonding of R ^q1 and R ^q2 is preferably an alkylene group (preferably having 1 to 5 carbon atoms). Among them, when one or more of m is 1, it is preferable that R ^q1 and R ^q2 in [R ^q1 -(-O-AL-)] present in the general formula (X1) are bonded to each other to form a ring . In this case, in the group formed by bonding R ^q1 and R ^q2 to each other, the atom directly bonded to (-O-AL-) is a carbon atom other than the carbonyl carbon (for example, the carbon constituting the alkylene group atom) is preferred.

When there are a plurality of [R ^q1 -(-O-AL-) _m ] in the general formula (X1), the plurality of [R ^q1 -(-O-AL-) _m ] may be the same or different. In the general formula (X1), at least one R ^q1 is an aromatic ring group (preferably having 6 to 15 carbon atoms), more preferably an aryl group (preferably having 6 to 15 carbon atoms), and more preferably a phenyl group. good.

Moreover, it is preferable that an ether compound does not have a fluorine atom.

In the resist composition, the mass ratio R1 of the content of the ether compound to the content of the acid diffusion controller (content of the ether compound/content of the acid diffusion controller) is 0.2 or more, preferably 0.2 to 100, and 0.2 to 20 More preferably, 0.2-1 is still more preferable. In addition, in the resist composition, the mass ratio R2 (content of ether compound/content of resin) of the content of the ether compound to the content of the resin is 0.1 or less, preferably 0.0002 to 0.05, more preferably 0.0002 to 0.01, 0.0003 to 0.005 is still more preferable. The acid diffusion controller and the resin will be described in detail in the following paragraphs. In the resist composition, the content of the ether compound is not particularly limited as long as it satisfies the above-mentioned requirements of R1 and R2. For example, it is preferably 0.006 to 8% by mass relative to the total solid content of the resist composition, and 0.01 -1 mass % is more preferable, and 0.02-0.5 mass % is still more preferable. In addition, the solid content means the component which forms a resist film, and does not contain a solvent. In addition, as long as it is a resist film forming component, even if its property is liquid, it is regarded as a solid component. An ether compound may be used individually by 1 type, and may use 2 or more types. When two or more ether compounds are used, the total content thereof is preferably within the above range.

＜Resin＞ The resist composition of the present invention includes a resin (also simply referred to as "resin B" or "resin") that includes a repeating unit having a phenolic polar group and a repeating unit having an acid-decomposable group.

(Repeating units with phenolic polar groups) Resin B contains repeating units with phenolic polar groups. The phenolic polar group refers to a group in which a polar group is bonded to an aromatic ring group. The aforementioned aromatic ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. In addition, the aromatic ring group may be monocyclic or polycyclic. Also, a non-aromatic ring may be fused to the aromatic ring group. As the aromatic ring group, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a benzene ring group, a naphthalene ring group, and an anthracenyl ring group, or, for example, a thiophene ring group, a furan ring group, a pyrrole ring group, a benzothiophene ring group, Aromatic heterocycles containing heterocycles such as benzofuran ring group, benzopyrrole ring group, sankoujing ring group, imidazole ring group, benzimidazole ring group, triazole ring group, thiadiazole ring group and thiazole ring group base is better. Among them, the above-mentioned aromatic ring group is preferably an aromatic hydrocarbon group, and more preferably a benzene ring group.

As the polar group bonded to the aromatic ring group, an alkali-soluble group is preferred, for example, a hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, an (alkyl group) Sulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide , bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene and other acidic groups .

･General formula (P01) The repeating unit having a phenolic polar group is preferably a repeating unit represented by the general formula (P01).

[chemical 1]

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 ₄₁ , R ₄₂ and R ₄₃ are preferably hydrogen atoms.

Alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group as R ₄₁ , R ₄₂ and R ₄₃ An alkyl group having 20 or less carbon atoms is preferred, and an alkyl group having 8 or less carbon atoms is more preferred.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R ₄₁ , R ₄₂ and R ₄₃ described above.

The cycloalkyl group may be monocyclic or polycyclic, and a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl is preferable.

As the halogen atom, a fluorine atom is preferable.

R ₄₂ may be bonded to a substituent of Ar ₄ described later or L ₄ to form a ring.

X ₄ represents a single bond, -COO- or -CONR ₄₄ -. R ₄₄ represents a hydrogen atom or an alkyl group. As the above-mentioned alkyl group, the same ones as those of R ₄₁ to R ₄₃ are preferred. As X ₄ , a single bond, -COO- or -CONH- is preferable, a single bond or -COO- is more preferable, and a single bond is still more preferable.

L ₄ represents a single bond or a divalent linking group. As a divalent linking group, for example, an ether group, a carbonyl group, an ester group, a thioether group, -SO ₂ -, -NR- (R represents a hydrogen atom or an alkyl group), a divalent hydrocarbon group (for example, a Alkyl, alkenylene (eg -CH=CH-), alkynylene (eg -C≡C-) and arylylene) or a combination thereof. Among them, as a divalent linking group, an alkylene group is preferable, and as an alkylene group, a methylene group, an ethylene group, a propylidene group, a butylene group, a hexylene group, and an octylene group have 1 to 8 carbon atoms. The alkylene group is more preferable. Also, when L ₄ and R ₄₂ are bonded to form a ring, L ₄ represents a trivalent linking group. In this case, among the above-mentioned groups that may further have a substituent as the divalent linking group of L ₄ , the substituent and R ₄₂ are bonded to each other to form a single bond or a divalent bond Groups (for example, the above-mentioned groups) are preferred, and form a single bond or an alkylene group (methylene, ethylidene, propylidene, butylene, hexylene, and octyl, etc., with 1 to 8 carbon atoms. alkylene is preferred) is more preferred. The ring formed when R ₄₂ and L ₄ are bonded is preferably a 5- or 6-membered ring. Among them, L ₄ is preferably a single bond.

Ar ₄ represents a (n+1)-valent aromatic ring group. In addition, Ar ₄ may have a substituent other than Y, and it is preferable that the substituent other than Y is not a polar group. Also, when a substituent of Ar ₄ is bonded to R ₄₂ to form a ring, Ar ₄ represents an aromatic ring group having a valence of (n+2). As the aromatic ring group of Ar ₄ , the above-mentioned aromatic ring groups are similarly exemplified. Among them, Ar ₄ is preferably an aromatic hydrocarbon ring group with 6 to 18 carbon atoms, and more preferably a benzene ring group. As for the substituents of Ar ₄ that are bonded to R ₄₂ , it is preferable to form a single bond or a divalent linking group (for example, the above-mentioned groups), and to form a single bond or an alkene group (methylene, alkene group) An alkylene group having 1 to 8 carbon atoms such as an ethyl group, a propylidene group, a butylene group, a hexylene group, and an octylene group is more preferable).

Y represents a polar group. As the polar group, the above-mentioned polar groups are also exemplified in the same manner. Among them, a hydroxyl group is preferable as a polar group. Also, when Ar ₄ is an aromatic heterocyclic group having a benzene ring group, it is preferable that Y is bonded to the benzene ring group included in the aromatic hetero ring group.

n represents an integer of 1-4.

Examples of substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, aromatic ring group, and aromatic hydrocarbon ring group may have include the above-mentioned substituent T. In addition, the number of carbon atoms in the substituent is not included in the carbon numbers described for the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, aromatic ring group, and aromatic hydrocarbon ring group.

The content of the repeating unit having a phenolic polar group is preferably 20 to 74 mol%, more preferably 30 to 64, and still more preferably 45 to 64 mol%, based on all the repeating units of resin B. The repeating unit having a phenolic polar group may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, it is preferable that the total content of these is within the said range.

(repeating unit with acid decomposable group) Resin B contains repeating units having acid decomposable groups. The acid-decomposable group refers to a group having a structure in which a polar group is protected by a protecting group detached by the action of an acid. A protecting group refers to a group detached by the action of an acid. It is preferable that the above-mentioned protecting group is an acid-decomposable group formed by substituting a hydrogen atom of a polar group. Resin B is a kind of resin as follows: Since resin B contains repeating units having such acid-decomposable groups, typically, resin B is an alkali-insoluble or poorly soluble resin, and is detached from the protecting group by the action of acid, thereby protecting the Alkali solubility increases. Also, similarly, resin B is typically a resin soluble in organic solvents, and the protecting group is detached by the action of an acid, thereby reducing the solubility in organic solvents.

As the polar group protected by a protecting group, an alkali-soluble group is preferred, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, an (alkyl group) Sulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide , bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene and other acidic groups , and alcoholic hydroxyl groups. Among them, as the polar group protected by the protecting group, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group (preferably hexafluoroisopropanol group) or sulfonic acid group is preferred, carboxyl group or phenolic hydroxyl group is more preferred, carboxyl group for further improvement.

As said protecting group, the group represented by formula (Y1)-(Y4) is mentioned, for example. 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 independently represent alkyl (straight chain or branched chain), cycloalkyl (monocyclic or polycyclic), aryl, aralkyl or Alkenyl. Furthermore, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups. Among them, it is preferable that Rx ₁ to Rx ₃ each independently represent a linear or branched alkyl group, and it is more preferable that each of Rx ₁ to Rx ₃ independently represent a linear alkyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic or polycyclic ring. As the alkyl group for Rx ₁ to Rx ₃ , an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or tert-butyl group is preferable. As the cycloalkyl group of Rx ₁ to Rx ₃ , a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic group such as norbornyl, tetracyclodecanyl, tetracyclododecyl, or adamantyl Cycloalkyl groups are preferred. The aryl group of Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, for example, phenyl, naphthyl, anthracenyl, and the like. The aralkyl group of Rx ₁ to Rx ₃ is preferably an aralkyl group having 7 to 12 carbon atoms, for example, benzyl group, phenethyl group, naphthylmethyl group and the like. The alkenyl group of Rx ₁ to Rx ₃ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, butenyl, and cyclohexenyl. Cycloalkyl group formed as two bonds among Rx ₁ to Rx ₃ , monocyclic cycloalkyl group such as cyclopentyl group or cyclohexyl group, or norbornyl group, tetracyclodecanyl group, tetracyclododecyl group , or a polycyclic cycloalkyl group such as adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. Regarding the cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. Regarding the group 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 aforementioned cycloalkyl group is also preferable.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or 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 groups represented by the above-mentioned formula (Y1) and alkyl groups other than groups represented by the formula (Y1) (which may be linear or branched or Can have a ring structure. For example, carbon number 1-10, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and 1-adamantyl, etc.), aryl, aralkyl and alkenyl etc. R ₃₆ is also preferably a hydrogen atom. Examples of the above-mentioned aryl group, aralkyl group and alkenyl group include, for example, the groups mentioned as the aryl group, aralkyl group and alkenyl group in the above-mentioned Rx ₁ to Rx ₃ in the same manner. In addition, R ₃₈ may be mutually bonded to a group other than the group represented by the formula (Y3) in the repeating unit. For example, R ₃₈ may be bonded to a group included in the main chain of the repeating unit. When R ₃₈ is bonded to other groups in the repeating unit, it is preferred that R ₃₈ and other groups form a single bond or a divalent linking group (alkylene group, etc.). Also, when R ₃₈ is bonded to other groups in the repeating unit, the repeating unit forms a ring including the group represented by formula (Y3).

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

[Chem 2]

Wherein, L ₁ and L ₂ 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 have a heteroatom, a cycloalkyl group that may have a heteroatom, an aryl group that may have a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group that combines these (such as , a combination of an alkyl group and a cycloalkyl group). Among the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be substituted with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. In addition, it is preferable that one of L ₁ and L ₂ is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M, and L may be bonded to form _a ring (preferably, a 5-membered ring or a 6-membered ring). From the viewpoint of pattern miniaturization, L ₂ is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl, cyclohexyl, and norbornyl, and examples of the tertiary alkyl group include tert-butyl or adamantyl. In these aspects, Tg (glass transition temperature) and/or activation energy become high, so film strength can be ensured, and fogging can be suppressed.

In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group. As the above-mentioned alkyl group, cycloalkyl group and aryl group, for example, the groups mentioned as the alkyl group, cycloalkyl group and aryl group in the above-mentioned Rx ₁ to Rx ₃ are similarly exemplified.

･General formula (A02) The repeating unit having an acid-decomposable group may be a repeating unit represented by general formula (A02).

[Chem 3]

In the general formula (A02), Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Among them, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups. Two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the optionally substituted alkyl group represented by Xa ₁ include a methyl group or a group represented by -CH ₂ -R ₁₁ . R ₁₁ represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, and an alkyl group having 3 or less carbon atoms is preferred. Preferably, methyl is more preferred. As Xa ₁ , a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group is preferable.

Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene or cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents the -COO-Rt- group, Rt is preferably an alkylene group with 1 to 5 carbons, and the -CH ₂ - group, -(CH ₂ ) ₂ - group or -(CH ₂ ) ₃ - group is better.

As the alkyl group for Rx ₁ to Rx ₃ , an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or tert-butyl group is preferable. Cycloalkyl groups for Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic ones such as norbornyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl Cycloalkyl is preferred. As the cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl are preferred, and in addition, norbornyl, tetracyclodecanyl Polycyclic cycloalkyl groups such as tetracyclododecyl group and adamantyl group are preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. In the cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted by a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. Among the repeating units represented by the general formula (AI), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the aforementioned cycloalkyl group, which is preferable.

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

The content of the repeating unit having an acid-decomposable group is preferably 10 to 80 mol%, more preferably 15 to 60 mol%, and still more preferably 20 to 45 mol%, based on all the repeating units of resin B. The repeating unit having an acid-decomposable group may be used alone or in two or more kinds. When two or more kinds are used, the total content thereof is preferably within the above-mentioned range.

(repeating unit represented by general formula (VW)) It is also preferable that the resin B has a repeating unit represented by the general formula (VW).

[chemical 4]

In the general formula (VW), Rv represents a hydrogen atom, an alkyl group or -CH ₂ -O-Rv2. Rv2 represents a hydrogen atom, an alkyl group or an acyl group. Rv is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.

Rw represents a hydrocarbon group having an alicyclic group. Regarding Rw, Rw may be an alicyclic group itself, and Rw may be a group partially containing an alicyclic group. The above-mentioned hydrocarbon group may have a substituent, and the optional substituent is preferably a group other than a polar group (as a more specific example, a group exemplified so far as a polar group). The alicyclic group that Rw has may be monocyclic (monocyclic hydrocarbon ring group) or polycyclic (polycyclic hydrocarbon ring group).

As the monocyclic hydrocarbon ring group, a monocyclic alicyclic group is preferable, and a cyclopentane ring group or a cyclohexane ring group is more preferable. The polycyclic hydrocarbon ring group includes a ring-assembled hydrocarbon ring group and a cross-linked ring hydrocarbon ring group. Examples of the ring-aggregating hydrocarbon ring group include a bicyclohexane ring group and a perhydronaphthalene ring group. As the above-mentioned crosslinked cyclic hydrocarbon ring group, for example, pinane ring group, bornane (bornane) ring group, norpinane ring group, norbornane ring group and bicyclooctane ring group (bicyclo[2.2. 2] octane ring group, bicyclo [3.2.1] octane ring group, etc.) and other 2-ring hydrocarbon ring groups; homobledane (homobledane) ring group, adamantane ring group, tricyclic [5.2.1.0 ^{2, 6} ] decane ring group and tricyclic [4.3.1.1 ^2,5 ] undecane ring group and other 3-ring hydrocarbon ring groups; and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane ring 4-ring hydrocarbon ring groups such as perhydro-1,4-methylene-5,8-methylenenaphthalene ring groups, etc. Also, the crosslinked cyclic hydrocarbon ring group also includes condensed ring hydrocarbon ring group (for example, perhydronaphthalene (decalin) ring group, perhydroanthracyclyl, perhydrophenanthrene ring group, perhydroacenaphthyl ring group, A condensed ring group in which multiple 5- to 8-membered cycloalkane ring groups such as perhydroindenyl ring group, perhydroindene ring group, and perhydroindene ring group are condensed).

As a cross-linked cyclic hydrocarbon ring group, norbornane ring group, adamantane ring group, bicyclooctane ring group or tricyclic [5, 2, 1, 0 ^2,6 ] decane ring group is preferred, norbornane ring group Alkyl ring group or adamantyl ring group is more preferable.

As the substituent which these alicyclic groups may have, for example, a halogen atom or an alkyl group is preferable.

In addition, the repeating unit represented by the general formula (VW) does not have an acid decomposable group. That is, for example, Rw does not represent a protecting group detached by the action of an acid as described above (for example, a group represented by formula (Y1)).

Hereinafter, the repeating unit represented by general formula (VW) is illustrated. In the formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

[chemical 5]

When resin B has a repeating unit represented by the general formula (VW), its content relative to all repeating units of resin B is preferably 1-40 mol%, 3-25 mol% is more preferable, 5-15 Mole% is further preferred. The repeating unit represented by the general formula (VW) may be used alone or in two or more kinds. When two or more kinds are used, the total content thereof is preferably within the above-mentioned range.

Resin B may have repeating units other than the above-mentioned repeating units. As such a repeating unit, for example, among the repeating units represented by the general formula (P01), such as repeating units in which n is 0 (benzyl (meth)acrylate-based repeating units, etc.).

Among all the repeating units of resin B, the content of the repeating unit having a phenyl ring group is preferably 80 mol % or less, more preferably less than 65 mol %, and even more preferably 60 mol % or less. The lower limit is not particularly limited. For example, 20 mol% or more is preferable, 30 mol% or more is more preferable, and 45 mol% or more is still more preferable. In addition, when the aromatic ring group of the repeating unit having a phenolic polar group in the resin B is a benzene ring group, the repeating unit having a phenolic polar group corresponds to a repeating unit having a benzene ring group.

Resin B can be synthesized by a conventional method (for example, by radical polymerization). The weight average molecular weight of the resin B is preferably from 1,000 to 200,000, more preferably from 3,000 to 25,000, and still more preferably from 10,000 to 25,000 as a polystyrene conversion value based on the GPC method. By setting the weight average molecular weight of the resin B to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance and dry etching resistance, and further, deterioration of developability and deterioration of film forming properties due to increase in viscosity. The dispersion degree (molecular weight distribution) of resin B is 1-5 normally, Preferably it is 1-3, More preferably, it is 1.2-3.0, More preferably, it is 1.2-2.0. The smaller the degree of dispersion, the better the resolution and the shape of the photoresist, and the smoother the sidewall of the photoresist pattern, the better the roughness.

In the resist composition of the present invention, the content of the resin B is not limited as long as it satisfies the aforementioned mass ratio R2, for example, it is preferably 70 to 99.9% by mass, 80 to 99.0% by mass relative to the total solid content It is more preferable, and 95-98.5 mass % is still more preferable. Moreover, resin B may use only 1 type, and may use 2 or more types, When using 2 or more types, it is preferable that these total content exists in the said range.

＜Photoacid generator＞ The resist composition of the present invention further contains a photoacid generator. A photoacid generator is a compound that generates acid upon irradiation with actinic rays or radiation. As the photoacid generator, a compound that generates an organic acid by irradiation with actinic rays or radiation is preferable. For example, percite salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazonium disulfide compounds, disulfide compounds, and o-nitrobenzyl Sulfonate compounds.

As the photoacid generator, a known compound that generates an acid upon irradiation with actinic rays or radiation can be used alone, or a mixture thereof can be appropriately selected and used. For example, paragraphs <0125> to <0319> of US Patent Application Publication 2016/0070167A1, paragraphs <0086> to <0094> of US Patent Application Publication 2015/0004544A1, and US Patent Application Publication 2016/0237190A1 Known compounds disclosed in paragraphs <0323> to <0402> of the specification are preferably used as the photoacid generator (C).

As the photoacid generator, for example, a compound represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) is preferable.

[chemical 6]

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The carbon number of the organic groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is preferably 1-30, more preferably 1-20.

The organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include independently aryl groups (preferably having 6 to 15 carbons), linear or branched alkyl groups (with 1 to 10 carbons being preferably) and cycloalkyl (preferably with 3 to 15 carbons), etc. In addition, the preferable carbon number of these aryl groups, alkyl groups and cycloalkyl groups does not include the number of carbon atoms included in the substituents these groups have.

In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of groups formed by bonding two of R ₂₀₁ to R ₂₀₃ include alkylene (for example, butylene, pentylene) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -Wait. Z ^- represents anion (non-nucleophilic anion is preferred.).

As a preferred aspect of the cation in the general formula (ZI), the corresponding ones in the compound (ZI-1), compound (ZI-2), compound (ZI-3) and compound (ZI-4) described later can be mentioned. group. In addition, the photoacid generator may be a compound having a plurality of structures represented by general formula (ZI). For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by general formula (ZI) may be obtained by A compound with a structure linked by a single bond or a linking group.

First, compound (ZI-1) will be described. The compound (ZI-1) is an aryl permeicum compound in which at least one of R ₂₀₁ to R ₂₀₃ of the general formula (ZI) is an aryl group, that is, a compound in which aryl permeicium is used as a cation. Regarding the aryl permeicium compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, or a part of R ₂₀₁ to R ₂₀₃ may be aryl groups, and the rest may be alkyl groups or cycloalkyl groups. Examples of the aryl permeium compounds include triaryl permedium compounds, diarylalkyl permeable compounds, aryl dialkyl permeable compounds, diarylcycloalkyl permeable compounds and aryl dicycloalkyl permeable compounds.

As the aryl group contained in the aryl permeicium compound, phenyl or naphthyl is preferable, and phenyl is more preferable. The aryl group may be an aryl group including a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl permeate compound has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the aryl permeate compound can have is a linear alkyl group with 1 to 15 carbons, a branched chain alkyl group with 3 to 15 carbons, or a cycloalkyl group with 3 to 15 carbons. Preferable examples include methyl, ethyl, propyl, n-butyl, second-butyl, third-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

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

Next, compound (ZI-2) will be described. In the compound (ZI-2), R ₂₀₁ to R ₂₀₃ in the formula (ZI) are each independently a compound representing an organic group not having an aromatic ring. Aromatic rings here also include aromatic rings which include heteroatoms. The organic groups having no aromatic ring as R ₂₀₁ to R ₂₀₃ preferably have 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. R ₂₀₁ to R ₂₀₃ are independently alkyl, cycloalkyl, allyl or vinyl, preferably linear or branched 2-oxoalkyl, 2-oxocycloalkyl or alkane Oxycarbonylmethyl is more preferred, and linear or branched 2-oxoalkyl is still more preferred.

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

Next, compound (ZI-3) will be described. Compound (ZI-3) is a compound represented by general formula (ZI-3).

[chemical 7]

In the general formula (ZI-3), R ₁ represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group. When R ₁ has a ring structure, the above-mentioned ring structure may have an oxygen atom, a sulfur atom, an ester group, an amido group or a carbon-carbon double bond. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group. In addition, R ₂ and R ₃ may be bonded to each other to form a ring. In addition, R ₁ and R ₂ may be bonded to each other to form a ring, and the formed ring preferably has a carbon-carbon double bond. In addition, R _x and R _y may be bonded to each other to form a ring, and the formed ring preferably has an oxygen atom, a sulfur atom, an ester group, an amido group or a carbon-carbon double bond. Z ^- represents anion.

In the general formula (ZI-3), as the alkyl group and cycloalkyl group represented by R ₁ , straight-chain alkyl groups having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), straight-chain alkyl groups having 3 to 15 carbon atoms ( Preferably a branched chain alkyl group with 3 to 10 carbons) or a cycloalkyl group with 3 to 15 carbons (preferably 1 to 10 carbons), specifically, methyl, ethyl Base, propyl, n-butyl, second butyl, third butyl, cyclopropyl, cyclobutyl, cyclohexyl and norbornyl, etc. As the aryl group represented by R1, phenyl or _naphthyl is preferable, and phenyl is more preferable. The aryl group may be an aryl group including a heterocyclic structure having an oxygen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.

It is also preferable that the above-mentioned R ₁ further has a substituent (for example, substituent group T). In addition, when R ₁ has a ring structure, the above-mentioned ring structure may have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbon-carbon double bond.

Examples of the alkyl group, cycloalkyl group and aryl group represented by R ₂ and R ₃ include the same ones as those described above for R ₁ , and their preferred aspects are also the same. Also, R ₂ and R ₃ may be bonded to form a ring. Examples of the halogen atom represented by R ₂ and R ₃ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl and cycloalkyl groups represented by R _x and R _y include the same ones as those described above for R ₁ , and their preferred embodiments are also the same. Examples of the 2-oxoalkyl group represented by R _x and R _y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), specifically, 2-oxopropane base, and 2-oxobutyl, etc. Examples of the alkoxycarbonylalkyl group represented by R _x and R _y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). In addition, R _x and R _y may be bonded to form a ring. In addition, R _x and R _y may be bonded to each other to form a ring, and the ring formed by R _x and R _y bonded to each other may have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbon-carbon double bond. In addition, the formed ring has an oxygen atom, etc. means, for example, two groups that can be bonded to each other (for example, R _x and R _y ) are bonded to each other to form an alkylene group, and the alkylene group in this A form in which a methylene group is substituted by an oxygen atom, etc. The ring formed by bonding R _x and R _y to each other is preferably a 3-10-membered ring, more preferably a 4-8-membered ring, and still more preferably a 5- or 6-membered ring.

In the general formula (ZI-3), R ₁ and R ₂ may be bonded to form a ring structure, and the formed ring structure may have a carbon-carbon double bond.

Among the above compounds (ZI-3), compound (ZI-3A) is preferred. The compound (ZI-3A) is a compound represented by the following general formula (ZI-3A), and is a compound having a benzoylmethyl percite salt structure.

[chemical 8]

In the general formula (ZI-3A), R _1c to R _5c independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a ring An alkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group. R _6c and R _7c have the same meaning as R ₂ and R ₃ in the above general formula (ZI-3), and their preferred embodiments are also the same. R _x and R _y have the same meanings as R _x and R _y in the above general formula (ZI-3), and their preferred embodiments are also the same.

Any two or more of R _1c to R _5c , R _x and R _y may be bonded to form a ring, and the ring may independently have an oxygen atom, a sulfur atom, an ester group, an amido group, or a carbon-carbon double bond . In addition, R _5c and R _6c , and R _5c and R _x may be bonded to form a ring, and it is also preferable that the rings each independently have a carbon-carbon double bond. Also, R _6c and R _7c may be bonded to each other to form a ring. In addition, the formed ring has an oxygen atom, etc. means, for example, two groups that can be bonded (for example, R _x and R _y ) are bonded to each other to form an alkylene group, and the alkylene group in such an alkylene group A form in which a methyl group is substituted by an oxygen atom, etc. In addition, examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring obtained by combining two or more of these rings. As the ring, a 3- to 10-membered ring is preferable, a 4- to 8-membered ring is more preferable, and a 5- or 6-membered ring is further preferable.

Examples of groups formed by bonding any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include butyl, pentylene, and -CH ₂ -CH ₂ -O- _CH2 - _CH2 -etc. As the group formed by bonding R _5c and R _6c and R _5c and R _x , a single bond or an alkylene group is preferable. Examples of the alkylene group include a methylene group, an ethylene group, and the like. Zc ^- represents an anion.

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

[chemical 9]

In general formula (ZI-4), l represents the integer of 0-2. r represents an integer of 0-8. R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (it may be a cycloalkyl group itself, or a group partially containing a cycloalkyl group) group. The cycloalkyl part can be monocyclic or polycyclic). These groups may have substituents. R ₁₄ represents a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a group having a cycloalkyl group (it may be a cycloalkyl group itself, or it may be a group containing a ring in part. An alkyl group. The cycloalkyl part can be monocyclic or polycyclic. For example, cycloalkylsulfonyl, cycloalkoxy, etc.). These groups may have substituents. When there are plural _R14s , the plural _R14s may be the same or different. R ₁₅ each independently represent an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have substituents. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, a heteroatom such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. In one aspect, two R ₁₅ are alkylene groups, and it is preferable to bond with each other to form a ring structure.

In the general formula (ZI-4), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched. The carbon number of the alkyl group is preferably 1-10. As the alkyl group, methyl group, ethyl group, n-butyl group or t-butyl group are more preferable.

Next, general formulas (ZII) and (ZIII) will be described. In general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group. As the aryl group for R ₂₀₄ to R ₂₀₇ , phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl groups of R ₂₀₄ to R ₂₀₇ may be aryl groups including a heterocyclic structure having 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 of R ₂₀₄ ~ R ₂₀₇ , a straight chain alkyl group with 1 ~ 10 carbons or a branched chain alkyl group with 3 ~ 10 carbons (for example, methyl, ethyl, propyl, butyl, etc.) and pentyl), or cycloalkyl groups with 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl) are preferred.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may each independently have a substituent. As substituents that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have, for example, an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), 15), aryl group (eg, carbon number 6-15), alkoxy group (eg, carbon number 1-15), halogen atom, hydroxyl group and thiophenyl group, etc. Z ^- represents anion.

As Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI-3) and Z ^- in the general formula (ZI ^- 4), the following general formula ( 3) The anions indicated are preferred.

[chemical 10]

In general formula (3), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The carbon number of the alkyl group is preferably 1-10, more preferably 1-4. Also, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ . In particular, it is still more preferable that Xf of both is a fluorine atom.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When R ₄ and R ₅ exist in plural, R ₄ and R ₅ may be the same or different. The alkyl groups represented by R ₄ and R ₅ may have substituents, preferably having 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms. Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in the general formula (3).

L represents a divalent linking group. When there are plural Ls, L may be respectively the same or different. Examples of divalent linking groups include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S- , -SO-, -SO ₂ -, alkylene (preferably 1 to 6 carbons), cycloalkylene (preferably 3 to 15 carbons), alkenylene (preferably 2 to 15 carbons 6) and a divalent linking group formed by combining a plurality of them. Among them, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene- or -NHCO-alkylene- is preferred, -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene - for better.

W represents an organic group including a ring structure. Among these, a cyclic organic group is preferable. As a cyclic organic group, an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example. The alicyclic group may be a monocyclic alicyclic group or a polycyclic alicyclic group. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl. Among them, norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, adamantyl and other alicyclic groups having a bulky structure with 7 or more carbon atoms are preferred.

The aryl group may be a monocyclic aryl group or a polycyclic aryl group. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl and anthracenyl. The heterocyclic group may be monocyclic or polycyclic. Polycyclic rings are more resistant to acid diffusion. Moreover, a heterocyclic group may or may not have aromaticity. As an aromatic heterocycle, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring are mentioned, for example. As a non-aromatic heterocycle, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring are mentioned, for example. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferable.

The above-mentioned cyclic organic group may have a substituent. As the substituent, for example, an alkyl group (which may be any of straight chain and branched chain, preferably having 1 to 12 carbon atoms), cycloalkyl group (which may be monocyclic, polycyclic (including any one of spiro ring), carbon number 3-20 is better), aryl group (carbon number 6-14 is better), hydroxyl group, alkoxyl group, ester group, amido group, polyurethane group, urea group, Thioether group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (the carbon contributing to the formation of the ring) may be carbonyl carbon.

As anions represented by general formula (3), SO ₃ ^- -CF ₂ -CH ₂ -OCO-(L)q'-W, SO ₃ ^- -CF ₂ -CHF-CH ₂ -OCO-(L)q' -W, SO ₃ ^- -CF ₂ -COO-(L)q'-W, SO ₃ ^- -CF ₂ -CF ₂ -CH ₂ -CH ₂ -(L)qW, SO ₃ ^- -CF ₂ -CH( CF ₃ )-OCO-(L)q'-W is preferred. Among them, L, q and W are the same as the general formula (3). q' represents the integer of 0-10.

In one aspect, as Z - in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI-3), and Z ^- in the general formula (ZI ^- 4) , Fluoroalkylsulfonic acid anion (more preferably perfluoroalkylsulfonic acid anion) is also preferred. The carbon number of the above-mentioned fluoroalkylsulfonic acid anion (including perfluoroalkylsulfonic acid anion) is 2-10, preferably 3-5.

The anions and cations of the photoacid generator are exemplified below, respectively.

[chemical 11]

[chemical 12]

[chemical 13]

Any combination of the above-mentioned cations and anions can be used as a photoacid generator.

The photoacid generator may be in the form of a low-molecular compound, or may be partially incorporated into a polymer. Moreover, the form of a low-molecular-weight compound and the form mixed with the part of a polymer can also be used together. The photoacid generator is preferably in the form of a low-molecular compound. When the photoacid generator is in the form of a low molecular weight compound, its molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. In the resist composition of the present invention, the content of the photoacid generator is preferably 0.1 to 35% by mass, more preferably 0.5 to 20% by mass, further preferably 1 to 10% by mass, based on the total solid content of the composition. More preferably, 1 to 5% by mass is particularly preferred. Moreover, resin B may use only 1 type, and may use 2 or more types, When using 2 or more types, it is preferable that these total content exists in the said range.

＜Acid diffusion control agent＞ The resist composition of the present invention further includes an acid diffusion control agent as a compound different from the aforementioned ether compound. The acid diffusion control agent preferably captures acid generated from a photoacid generator or the like during exposure and functions as a quencher that suppresses the reaction of the resin B in the unexposed portion due to excess generated acid. For example, a basic compound (DA), a basic compound (DB) that can reduce or disappear alkalinity by irradiation of actinic rays or radiation (having a proton-accepting functional group, and irradiated to decompose and the proton-accepting property decreases, disappears, or becomes acidic from the proton-accepting property), an onium salt (DC) that becomes a relatively weak acid relative to the photoacid generator, has a nitrogen atom and has a A low-molecular compound (DD) of a group detached by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in a cationic portion is used as an acid diffusion control agent. Among them, the acid diffusion control agent is preferably a basic compound (DA) and a low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid.

(basic compound (DA)) As the basic compound (DA), compounds having structures represented by the following formulas (A) to (E) are preferred.

[chemical 14]

In the general formulas (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group ( Preferably, it is an aryl group (with 3 to 20 carbon atoms) or an aryl group (with 6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbons.

The alkyl groups in the general formulas (A) and (E) may have a substituent or may be unsubstituted. Regarding the above-mentioned alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbons, a hydroxyalkyl group having 1 to 20 carbons, or a cyanoalkyl group having 1 to 20 carbons are preferable. The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidinium, pyrazole, pyrazoline, piperidine, aminoindoline, aminoalkylinoridine, or piperidine are preferred, with imidazole structure, diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives with hydroxyl, or aniline derivatives with hydroxyl, etc. for better.

(A low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid) Moreover, it is also preferable that the acid diffusion control agent is a low-molecular compound (DD) (hereinafter also referred to as "compound (DD)") having a nitrogen atom and a group detached by the action of an acid. Compound (DD) is preferably an amine derivative having a group detached by the action of an acid on the nitrogen atom. As the group detached by the action of acid, acetal group, carbonate group, carbamate group, tertiary ester group, tertiary hydroxyl group or hemiaminal ether are preferred, carbamate group or Hemiaminal ethers are more preferred. The molecular weight of the compound (DD) is preferably from 100 to 1,000, more preferably from 100 to 700, and still more preferably from 100 to 500. Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the urethane group is represented by the following general formula (d-1).

[chemical 15]

In general formula (d-1), Rb independently represent a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an arane group (preferably having 1 to 10 carbon atoms) or alkoxyalkyl group (preferably having 1 to 10 carbon atoms). Rb may be bonded to each other to form a ring. The substituents that the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkoxyalkyl group represented by Rb may have are independently hydroxyl, cyano, amino, pyrrolidinyl, and piperidinyl Functional groups such as , perolyl, and bridged oxy groups, alkoxy groups, or halogen atoms are preferred.

Rb is preferably a straight-chain or branched alkyl group, cycloalkyl group, or aryl group, and more preferably a straight-chain or branched alkyl group or cycloalkyl group. Examples of the ring in which two Rb are bonded to each other include an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring, a heterocyclic hydrocarbon ring, derivatives thereof, and the like. Specific structures of the group represented by the general formula (d-1) include structures disclosed in paragraph <0466> of US Patent Publication No. US2012/0135348A1, but are not limited thereto.

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

[chemical 16]

In general formula (6), l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l+m=3 is satisfied. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may be bonded to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may have heteroatoms other than the nitrogen atom in the formula. Also, as the substituent of the heterocyclic ring, a hydroxyl group is preferable. Rb has the same meaning as Rb in the above general formula (d-1), and preferred examples are also the same. In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb each independently have substituents that the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb may have. The exemplified substituents are also preferable.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted by the above-mentioned groups) of the aforementioned Ra include the same groups as those described above for Rb. Specific examples of particularly preferable compound (DD) in the present invention include compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012/0135348A1, but are not limited thereto.

Preferred examples of the acid diffusion control agent are shown below.

[chemical 17]

[chemical 18]

In the resist composition of the present invention, the content of the acid diffusion control agent is not limited as long as it satisfies the above-mentioned mass ratio R1, but for example, it is preferably 0.006 to 8% by mass relative to the total solid content, and 0.01 to 8% by mass. 1 mass % is more preferable, and 0.02-0.1 mass % is further more preferable.

<Solvent> The resist composition of the present invention contains a solvent. In the resist composition of the present invention, known resist solvents can be appropriately used. For example, paragraphs <0665> to <0670> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication 2015/0004544A1, US Patent Application Publication 2016 Known solvents disclosed in paragraphs <0424> to <0426> of specification No. /0237190A1 and paragraphs <0357> to <0366> of specification US Patent Application Publication No. 2016/0274458A1. Examples of solvents that can be used in the preparation of the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkylene alkoxy propionate, etc. base esters, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have rings (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxy acetates and Organic solvents such as alkyl pyruvate.

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent not having a hydroxyl group can be used. As a solvent with a hydroxyl group and a solvent without a hydroxyl group, the aforementioned exemplary compounds can be appropriately selected. As a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or lactic acid alkyl group is preferred, and propylene glycol monomethyl ether (PGME ), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate are more preferred. Also, as a solvent not having a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound which may have a ring, cyclic lactone or alkyl acetate, etc. Preferably, among these, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, gamma-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate More preferably, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, cyclohexanone, cyclopentanone or 2-heptanone are further more preferable. Propylene carbonate is also preferable as a solvent having no hydroxyl group. The mixing ratio (mass ratio) of the solvent having a hydroxyl group to the solvent not having a hydroxyl group is 1/99-99/1, preferably 10/90-90/10, more preferably 20/80-60/40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent not having a hydroxyl group is preferable. It is preferable that the solvent contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate, or may be a mixed solvent of two or more types of propylene glycol monomethyl ether acetate.

＜Surfactant＞ The resist composition of the present invention may further contain a surfactant. As the surfactant, fluorine-based and/or silicon-based surfactants (specifically, fluorine-based surfactants, silicon-based surfactants, or surfactants having both fluorine atoms and silicon atoms) are preferred.

Examples of the fluorine-based and/or silicon-based surfactant include those described in paragraph <0276> of US Patent Application Publication No. 2008/0248425. In addition, other surfactants than the fluorine-based and/or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008/0248425 can also be used.

Surfactants may be used alone or in combination of two or more. When the resist composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. Surfactants may be used alone or in combination of two or more. When two or more surfactants are used, the total content thereof is preferably within the above range.

(other additives) The resist composition of the present invention may further contain various components, for example, may contain a group selected from the group consisting of hydrophobic resins, acid proliferators, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors and one or more components in the group of a dissolution accelerator and the like.

＜Preparation method＞ The solid content concentration of the resist composition of the present invention is more than 20% by mass, more preferably 21 to 50% by mass, more preferably 22 to 40% by mass, and still more preferably 23 to 35% by mass. In addition, the solid content concentration refers to the percentage by mass of the total solid content (total mass of resist components other than the solvent) relative to the total mass of the composition.

The resist composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably in the above-mentioned mixed solvent, filtering it with a filter, and applying it on on the specified 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 still more preferably 0.03 μm or less. Also, when the solid content concentration of the composition is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and 0.3 μm or less for further improvement. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-062667 (Japanese Patent Application Laid-Open No. 2002-062667 ), it is possible to perform cyclic filtration, or to perform filtration by connecting multiple types of filters in series or in parallel. . Also, the composition can be filtered multiple times. Furthermore, the composition may be degassed before and after filtering through the filter.

The viscosity of the resist composition of the present invention is preferably 20 to 500 mPa·s. The viscosity of the resist composition of the present invention is more preferably 20 to 300 mPa·s from the viewpoint of better coatability. In addition, at room temperature (23° C.), the viscosity can be measured using an E-type viscometer.

＜Use＞ The resist composition of the present invention relates to an actinic radiation-sensitive or radiation-sensitive resin composition whose properties are changed by reacting with irradiation of actinic rays or radiation. More specifically, the resist composition of the present invention relates to a mold structure used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing circuit boards such as liquid crystals and thermal heads, and imprinting. Actinic radiation-sensitive or radiation-sensitive resin compositions in fabrication, other photoetching processing steps or lithographic printing plates, or the manufacture of acid-hardening compositions. The pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode formation step, a rewiring formation step, MEMS (Micro Electro Mechanical Systems: Micro Electro Mechanical Systems) and the like.

[Resist film, pattern forming method] The present invention also relates to a pattern forming method using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. In addition, the resist film (actinic radiation-sensitive or radiation-sensitive 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 step of forming a resist film (actinic radiation-sensitive or radiation-sensitive film) on a support using the above-mentioned resist composition (actinic radiation-sensitive or radiation-sensitive resin composition) (resist film formation step); (ii) A step of exposing (irradiating actinic rays or radiation) to the above resist film (exposure step); and (iii) A step of developing the above-mentioned exposed resist film using a developer (developing step).

The pattern forming method of the present invention is not particularly limited as long as it includes the above steps (i) to (iii), and may further include the following steps. In the pattern forming method of the present invention, the exposure method in (ii) the exposure step may be liquid immersion exposure. In the pattern forming method of the present invention, it is preferable to include (iv) a preheating (PB: PreBake) step before the (ii) exposure step. In the pattern forming method of the present invention, it is preferable to include (v) a post-exposure heating (PEB: Post Exposure Bake) step after the (ii) exposure step and before the (iii) image development step. In the pattern forming method of the present invention, the (ii) exposure step may be included a plurality of times. In the pattern forming method of the present invention, a plurality of (iv) preheating steps may be included. In the pattern forming method of the present invention, a plurality of (v) post-exposure heating steps may be included.

In the pattern forming method of the present invention, the above-mentioned (i) film-forming step, (ii) exposing step, and (iii) developing step can be performed by commonly known methods.

(i) The film thickness of the resist film formed in the resist film forming step is preferably 500 to 11000 nm, more preferably 1000 to 9000 nm, and still more preferably 3000 to 7000 nm.

Also, if necessary, a resist underlayer film (for example, SOG (Spin On Glass: Spin On Glass), SOC (Spin On Carbon: Spin On Carbon) and an antireflection film can be formed between the resist film and the support. ). As the material constituting the resist underlayer film, known organic or inorganic materials can be used as appropriate. A protective film (top coat layer) may be formed on the upper layer of the resist film. As a protective film, a well-known material can be used suitably. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, and U.S. Patent Application Publication No. 2016/0299432 . The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016/157988A. As a composition for protective film formation, what contains the said acid diffusion control agent is preferable. A protective film can be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.

The support is not particularly limited, and substrates generally used in the lithography process of other photosensitive etching processes, etc., can be used in addition to the manufacturing steps of semiconductors such as ICs or the manufacturing steps of circuit substrates such as liquid crystals and thermal heads. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ , and SiN.

Regarding the heating temperature, in any one of the (iv) preheating step and (v) post-exposure heating step, 70 to 160°C is preferable, 70 to 155°C is more preferable, and 80 to 150°C is further preferable. better. Regarding the heating time, it is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and 30 to 90 seconds in either of the (iv) preheating step and (v) post-exposure heating step for further improvement. Heating can be performed using the mechanisms provided in the exposure device and the developing device, or can be performed using a hot plate or the like.

The wavelength of the light source used in the exposure step is not particularly limited, and examples include infrared light, visible light, ultraviolet light, deep ultraviolet light, extreme ultraviolet light (EUV light), X-rays, and electron beams. Among them, far-ultraviolet light is preferred, and its wavelength is preferably below 250 nm. Specifically, KrF excimer laser ( ₂₄₈ nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV light (13 nm) and electron beams, etc. KrF excimer laser, ArF excimer laser, EUV light or electron beam are preferred, and KrF excimer laser is more preferred.

(iii) The developer used in the image development step may be an alkali developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

Quaternary ammonium salts typified by tetramethylammonium hydroxide are generally used as alkaline developing solutions, and aqueous alkaline solutions such as inorganic alkalis, primary to tertiary amines, alcohol amines, and cyclic amines can also be used. Furthermore, the above-mentioned alkali developing solution may contain alcohols and/or surfactants in an appropriate amount. The alkali concentration of an alkali developing solution is 0.1-20 mass % normally. The pH of the alkaline developing solution is usually 10-15. The development time using an alkaline developing solution is usually 10 to 300 seconds. The alkali concentration, pH, and developing time of an alkali developing solution can be adjusted suitably according to the pattern to be formed.

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

Examples of ketone-based solvents 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, acetylacetone, acetonylacetone, violet Ketone, Diacetone Alcohol, Acetyl Methanol, Acetophenone, Methyl Naphthyl Ketone, Isophorone and Propylene Carbonate, etc.

Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, Alcohol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, Methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, butyl propionate, etc.

As the alcohol-based solvent, amide-based solvent, ether-based solvent, and hydrocarbon-based solvent, 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, and may be mixed with solvents other than the above-mentioned ones or water. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably not substantially containing water.

The content of the organic solvent relative to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and 95 to 100% by mass relative to the total amount of the developer. Quality % is especially good.

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

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

The organic developer may contain the above-mentioned acid diffusion control agent.

As the developing method, for example, a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dipping method); The method of spraying the developer on the surface of the substrate (spray method); and the method of continuously spraying the developer while scanning the nozzle of the developer at a certain speed on the substrate rotating at a certain speed (dynamic distribution method), etc.

A step of developing using an aqueous alkali solution (alkali developing step) and a step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined. Thereby, since it is possible to form a pattern without dissolving only a region of an intermediate level of exposure intensity, it is possible to form a finer pattern.

After the (iii) developing step, it is preferable to include a step of washing with a rinse solution (rinsing step).

As the rinse solution used in the rinse step after the development step using an alkaline developing solution, for example, pure water can be used. Pure water may contain a suitable amount of surfactant. In this case, after the developing step or the rinsing step, a process of removing a developing solution or a rinsing solution adhering to the pattern with a supercritical fluid may be added. Furthermore, in order to remove moisture remaining in the pattern, heat treatment may be performed after rinsing treatment or treatment with a supercritical fluid.

The rinse solution used in the rinse step after the developing step using a developer 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 better to use a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. good. Specific examples of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents include the same ones described in the developer containing an organic solvent. As the rinsing liquid used in the rinsing step at this time, a rinsing liquid containing monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the rinsing step include linear, branched or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methanol 2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol , 4-octanol and methyl isobutyl carbinol. Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl alcohol. Isobutyl Methanol etc.

Each component may mix plural types, and may mix and use it with the organic solvent other than the above. The water content in the rinse liquid is preferably at most 10% by mass, more preferably at most 5% by mass, and still more preferably at most 3% by mass. Favorable image development characteristics can be acquired by making water content into 10 mass % or less.

The rinse solution may contain a suitable amount of surfactant. In the rinsing step, the substrate to be developed is cleaned with a rinsing solution. The method of cleaning treatment is not particularly limited, and examples include a method of continuously spraying a rinse solution on a substrate rotating at a constant speed (spin coating method), and a method of immersing the substrate in a tank filled with a rinse solution for a certain period of time. (dipping method), or the method of spraying the developer on the surface of the substrate (spray method), etc. Among them, it is preferable to perform cleaning treatment by a spin coating method, and to remove the rinse solution from the substrate by rotating the substrate at a rotation speed of 2,000 to 4,000 rpm (revolution per minute) after cleaning. In addition, it is also preferable to include a heating step (Post Bake: post-baking) after the rinsing step. The developing solution and rinse solution remaining between the patterns and inside the patterns are removed by this heating step. In the heating step after the rinsing step, the heating temperature is usually 40 to 160°C, preferably 70 to 120°C, more preferably 70 to 115°C. The heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The film thickness (height of the pattern) of the pattern obtained in the pattern forming method of the present invention is preferably 500 to 11000 nm, more preferably 1000 to 9000 nm, and still more preferably 3000 to 7000 nm. When the formed pattern is linear, the aspect ratio obtained by dividing the pattern height by the line width is preferably 0.3-20, more preferably 0.5-15, and more preferably 1-10. When the formed pattern is a groove (groove) pattern or a contact hole pattern, the aspect ratio obtained by dividing the pattern height by the value of the groove width or aperture is preferably 0.3-20, 0.5-15 1-10 is more preferable.

Various materials used in the resist composition of the present invention and the pattern forming method of the present invention (for example, resist solvent, developer, rinse solution, composition for forming an antireflection film, or composition for forming a top coat layer) It is better not to contain impurities such as metal components, isomers and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably not more than 1 ppm, more preferably not more than 100 ppt, and still more preferably not more than 10 ppt, and substantially not contained (below the detection limit of the measuring device) is Excellent.

As a method of removing impurities such as metals from the above-mentioned various materials, for example, filtration using a filter is mentioned. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. Filters can be used pre-cleaned with organic solvents. In the filter filtration step, a plurality of types of filters can be connected in series or in parallel and used. When using multiple types of filters, filters with different pore diameters and/or materials can be used in combination. In addition, various materials may be filtered multiple times, and the step of performing multiple times of filtration may be a circulating filtration step. As a filter, a filter with reduced extractables as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426) is preferable. In addition to filter filtration, removal of impurities by adsorption materials can be performed, and filter filtration and adsorption materials can also be used in combination. As the adsorbent, a known adsorbent can be used, for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Laid-Open No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500). Also, as a method of reducing impurities such as metals contained in the above-mentioned various materials, it is possible to select raw materials with a small metal content as raw materials constituting various materials, filter the raw materials constituting various materials, or use Teflon (registered Trademark) to line the inside of the device, etc., to conduct distillation under the conditions of suppressing pollution as much as possible. Preferable conditions in filter filtration of raw materials constituting various materials are the same as those described above. In order to reduce the content of metal impurities in the resist composition to a small amount (for example, ppt level by mass), in the production steps (steps of synthesizing raw materials, etc.) of the materials (resin, photoacid generator, etc.) of the resist composition It is also preferable to perform partial or whole glasslining treatment in the device of the device used. Such a method is described, for example, in Chemical Industry Daily on December 21, 2017.

In order to prevent the mixing of impurities, it is better to store the above-mentioned various materials 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.

A method of improving the surface roughness of the pattern can be applied to the pattern formed by the pattern forming method of the present invention. As a method for improving the surface roughness of a pattern, for example, a method of treating a pattern with a hydrogen-containing gas plasma disclosed in US Patent Application Publication No. 2015/0104957 can be mentioned. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297 and Proc. of SPIE Vol.8328 83280N-1 "EUV Resist Curing Known methods described in "Technique for LWR Reduction and Etch Selectivity Enhancement". In addition, the pattern formed by the above method can be used, for example, as a spacer manufacturing process disclosed in Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and U.S. Patent Application Publication No. 2013/0209941. Core material (Core).

[Manufacturing method of electronic components] Moreover, the present invention also relates to a method of manufacturing an electronic component including the above pattern forming method. The electronic component produced by the method for producing an electronic component of the present invention is preferably mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation: Office Automation)-related equipment, media-related equipment, optical equipment, communication equipment, etc.). [Example]

Hereinafter, the present invention will be described in more detail based on examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the Examples shown below.

[Preparation of resist composition (actinic radiation-sensitive or radiation-sensitive resin composition)] A resist composition (actinic radiation-sensitive or radiation-sensitive resin composition) was prepared using the components shown below.

＜Ether compound＞ As ether compounds, the compounds shown below were used.

[chemical 19]

＜Resin＞ As the resin, the resins shown below were used.

[chemical 20]

The following table shows the composition ratio (molar ratio, corresponding from left) of each repeating unit, weight average molecular weight, and degree of dispersion (weight average molecular weight/number average molecular weight) in each resin.

[Table 1]

＜Photoacid generator＞ As the photoacid generator, the photoacid generator shown below was used.

＜酸擴散控制劑＞ 作為酸擴散控制劑，使用了以下化合物。[chem 21]

<Acid diffusion control agent> As the acid diffusion control agent, the following compounds were used.

[chem 22]

＜Surfactant＞ As surfactants, the following compounds were used.

G1: Compounds shown below G2: MEGAFACE-R4 (fluorine-based surfactant, manufactured by DIC Corporation)

[chem 23]

<Solvent> As a solvent, a mixed solvent of PGMEA (propylene glycol monomethyl ether acetate) and PGME (propylene glycol monomethyl ether) (mixing ratio: PGMEA/PGME=80/20 (mass ratio)) was used. <Preparation of resist composition>

Dissolve the ether compound, resin, photoacid generator, acid diffusion controller, and surfactant in a solvent so that the solid content described in the following table is satisfied, and the solution is prepared as a solid described in the table Ingredient concentration. The obtained solution was micro-filtered using a membrane filter with a diameter of 0.3 μm to obtain a resist composition. The composition of the resist composition used in each Example or Comparative Example is shown in the following table. The notation of the content in the table shows the content (mass %) of each component with respect to the total solid content.

[Table 2]

[Evaluation] ＜Formation of patterns＞ An 8-inch Si substrate (manufactured by Advanced Materials Technology, Inc.) subjected to hexamethyldisilazane treatment using a spin coater "ACT-8" manufactured by Tokyo Electron Limited. (hereinafter also referred to as "substrate". )) on which the resist composition was spin-coated. This substrate was heated (PB: PreBake) at 140° C. for 60 seconds and dried to form a resist film with a film thickness of 4.2 μm. Then, using a KrF excimer laser scanner (manufactured by ASML, PAS5500/850C wavelength 248 nm), exposure was performed at various exposure amounts through a mask with a line width of 500 nm and a space width of 300 nm. At 115°C, the exposed resist film was further heated for 60 seconds, then immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and developed to obtain a line and Space pattern. After the obtained pattern was rinsed with pure water for 30 seconds, it heated at 110 degreeC for 60 seconds.

＜Evaluation of spacing (measurement of space)＞ The produced pattern was observed using a side length SEM S-9380 manufactured by Hitachi, Ltd. The minimum exposure dose at which it can be confirmed that the exposed portion of the resist film is completely developed (removed) so that the surface of the substrate is exposed is taken as the optimum exposure dose Eopt. The amplitude (space (nm)) between adjacent lines when the pattern was formed by this Eopt was measured. It can be evaluated that the smaller this value is, the more excellent the resolution can be and form a pattern with a narrower pitch. In addition, the above-mentioned "width between adjacent lines" refers to the distance between positions connecting adjacent lines having a height of d/2 when the thickness of the pattern is defined as d.

＜Evaluation of cross-sectional shape (rectangularity)＞ The cross-section of the pattern formed at the optimum exposure amount Eopt was observed with a scanning electron microscope, and the cross-sectional shape (rectangularity) was evaluated for the shape of the observed line with reference to the following references.

A: The shape of the line is a rectangle. B: The shape of the wire is tapered. C: The shape of the line is tapered, and a part of the non-exposed portion was removed during image development, resulting in thinning. -: Pattern collapse occurs without being able to form a pattern. In addition, when the width of the upper side of the groove (the region where the resist was removed by exposure) was greater than the width of the bottom side by 1.5 times or more, the shape of the line was evaluated as tapered.

[Results] The evaluation results in each Example or Comparative Example and the characteristics of the resist composition used in each Example or Comparative Example are shown in the following table. In the table, the column "R1" shows the mass ratio of the content of the ether compound to the content of the acid diffusion controller in the resist composition (content of ether compound/content of acid diffusion controller). The column of "R2" shows the mass ratio of the content of the ether compound to the content of the resin B in the resist composition (content of the ether compound/content of the resin B). In the column of "nitrogen-containing", whether or not the ether compound in the resist composition is a nitrogen-containing compound is shown. When this necessary condition is satisfied, it is regarded as A, and when it is not satisfied, it is regarded as B. In the column of "Formula (X1)", whether or not the ether compound in the resist composition is represented by the general formula (X1) is shown. When this necessary condition is satisfied, it is regarded as A, and when it is not satisfied, it is regarded as B. The column "R ^q1 : phenyl ring group" indicates whether R ^q1 is a benzene ring group when the ether compound in the resist composition is a compound represented by formula (X1). When this necessary condition is satisfied, it is regarded as A, and when it is not satisfied, it is regarded as B. The column of "phenolic polar unit" shows whether or not the resin in the resist composition contains a repeating unit having a phenolic polar group. When this necessary condition is satisfied, it is regarded as A, and when it is not satisfied, it is regarded as B. The column of "benzene unit content" shows the content (mass %) of the repeating unit having a benzene ring group in the resin in the resist composition with respect to the total mass of the resin. In the column of "formula (Z1-3)", whether the photoacid generator in a resist composition is a compound represented by general formula (Z1-3) is shown. When this necessary condition is satisfied, it is regarded as A, and when it is not satisfied, it is regarded as B.

[table 3]

As shown in the above table, it was confirmed that a pattern with a high aspect ratio and a narrow pitch can be formed by using the resist composition of the present invention. Also, the cross-sectional shape of the formed pattern was better than that of the pattern obtained by using the resist composition of the comparative example. On the other hand, the desired pattern could not be obtained with the resist composition of the comparative example. Furthermore, in Comparative Example 4, cracks occurred in the resist film after PB, and pattern formation was not possible. Also, as a result of a test using a resist composition having a solid content concentration of 10% by mass, it was not possible to form a resist film having a film thickness (4.2 μm) as an evaluation standard.

From the results shown in the table, it was confirmed that when the ether compound is a nitrogen-containing compound, a pattern with a narrower pitch can be formed (comparison of Examples 1 to 4). It was confirmed that when the ether compound is a compound represented by the general formula (X1) and the group corresponding to R ^q1 is a phenyl ring group, a pattern with a narrower pitch can be formed, and the cross-sectional shape of the obtained pattern is also more excellent (Comparison of Examples 1 to 3). It was confirmed that when the content of the repeating unit having a benzene ring group was less than 65 mol% relative to the total mass of the resin, a pattern with a narrower pitch could be formed, and the cross-sectional shape of the obtained pattern was also more excellent (Example 1 , 5 and 6 comparison). It was confirmed that when the photoacid generator is a compound represented by the formula (ZI-3), a pattern with a narrower pitch can be formed (comparison of Examples 1, 7, and 10).

Claims (7)

An actinic radiation-sensitive or radiation-sensitive resin composition, which comprises: an ether compound; a resin comprising repeating units with phenolic polar groups and repeating units with acid-decomposable groups; photoacid generators; acid diffusion control agents, It is a compound different from the ether compound; and a solvent, the ether compound in the actinic radiation-sensitive or radiation-sensitive resin composition is a compound represented by the general formula (X2), and the resin further has the general formula (VW) The repeating unit represented, among all the repeating units of the resin, the content of the repeating unit having a benzene ring group is less than 65 mole%, and the mass ratio of the content of the ether compound to the content of the acid diffusion control agent is 0.2 or more, The mass ratio of the content of the ether compound to the content of the resin is 0.0002~0.05, the solid content concentration is greater than 20% by mass, [R ^q1 -(-O-AL-) _m ] ₃ -N (X2) general formula (X2 ), m represents an integer from 1 to 10, AL represents an alkylene group, and R ^q1 represents a hydrogen atom or a substituent, and there are plural ms that may be the same or different; multiple ALs may be the same or different. different; there are plural R ^q1 can be the same or different,

In the general formula (VW), Rv represents a hydrogen atom, an alkyl group or -CH ₂ -O-Rv2, Rv2 represents a hydrogen atom, an alkyl group or an acyl group, and Rw represents a hydrocarbon group with an alicyclic group. Among them, the general formula (VW) The represented repeating unit does not have an acid decomposable group. The actinic radiation-sensitive or radiation-sensitive resin composition described in claim 1, wherein at least one R ^q1 is a phenyl ring group. The actinic radiation-sensitive or radiation-sensitive resin composition as described in item 1 or item 2 of the scope of the patent application, wherein the content of repeating units with benzene ring groups in all repeating units of the resin is more than 45 mole % . The actinic radiation-sensitive or radiation-sensitive resin composition as described in item 1 or item 2 of the scope of patent application, wherein the photoacid generator is selected from compounds represented by general formula (ZI-3) and general formula One or more compounds in the group of compounds represented by (ZI-4),

In the general formula (ZI-3), R ₁ represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when R ₁ has a ring structure, the ring structure can have an oxygen atom, a sulfur atom, an ester group, an amido group or a carbon-carbon double bond, R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group, and R _x and R _y independently represent an alkyl group or a cycloalkyl group , 2-oxoalkyl, alkoxycarbonylalkyl, allyl or vinyl, R ₂ and R ₃ can be bonded to each other to form a ring, R ₁ and R ₂ can be bonded to each other to form a ring, R _x and R _y can be bonded to each other to form a ring, Z ^- represents an anion, in the general formula (ZI-4), l represents an integer from 0 to 2, r represents an integer from 0 to 8, R ₁₃ represents a hydrogen atom, a fluorine atom, or a hydroxyl group , alkyl, alkoxy, alkoxycarbonyl or a group with cycloalkyl, R ₁₄ represents hydroxyl, alkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl or a group with cycloalkyl When there are multiple R _14s , the multiple R _14s may be the same or different, each R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group, and two R _15s may be bonded to each other When forming a ring, when two _R15 are bonded to each other to form a ring, heteroatoms such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. A resist film formed using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of the first to fourth claims of the patent application. A pattern forming method, which includes: the step of using a resist film formed from an actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of the first to fourth claims of the patent application; a step of exposing the resist film; and a step of developing the exposed resist film using a developing solution. A method for manufacturing electronic components, which includes the pattern forming method described in item 6 of the scope of the patent application.