TWI804673B - Actinic radiation-sensitive or radiation-sensitive resin composition, actinic radiation-sensitive or radiation-sensitive film, pattern forming method, photomask, manufacturing method and compound of electronic device - Google Patents

Abstract

The present invention provides an actinic radiation-sensitive or radiation-sensitive resin composition containing (A) a compound that generates an acid upon irradiation with actinic rays or radiation and represented by a specific structure, and uses the actinic radiation-sensitive or radiation-sensitive resin composition. Actinic ray-sensitive or radiation-sensitive film of a radioactive resin composition, pattern forming method, photomask, manufacturing method and compound of an electronic device.

Description

Actinic radiation-sensitive or radiation-sensitive resin composition, actinic radiation-sensitive or radiation-sensitive film, pattern forming method, photomask, manufacturing method and compound of electronic device

The present invention relates to an actinic radiation-sensitive or radiation-sensitive resin composition, an actinic radiation-sensitive or radiation-sensitive film, a pattern forming method, a photomask, an electronic device, and a method for manufacturing the compound. More specifically, the present invention relates to a manufacturing process applicable to ultra-LSI (Large Scale Integration) and high-capacity microchips, a mold manufacturing process for nanoimprinting, and a high-density information recording medium The ultralithography method of the manufacturing process, etc., and the actinic radiation-sensitive or radiation-sensitive resin composition, actinic radiation-sensitive or radiation-sensitive film, pattern forming method, photosensitive Manufacturing methods and compounds for covers and electronic devices.

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs, microfabrication by lithography using resist compositions has been performed. In recent years, with the high integration of integrated circuits, ultrafine pattern formation in the sub-micron region or the quarter-micron region has been increasingly required. At the same time, it is found that the exposure wavelength also has a tendency to shorten the wavelength from g-rays to i-rays, and further shorten the wavelength to KrF excimer laser light. Currently, an exposure using ArF excimer laser with a wavelength of 193nm as a light source has been developed. machine. Also, as a technique for further improving resolution, a so-called liquid immersion method in which a liquid having a high refractive index (hereinafter also referred to as "immersion liquid") is filled between a projection lens and a sample has been developed.

Also, currently, in addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), and the like are also being developed. Along with this, a chemically amplified resist composition that effectively senses various radiations and is excellent in sensitivity and resolution has been developed.

For example, Patent Document 1 describes the actinic radiation properties of a resin that is decomposed by the action of an acid and whose solubility in an alkaline developing solution is increased, and a compound that generates an acid by irradiation with actinic rays or radiation. or a radiation-sensitive resin composition, whereby an actinic-ray-sensitive or radiation-sensitive resin composition capable of providing developing residue and excellent outgas characteristics is described. Patent Document 2 describes an electron beam, X-ray, or EUV resist composition containing a compound that generates an acid upon irradiation with actinic rays or radiation. Resist composition for electron beam, X-ray or EUV with suppressed outgas. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2010-237654 [Patent Document 2] Japanese Patent Laid-Open No. 2009-053518

However, in recent years, along with the further miniaturization of the formed pattern, etc., an actinic radiation-sensitive or radiation-sensitive resin composition that can further improve the resolution and reduce development defects in the pattern forming method is required.

The object of the present invention is to provide an actinic radiation-sensitive or radiation-sensitive resin composition capable of achieving both high-end resolution improvement and development defect reduction. Furthermore, another object of the present invention is to provide an actinic radiation-sensitive or radiation-sensitive film, a pattern forming method, a photomask, a method of manufacturing an electronic device, and a compound using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition. .

According to the research of the inventors of the present invention, it was found that the above-mentioned problems can be solved by using the following compound as a compound that generates an acid by irradiation of actinic rays or radiation in an actinic ray-sensitive or radiation-sensitive resin composition, and completed According to the present invention, the compound has a bulky group at the 2nd and 6th positions of the benzenesulfonic acid anion, and a group containing a polar group at the 3rd, 4th or 5th position of the benzenesulfonic acid anion, A group having a group whose polarity is increased by decomposition by the action of an acid, or a group having a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer is used. That is, the inventors of the present invention have found that the above-mentioned subject can be achieved by the following configuration.

[1] An actinic radiation-sensitive or radiation-sensitive resin composition containing the following (A). (A) A compound that generates an acid by irradiation with actinic rays or radiation and is a compound represented by the general formula (1)

[chemical formula 1]

In the general formula (1), R ₁ and R ₂ each independently represent a group represented by any one of the following general formulas (R-1) to (R-3). R ₃ to R ₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₃ to R ₅ represents a group represented by the following general formula (R-4). M ^m+ represents a cation. m represents an integer of 1 or more.

[chemical formula 2]

In the general formulas (R-1) to (R-3), R ₆ to R ₂₇ each independently represent a hydrogen atom or a substituent. In the general formula (R-1), at least two of R ₆ to R ₁₃ may be bonded to each other to form a ring. In the general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to each other to form a ring. In the general formula (R-3), at least two of R ₁₉ to R ₂₇ may be bonded to each other to form a ring. * represents a bond to the benzene ring in the general formula (1).

[chemical formula 3]

In general formula (R-4), A represents a single bond or a linking group of (n+1) valence. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different. * represents a bond to the benzene ring in the general formula (1).

[2] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [1], wherein the compound (A) is represented by the following general formula (2).

[chemical formula 4]

In the general formula (2), R ₁ and R ₂ each independently represent a group represented by any one of the above general formulas (R-1) to (R-3). R ₃ to R ₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₃ to R ₅ represents a group represented by the above general formula (R-4). R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.

[3] The actinic radiation-sensitive or radiation-sensitive resin composition according to [2], wherein the compound represented by the above general formula (2) is represented by the following general formula (3).

[chemical formula 5]

In the general formula (3), R ₁ and R ₂ each independently represent a group represented by any one of the above general formulas (R-1) to (R-3). R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. A represents a single bond or a linking group of (n+1) valence. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.

[4] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [3], wherein in the above-mentioned general formula (R-1) in the above-mentioned general formula (3), at least one of R ₆ to R ₈ One is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ to form a ring, and in the above general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to R ₁₇ And at least one of R ₁₈ is bonded to form a ring. In the above general formula (R-3), at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or R ₂₅ to R ₂₇ at least one bond to form a ring.

[5] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [4], wherein in the above-mentioned general formula (R-1) in the above-mentioned general formula (3), at least one of R ₆ to R ₈ A ring formed by bonding with at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R _13. In the above general formula (R-2), at least one of R ₁₄ to R ₁₆ and R ₁₇ and a ring formed by bonding at least one of R ₁₈ , and in the above general formula (R-3), at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or R ₂₅ to In the ring formed by bonding at least one of R ₂₇ , the number of carbon atoms constituting the ring members is 5-10, respectively.

[6] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the compound (A) is represented by the following general formula (4).

[chemical formula 6]

In the general formula (4), R ₃₁ to R ₄₀ each independently represent a hydrogen atom or a substituent. At least two of R ₃₁ to R ₄₀ may be bonded to each other to form a ring. R ₄₁ to R ₅₀ each independently represent a hydrogen atom or a substituent. At least two of R ₄₁ to R ₅₀ may be bonded to each other to form a ring. R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. A represents a single bond or a linking group of (n+1) valence. n represents an integer of 1 or more. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.

[7] The actinic radiation-sensitive or radiation-sensitive resin composition according to [6], wherein the compound represented by the above general formula (4) is represented by the following general formula (5).

[chemical formula 7]

In the general formula (5), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. A represents a single bond or a linking group of (n+1) valence. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.

[8] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [7], wherein A in each of the above general formulas is an aromatic group.

[9] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the compound (A) is represented by the following general formula (6).

[chemical formula 8]

In the general formula (6), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. R ₅₁ to R ₅₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₅₁ to R ₅₅ represents a group represented by the following general formula (R-5).

[chemical formula 9]

In general formula (R-5), B represents a single bond or a (n+1) valence linking group. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different. * represents a bond to the benzene ring in the general formula (6).

[10] The actinic radiation-sensitive or radiation-sensitive resin composition according to [9], wherein in the above general formula (6), B is a single bond or a methylene group.

[11] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [10], wherein Y in each of the above general formulas represents hydroxyl, carboxyl, a group with a carbonyl bond, acyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, aryloxycarbonyl, alkoxycarbonyl, carboxylate group or imide group.

[12] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [11], wherein Y in each of the above formulas represents a hydroxyl group, a carboxyl group or an alkoxycarbonyl group.

[13] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [12], wherein the acid of the above-mentioned compound (A) is generated by irradiation with actinic rays or radiation. pKa is -10 or more and 5 or less.

[14] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [13], which is used for producing a photomask.

[15] An actinic radiation-sensitive or radiation-sensitive film formed using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of [1] to [14]. [16] A method for forming a pattern, comprising: Resist film forming step of forming a resist film using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of [1] to [14]; Exposure of exposing the above resist film steps; and a developing step of developing the exposed resist film using a developer.

[17] A photomask manufactured using the pattern forming method described in [16]. [18] A method of manufacturing an electronic device, including the pattern forming method described in [16].

[19] A compound represented by the following general formula (A).

[chemical formula 10]

In the general formula (A), R ₁ and R ₂ each independently represent a group represented by any one of the following general formulas (R-1) to (R-3). R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. A represents a single bond or a linking group of (n+1) valence. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different. M ^m+ represents a cation. m represents an integer of 1 or more.

[chemical formula 11]

In the general formulas (R-1) to (R-3), R ₆ to R ₂₇ each independently represent a hydrogen atom or a substituent. In the general formula (R-1), at least two of R ₆ to R ₁₃ may be bonded to each other to form a ring. In the general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to each other to form a ring. In the general formula (R-3), at least two of R ₁₉ to R ₂₇ may be bonded to each other to form a ring. * represents a bond to the benzene ring in the general formula (1). In the above general formula (R-1) in the above general formula (3), at least one of R ₆ to R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ To form a ring, in the above general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form a ring, in the above general formula (R-3) , at least one of R ₁₉ to R ₂₁ is bonded to at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ to form a ring. In the above general formula (R-1) in the above general formula (3), at least one of R ₆ to R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ In the above general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form a ring, and in the above general formula (R- 3), in the ring formed by bonding at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ , the number of carbon atoms constituting the ring members is 5 to 10.

[20] The compound as described in [19], wherein the compound is represented by the following general formula (3).

[chemical formula 12]

In the general formula (3), R ₁ and R ₂ each independently represent a group represented by any one of the following general formulas (R-1) to (R-3). R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. A represents a single bond or a linking group of (n+1) valence. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.

[chemical formula 13]

In the general formulas (R-1) to (R-3), R ₆ to R ₂₇ each independently represent a hydrogen atom or a substituent. In the general formula (R-1), at least two of R ₆ to R ₁₃ may be bonded to each other to form a ring. In the general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to each other to form a ring. In the general formula (R-3), at least two of R ₁₉ to R ₂₇ may be bonded to each other to form a ring. * represents a bond to the benzene ring in the general formula (1). In the above general formula (R-1) in the above general formula (3), at least one of R ₆ to R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ To form a ring, in the above general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form a ring, in the above general formula (R-3) , at least one of R ₁₉ to R ₂₁ is bonded to at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ to form a ring. In the above general formula (R-1) in the above general formula (3), at least one of R ₆ to R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ In the above general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form a ring, and in the above general formula (R- 3), in the ring formed by bonding at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ , the number of carbon atoms constituting the ring members is 5 to 10.

[21] The compound according to [19] or [20], wherein The above compound is represented by the following general formula (9).

[chemical formula 14]

In the general formula (9), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. A represents a single bond or a linking group of (n+1) valence. n represents an integer of 1 or more. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.

[22] The compound as described in any one of [19] to [21], wherein the compound is represented by the following general formula (10).

[chemical formula 15]

In the general formula (10), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. R ₅₁ to R ₅₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₅₁ to R ₅₅ represents a group represented by the following general formula (R-5).

[chemical formula 16]

In general formula (R-5), B represents a single bond or a (n+1) valence linking group. n represents an integer of 1 or more. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. When n represents an integer of 2 or more, a plurality of Ys may be the same or different. * represents a bond to the benzene ring in the general formula (10).

[23] The compound as described in any one of [19] to [22], wherein Y in each of the above general formulas represents a hydroxyl group, a carboxyl group, a group having a carbonyl bond, an acyloxy group, an alkoxycarbonyloxy group , aryloxycarbonyloxy, aryloxycarbonyl, alkoxycarbonyl, carbamoyl or imide.

[24] The compound as described in any one of [19] to [23], wherein Y in each of the above formulas represents a hydroxyl group, a carboxyl group or an alkoxycarbonyl group. [Invention effect]

According to the present invention, it is possible to provide an actinic radiation-sensitive or radiation-sensitive resin composition that achieves both high-end resolution improvement and development defect reduction. According to the present invention, there can be provided an actinic radiation-sensitive or radiation-sensitive film using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition, a method for forming a pattern, a photomask, a method for producing an electronic device, and a compound.

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 rays" or "radiation" in this manual refer to, for example, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays and Electron beam (EB: Electron Beam), etc. "Light" in this specification refers to actinic rays or radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure using the clear spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also exposures using electron beams and Drawing by particle beams such as 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 at least one of acrylate and methacrylate. Also, (meth)acrylic acid means at least one of acrylic acid and methacrylic acid. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion (also called molecular weight distribution) (Mw/Mn) of the resin are defined as, based on 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: 1.0mL/min, detector: polystyrene conversion value of differential refractive index detector (Refractive Index Detector)).

In the notation of a group (atomic group) in this specification, the notation of substituted and unsubstituted includes a group having no substituent and 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). Also, the "organic group" in the present specification refers to a group containing at least one carbon atom.

The actinic radiation-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "the composition of the present invention") according to the present invention contains the following actinic radiation-sensitive or radiation-sensitive resin composition (A). (A) A compound that generates an acid by irradiation with actinic rays or radiation and is represented by the following general formula (1)

[chemical formula 17]

In the general formula (1), R ₁ and R ₂ each independently represent a group represented by any one of the following general formulas (R-1) to (R-3). R ₃ to R ₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₃ to R ₅ represents a group represented by the following general formula (R-4). M ^m+ represents a cation. m represents an integer of 1 or more.

[chemical formula 18]

In the general formulas (R-1) to (R-3), R ₆ to R ₂₇ each independently represent a hydrogen atom or a substituent. In the general formula (R-1), at least two of R ₆ to R ₁₃ may be bonded to each other to form a ring. In the general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to each other to form a ring. In the general formula (R-3), at least two of R ₁₉ to R ₂₇ may be bonded to each other to form a ring. * represents a bond to the benzene ring in the general formula (1).

[chemical formula 19]

In general formula (R-4), A represents a single bond or a linking group of (n+1) valence. n represents an integer of 1 or more. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. When n represents an integer of 2 or more, a plurality of Ys may be the same or different. * represents a bond to the benzene ring in the general formula (1).

The composition of the present invention is preferably a resist composition, and 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 resist composition of positive type, and a resist composition for alkali development are preferable. In addition, the composition of the present invention is preferably a chemically amplified resist composition, more preferably a chemically amplified positive resist composition.

[(A) A compound that generates an acid upon irradiation with actinic rays or radiation and is represented by the general formula (1)] As described above, the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention contains (B) a compound that generates an acid upon irradiation with actinic rays or radiation and is represented by the above general formula (1) (also known as as "compound (A)").

According to the present invention, by using the above-mentioned compound (A), it is possible to obtain an actinic radiation-sensitive or radiation-sensitive resin composition capable of achieving both an improvement in resolving power and a reduction in development defects at a high end. Although the reason for this is not clear, it is presumed that as follows.

First, in the general formula (1), R ₁ and R ₂ each independently represent a group represented by any one of the above-mentioned general formulas (R-1) to (R-3). Here, since R ₁ and R ₂ are respectively the 2nd and 6th positions on the basis of the carbon atom bonded to the sulfonic acid anion, they can be called the ortho positions of the sulfonic acid anion. Moreover, the group represented by any one of the above-mentioned general formulas (R-1) to (R-3) is a bulkier group than a methyl group, an ethyl group, or the like. Therefore, it is considered that R ₁ and R ₂ can function as steric hindrance groups with respect to the sulfonic acid anion. As a result, it is presumed that the compound (A) having such a sulfonic acid anion is one in which the acid generated in the exposed area is less likely to diffuse excessively to the unexposed area, and the resolving power is improved. However, generally, when a bulky group is introduced into an acid generator, there is a possibility that development defects accompanied by development residues may easily occur during alkali development due to the increase in hydrophobicity of the acid generator or the like. However, when Y uses a group containing a polar group, a group containing a group whose polarity is increased by decomposition by the action of an acid, or a group containing a group that is decomposed by the action of an alkali developer Surprisingly, when the compound (B) of the present invention is a group whose solubility is increased, development defects accompanied by development residue are further suppressed. The reason for this is not clear, but it is considered that the affinity of the compound (A) of the present invention containing the above-mentioned group to the alkali developing solution is improved in the exposed part of the resist film, so the development accompanied by development residue Defects are suppressed.

In the general formula (1), R ₁ and R ₂ each independently represent a group represented by any one of the above general formulas (R-1) to (R-3). R ₃ to R ₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₃ to R ₅ represents a group represented by the above general formula (R-4). M ^m+ represents a cation. m represents an integer of 1 or more.

[chemical formula 20]

In the general formulas (R-1) to (R-3), R ₆ to R ₂₇ each independently represent a hydrogen atom or a substituent. In the general formula (R-1), at least two of R ₆ to R ₁₃ may be bonded to each other to form a ring. In the general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to each other to form a ring. In the general formula (R-3), at least two of R ₁₉ to R ₂₇ may be bonded to each other to form a ring. * represents a bond to the benzene ring in the general formula (1).

[chemical formula 21]

In general formula (R-4), A represents a single bond or a linking group of (n+1) valence. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different. * represents a bond to the benzene ring in the general formula (1).

The substituent represented by R ₆ to R ₂₇ is not particularly limited as long as it is a monovalent substituent, for example, an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; a halogen atom; Groups of heteroatoms such as sulfur atom, nitrogen atom, and silicon atom; and combinations of two or more of these.

Examples of the alkyl group for R ₆ to R ₂₇ include alkyl groups having 1 to 30 carbon atoms. The alkyl group is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, etc., having 1 to 20 carbon atoms. An alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of alkenyl groups for R ₆ to R ₂₇ include alkenyl groups having 1 to 20 carbon atoms, preferably alkenyl groups having 1 to 8 carbon atoms. The cycloalkyl group for R ₆ to R ₂₇ may be monocyclic or polycyclic. The carbon number of the cycloalkyl group is not particularly limited, but is preferably 3-8.

The aryl group represented by R ₆ to R ₂₇ includes, for example, an aryl group having 6 to 15 carbon atoms. Specifically, preferable examples include phenyl, naphthyl, anthracenyl, and the like. Examples of the halogen atom represented by R ₂ to R ₄ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

Examples of groups containing heteroatoms include hydroxyl, carboxyl, alkoxy, thiol, thioether, nitro, nitroso, cyano, amine, acyloxy, amide, An ether bond, a carbonyl bond, and a combination of two or more of these.

The number of carbon atoms in an alkoxy group, an acyloxy group, and an amide group is preferably 20 or less, more preferably 8 or less. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy and octoxy. Among them, methoxy, ethoxy, propoxy, isopropoxy and tert-butoxy are particularly preferred. In addition, as for the thioether group, except that a sulfur atom is used instead of an oxygen atom, the same ones as those for the alkoxy group can also be mentioned. As an acyloxy group, an acetyloxy group is mentioned, for example. As the amide group, for example, an acetylamide group is mentioned.

An alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom as substituents for R ₆ to R ₂₇ may further have a substituent. As further substituents, for example, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, amino groups, amido groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group and nitro group, and combinations of two or more of these.

In the general formula (R-1), at least two of R ₆ to R ₁₃ may be bonded to form a ring. In the general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to form a ring. In addition, in the general formula (R-3), at least two of R ₁₉ to R ₂₇ may be bonded to form a ring.

In the above general formula (R-1), at least two of R ₆ to R ₁₃ are bonded to form a ring, and in the above general formula (R-2), at least two of R ₁₄ to R _{18 are} The ring formed by bonding, and the ring formed by bonding at least two of R ₁₉ to R ₂₇ in the above general formula (R-3) are not particularly limited, and examples thereof include aromatic or non-aromatic (For example, aliphatic) hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings in which two or more of these rings are combined. The ring structure (among polycyclic condensed rings, the ring structure of the single ring constituting it) includes 3 to 10 membered rings, preferably 4 to 8 membered rings, more preferably 5 or 6 membered rings.

The above-mentioned R ₆ to R ₂₇ can respectively constitute a group including a polar group described later, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group that is decomposed by the action of an alkali developing solution and is developed in an alkali. A group of groups whose solubility in liquid increases.

The substituent represented by R ₃ to R ₅ is not particularly limited as long as it is a monovalent substituent, for example, an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; a halogen atom; , sulfur atom, nitrogen atom, silicon atom and other heteroatom groups; and combinations of two or more of these. Alkyl group; alkenyl group; cycloalkyl group; aryl group _; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; Among the specific examples of substituents in ₂₇ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; The above combinations are the same.

An alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom, which are substituents for R ₃ to R ₅ , may further have a substituent. As further substituents, for example, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, amino groups, amido groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group and nitro group, and combinations of two or more of these.

As described above, at least one of R ₃ to R ₅ represents a group represented by the general formula (R-4). That is, the above-mentioned R ₃ to R ₅ can respectively constitute a group including a polar group described later, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group that is decomposed by the action of an alkali developer. The group (equivalent to Y of the formula (R-4)) and the linking group of the single bond or (n+1) valence (equivalent to the Y of the formula (R-4)) of the group whose solubility increases in the alkali developing solution A) A bonded group.

As the (n+1)valent linking group of A, for example, a divalent linking group is described below. It does not specifically limit as a divalent linking group, For example, an alkylene group, an alkenylene group, an alkynylene group, an aromatic group, or these combinations are mentioned. The alkylene group is not particularly limited, but a linear or branched alkylene group is preferred, and an alkylene group having 1 to 10 carbon atoms is further preferred. Although it does not specifically limit as an alkenylene group, The alkenylene group of 2-10 carbon atoms is preferable. The alkynylene group is not particularly limited, but an alkynylene group having 2 to 10 carbon atoms is preferred.

The aromatic group may be an aryl group, an aralkyl group, a heterocyclic group, and the like. Specific examples of the aryl group having 6 to 15 carbon atoms include phenyl, tolyl, naphthyl, anthracenyl and the like. As the aralkyl group, an aralkyl group having 6 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 12 carbon atoms is more preferable. Specifically, benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, etc. are mentioned. As the heterocyclic group, a heterocyclic group having 6 to 20 carbon atoms is preferable, and a heterocyclic group having 6 to 12 carbon atoms is more preferable. For example, thiophene, furan, and pyridine can be mentioned.

The above-mentioned divalent linking group may further have a substituent. Specific examples of further substituents are the same as specific examples of substituents for R ₆ to R ₂₇ described above. As the (n+1)-valent linking group of A, for example, a group obtained by removing (n-1) hydrogen atoms from a divalent linking group can be mentioned.

Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups.

As the polar group in the group containing the polar group of Y, for example, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonamide group, sulfonimide group, (alkylsulfonyl group) ( Alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkyl Acidic groups such as sulfonyl)methylene, bis(alkylsulfonyl)imide, tris(alkylcarbonyl)methylene, and tris(alkylsulfonyl)methylene, and alcoholic hydroxyl groups wait.

In addition, the alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group, which is a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring. Alcohols (for example, hexafluoroisopropanol, etc.) are excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20 is preferable. Among them, a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group (preferably a hexafluoroisopropanol group) is preferred as the polar group.

As a group containing a polar group, a group having a carbonyl bond can also be mentioned. As a group which has a carbonyl bond, an alkylcarbonyl group, an arylcarbonyl group etc. are mentioned, for example. Examples of the alkyl group in the alkylcarbonyl group include the same ones as the alkyl groups for R ₆ to R ₂₇ . Examples of the aryl group in the arylcarbonyl group include the same ones as the aryl groups for R ₆ to R ₂₇ . The group having a carbonyl bond is a group in which a carbonyl bond and an ether bond are not adjacently bonded.

The alkylcarbonyl and arylcarbonyl groups which are groups having a carbonyl bond may further have a substituent. As further substituents, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; more than one combination. Alkyl group; alkenyl group; cycloalkyl group; aryl group _; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; Among the specific examples of substituents in ₂₇ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; The above combinations are the same.

It does not specifically limit as a group containing a polar group, An organic group containing a polar group can be mentioned. Examples of organic groups containing polar groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; A combination of two or more types is used as a group having a polar group. Alkyl group; alkenyl group; cycloalkyl group; aryl group _; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; Among the specific examples of substituents in ₂₇ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; The above combinations are the same.

For example, examples of the group containing a polar group include an alkyl group containing a polar group and an aryl group containing a polar group. Examples of the alkyl group in the alkyl group including a polar group include the same ones as the alkyl groups for R ₆ to R ₂₇ . As the aryl group in the aryl group including a polar group, for example, the same ones as the aryl groups as R ₆ to R ₂₇ can be mentioned. Also, the group containing a polar group may be the polar group itself.

Among the groups of Y including a group whose polarity is increased by decomposing by the action of an acid, a group whose polarity is increased by decomposing by the action of an acid (hereinafter also referred to as "acid decomposable group") ) preferably has a structure protected by a group (leaving group) that decomposes a polar group and leaves it by the action of an acid. As a polar group, what is the same as the polar group in the group containing a polar group which is Y can be mentioned.

Examples of the group decomposed and detached by the action of an acid (leaving group) include groups represented by formulas (Y1) to (Y4). Formula (Y1): -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) Formula (Y2): -C (=O)OC (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) Formula (Y3): -C (R ₃₆ )(R ₃₇ )(OR ₃₈ ) Formula (Y4): -C(Rn)(H)(Ar) Formula (Y5): -Si(Rx ₁ )(Rx ₂ )(Rx ₃ )

In formula (Y1), formula (Y2) and formula (Y5), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). In addition, 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, Rx ₁ to Rx ₃ each independently represent a straight-chain or branched alkyl group is preferable, and Rx ₁ to Rx ₃ each independently represent a straight-chain alkyl group is more preferable. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic or polycyclic ring. As the alkyl group of 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 and tert-butyl group is preferable. As the cycloalkyl group of Rx ₁ to Rx ₃ , there are many monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl, etc. Cycloalkyl rings are preferred. Cycloalkyl formed as two bonds among Rx ₁ to Rx ₃ , monocyclic cycloalkyl such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecanyl, tetracyclododecane A polycyclic cycloalkyl group such as an adamantyl group and an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable. 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 with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. Among the groups represented by formula (Y1) or formula (Y2), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the aforementioned cycloalkyl group, which is 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. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. R ₃₆ is also preferably a hydrogen atom.

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

[chemical formula 22]

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group that may contain heteroatoms, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group that combines these ( For example, groups combining alkyl and cycloalkyl). Among the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be substituted by 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, cycloalkyl group, 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, since Tg (glass transition temperature) and activation energy increase, film strength can be secured 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.

The acid-decomposable group preferably has an acetal structure. The acetal structure is, for example, a structure in which a polar group such as a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group is protected by a group represented by the above formula (Y3).

The group containing an acid-decomposable group is not particularly limited as long as it is a group containing an acid-decomposable group, and examples thereof include organic groups containing an acid-decomposable group. Examples of organic groups containing acid-decomposable groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; And the combination of these 2 or more types is set as the group which has an acid-decomposable group. Alkyl group; alkenyl group; cycloalkyl group; aryl group _; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; Among the specific examples of substituents in ₂₇ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; The above combinations are the same.

Examples of the group containing an acid decomposable group include an alkyl group containing an acid decomposable group and an aryl group containing an acid decomposable group. As the alkyl group among the alkyl groups containing an acid decomposable group, for example, the same ones as the alkyl groups as R ₆ to R ₂₇ can be mentioned. As the aryl group in the aryl group including an acid-decomposable group, for example, the same ones as the aryl groups as R ₆ to R ₂₇ can be mentioned. In addition, the group containing an acid-decomposable group may be an acid-decomposable group itself.

Solubility in alkaline developing solution of Y that is decomposed by action of alkaline developing solution and that includes a group whose solubility in alkaline developing solution is increased The enlarged group is also called "polarity conversion group". As specific examples, lactone group, carboxylate group (-COO-), acid anhydride group (-C(O)OC(O)-), Acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO ₂ O-), sulfonate group (-SO ₂ O-) etc.

As a group containing a polarity converting group, for example, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aminoformyl group, an imide group, etc. base.

The carbon number of the acyl group in an acyloxy group becomes like this. Preferably it is 1-10, More preferably, it is 1-5. The carbon number of the alkoxy group in an alkoxycarbonyloxy group becomes like this. Preferably it is 1-10, More preferably, it is 1-5.

The carbon number of the aryl group in the aryloxycarbonyloxy group is preferably 6-20, more preferably 6-12. The carbon number of the aryl group in the aryloxycarbonyl group is preferably 6-20, more preferably 6-12. The number of carbon atoms in the alkoxy group in the alkoxycarbonyl group is preferably 6-20, more preferably 6-12. The imide group is a group obtained by removing one hydrogen atom from imide.

An acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, and an imide group may further have a substituent. As further substituents, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; more than one combination. Alkyl group; alkenyl group; cycloalkyl group; aryl group _; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; Among the specific examples of substituents in ₂₇ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; The above combinations are the same.

As a preferred aspect of the present invention, the polarity converting group is a group represented by X in the partial structure represented by general formula (KA-1) or (KB-1).

[chemical formula 23]

X in general formula (KA-1) or (KB-1) represents carboxylate group: -COO-, acid anhydride group: -C(O)OC(O)-, acid imide group: -NHCONH-, Carboxylic acid thioester group: -COS-, carbonate group: -OC(O)O-, sulfate ester group: -OSO ₂ O-, sulfonate group: -SO ₂ O-. Y ¹ and Y ² may be the same or different, and represent electron-attracting groups. In addition, as a preferred aspect of the present invention, the above-mentioned compound (B) contains a group having a partial structure represented by the general formula (KA-1) or (KB-1) as a group containing a polarity conversion group, but In the case of the partial structure represented by the general formula (KA-1) and the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent, when the above partial structure does not have a bond, it has the above The partial structure group refers to a group having a valence of 1 or more obtained by removing any hydrogen atom in the above partial structure.

The partial structure represented by the general formula (KA-1) forms a ring structure together with the group as X. X in the general formula (KA-1) is preferably a carboxylate group (that is, when KA-1 forms a lactone ring structure), an acid anhydride group, or a carbonate group. More preferred is a carboxylate group. The ring structure represented by the general formula (KA-1) may have substituents, for example, may have nka substituents Z _ka1 . When Z _ka1 is plural, each independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amido group, an aryl group, a lactone ring group or an electron-attracting group. Z _ka1 can link to each other to form a ring. Examples of rings formed by linking _Zka1 to each other include cycloalkyl rings and heterocycles (cyclic ether rings, lactone rings, etc.). nka represents an integer of 0-10. It is preferably an integer of 0-8, more preferably an integer of 0-5, further preferably an integer of 1-4, most preferably an integer of 1-3.

The electron-attracting group of Z _ka1 is the same as the electron-attracting group of ^Y1 and ^Y2 described later represented by a halogen atom. In addition, the above-mentioned electron-attracting groups may be substituted with other electron-attracting groups.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group or an electron-attracting group, more preferably an alkyl group, a cycloalkyl group or an electron-attracting group. Moreover, as an ether group, what is substituted with an alkyl group, a cycloalkyl group, etc., that is, an alkylether group etc. are preferable. Preferable examples of the electron-attracting group are the same as the electron-attracting groups of ^Y1 and ^Y2 described later. Examples of the halogen atom of Z _ka1 include fluorine atom, chlorine atom, bromine atom and iodine atom, among which fluorine atom is preferred. The alkyl group as Z _ka1 may have a substituent, and may be either a straight chain or a branched chain. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, for example, methyl, ethyl, n-propyl, n-butyl, second-butyl, and third-butyl Base, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. The branched chain alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, for example, isopropyl, isobutyl, tertiary butyl, isopentyl, tertiary pentyl, Isohexyl, tertiary hexyl, isoheptyl, tertiary heptyl, isooctyl, tertiary octyl, isononyl, tertiary decanyl, etc. A methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like are preferably those having 1 to 4 carbon atoms. The cycloalkyl group of Z _ka1 may have a substituent, may be monocyclic, may be polycyclic, or may be bridged. For example, a cycloalkyl group may have a crosslinked structure. As a monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, cyclobutyl, and cyclooctyl. As the polycyclic type, groups having a bicyclic, tricyclic, and tetracyclic structure with 5 or more carbon atoms can be mentioned, and cycloalkyl groups with 6 to 20 carbon atoms are preferable, for example, adamantyl, nor Camphenyl, isobornyl, camphenyl, dicyclopentyl, α-pinenyl, tricyclodecanyl, tetracyclododecyl, androstanyl group, and the like. As the cycloalkyl group, the following structures are also preferable. In addition, some of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

[chemical formula 24]

Preferable examples of the aforementioned alicyclic moieties include adamantyl, noradamantyl, decahydronaphthyl, tricyclodecanyl, tetracyclododecyl, norbornyl, cedrol, cyclohexyl, Cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl. More preferred are adamantyl, decahydronaphthyl, norbornyl, cedrol, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, and tricyclodecanyl. Examples of substituents of such alicyclic structures include alkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, carboxyl groups, and alkoxycarbonyl groups. As the alkyl group, lower alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl are preferred, and methyl, ethyl, propyl, and isopropyl are more preferred. As said alkoxy group, C1-C4 thing, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, can be mentioned preferably. Examples of substituents that the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), and the like.

Examples of the lactone ring group of Z _ka1 include groups obtained by removing a hydrogen atom from the structure represented by any one of (KA-1-1) to (KA-1-17) described below.

Examples of the aryl group in Z _ka1 include phenyl and naphthyl.

As substituents that the alkyl, cycloalkyl and aryl groups of Z _ka1 may further have include hydroxyl, halogen atoms (fluorine, chlorine, bromine, iodine), nitro, cyano, the above-mentioned alkyl groups, methoxy Alkoxy, methoxycarbonyl, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, second butoxy, third butoxy, etc. , ethoxycarbonyl and other alkoxycarbonyl, benzyl, phenethyl, cumyl and other aralkyl, aralkoxy, formyl, acetyl, butyryl, benzoyl , cyanamide, pentyloxy and other acyl groups, butyryloxy and other acyloxy groups, the above-mentioned alkenyl groups, vinyloxy, propyleneoxy, allyloxy, butenyloxy and other alkenyloxy groups, the above-mentioned An aryl group, an aryloxy group such as a phenoxy group, an aryloxycarbonyl group such as a benzoyloxy group, and the like.

X in the general formula (KA-1) is a carboxylate group, and the partial structure shown in the general formula (KA-1) is preferably a lactone ring, preferably a 5- to 7-membered lactone ring. In addition, as in the following (KA-1-1) to (KA-1-17), a bicyclic structure is formed on the 5- to 7-membered cyclic lactone ring which is a partial structure represented by the general formula (KA-1), In the form of spiro ring structure, other ring structures are preferred for the condensed ring. Regarding the surrounding ring structures to which the ring structure represented by the general formula (KA-1) can be bonded, for example, the structures in the following (KA-1-1) to (KA-1-17), or It is the benchmark.

As a structure containing a lactone ring structure represented by general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. In addition, the lactone structure may be directly bonded to the main chain. The preferred structure is as follows: (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA- 1-14), (KA-1-17).

[chemical formula 25]

The structure containing the above-mentioned lactone ring structure may or may not have a substituent. As a preferable substituent, the thing similar to the substituent which the ring structure represented by the said General formula (KA-1) may have is mentioned.

There may be an optically active substance in the lactone structure, and any optically active substance can be used. In addition, one kind of optically active substance may be used alone, or a plurality of kinds of optically active substances may be used in combination. When one optically active substance is mainly used, the optical purity (ee) thereof is preferably 90% or higher, more preferably 95% or higher, most preferably 98% or higher.

As X of general formula (KB-1), a carboxylate group (-COO-) can be mentioned preferably.

Y ¹ and Y ² in the general formula (KB-1) each independently represent an electron attracting group.

The electron attracting group is preferably a partial structure represented by the following formula (EW). * in the formula (EW) represents a bond directly bonded to (KA-1) or a bond directly bonded to X in (KB-1).

[chemical formula 26]

In formula (EW), _new is the number of repetitions of the linking group represented by -C(R _ew1 )(R _ew2 )-, and represents an integer of 0 or 1. When n _ew is 0, it means a single bond, which means that Y _{ew1 is} directly bonded. Y _ew1 can include halogen atom, cyano group, nitrile group, nitro group, halogenated (cyclo)alkyl group, halogenated aryl group, oxy group, carbonyl group represented by -C(R _f1 )(R _f2 )-R _f3 described later , sulfonyl, sulfinyl, and combinations thereof, the electron-attracting group can be, for example, the following structure. In addition, "halogenated (cyclo)alkyl" means an alkyl group and a cycloalkyl group at least partially halogenated. R _ew3 and R _ew4 each independently represent an arbitrary structure. Regardless of the structure of R _ew3 and R _ew4 , the partial structure represented by the formula (EW) has electron-withdrawing properties, and is preferably an alkyl group, a cycloalkyl group, or a fluorinated alkyl group.

[chemical formula 27]

When Y _ew1 is a group with a valence of 2 or more, the remaining bonds are those that form bonds with any atoms or substituents. Y _ew1 is preferably a halogen atom or a halogenated (cyclo)alkyl or halogenated aryl group represented by -C(R _f1 )(R _f2 )-R _f3 . R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. At least two of R _ew1 , R _ew2 and Ye _ew1 may be connected to each other to form a ring.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, and more preferably a fluorine atom or trifluoromethyl. R _f2 and R _f3 independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be connected to form a ring. The organic group includes, for example, an alkyl group, a cycloalkyl group, an alkoxy group, etc., which may be substituted by a halogen atom (preferably a fluorine atom), and R _f2 and R _f3 are more preferably (halogenated) alkyl groups. R _f2 preferably represents the same group as R _f1 or is linked to R _f3 to form a ring. R _f1 and R _f3 may be connected to form a ring, and examples of the formed ring include (halogenated) cycloalkyl rings, (halogenated) aryl rings, and the like. Examples of the (halogenated) alkyl group in R _f1 to R _f3 include the alkyl group in the aforementioned Z _ka1 and its halogenated structure. As the (per)halogenated cycloalkyl group and (perfect) halogenated aryl group in R _f1 to R _f3 or in the ring formed by R _f2 and R _f3 being connected, for example, the cycloalkyl group in the aforementioned Z _ka1 can be mentioned The halogenated structure is more preferably a fluorinated cycloalkyl group represented by -C _{( n )} F _{( 2n-2 )} H, and a perfluoroaryl group represented by -C _{( n )} F _{( n-1 )} . Here, the carbon number n is not particularly limited, but is preferably 5-13, and more preferably 6.

The ring formed by linking at least two of R _ew1 , R _ew2 and Y _ew1 to each other is preferably a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).

In addition, the above-mentioned compound (A) may have a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or a part of the general formula (KA-1) Both the structure and the partial structure of the general formula (KB-1). In addition, some or all of the partial structures of the general formula (KA-1) may also serve as electron-attracting groups of Y ¹ or Y ² in the general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylate group, the carboxylate group can function as an electron-attracting group of Y ¹ or Y ² in the general formula (KB-1).

It does not specifically limit as a group containing a polarity switching group, An organic group containing a polarity switching group can be mentioned. As the organic group containing a polarity switching group, for example, an alkyl group; an alkenyl group; a cycloalkyl group; an aryl group; a halogen atom; a group containing heteroatoms such as an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; A combination of these two or more types is used as a group having a polarity switching group. Alkyl group; alkenyl group; cycloalkyl group; aryl group _; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; Among the specific examples of substituents in ₂₇ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; The above combinations are the same.

As a group containing a polarity switching group, the alkyl group containing a polarity switching group, the aryl group containing a polarity switching group, etc. are mentioned, for example. Examples of the alkyl group in the alkyl group including a polarity switching group include the same ones as the alkyl groups for R ₆ to R ₂₇ . As the aryl group in the aryl group including the polarity switching group, for example, the same ones as the aryl groups as R ₆ to R ₂₇ can be mentioned.

n represents an integer of 1 or more. n is preferably an integer of 3 or less. n is preferably 1 or 2.

m in the anion portion of the general formula (1) represents the number of anions. m represents an integer of 1 or more. The upper limit of m is not particularly limited, and is, for example, 4. m is preferably 1.

M ^m+ in the above general formula (1) represents a cation. n in the cation part of general formula (1) represents the valence number of a cation. m represents an integer of 1 or more. The upper limit of m is not particularly limited, and is, for example, 4. m is preferably 1. The cation as M ^m+ is not particularly limited, but an onium cation is preferred, and a cation represented by the following general formula (ZIA) or general formula (ZIIA) is preferred.

[chemical formula 28]

In the above general formula (ZIA), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent a hydrogen atom or a substituent. As the substituent represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , an organic group is preferred, and the carbon number of the organic group is generally 1-30, preferably 1-20. In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring (also referred to as a ring structure), and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of groups formed by two mutual bonds in R ₂₀₁ to R ₂₀₃ include alkylene (for example, butylene, pentylene) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

As a preferred aspect of the cation represented by the general formula (ZIA), cations represented by the cation (ZI-11), the cation (ZI-12), and the general formula (ZI-13) described later (the cation (ZI-13) -13)) and the cation represented by the general formula (ZI-14) (cation (ZI-14)). When m is 2 or more, the divalent or higher cation may be a cation having a plurality of structures represented by the general formula (ZIA). Such cations include, for example, at least one of R ₂₀₁ to R 203 represented by the general formula (ZIA) and one of R ₂₀₁ to _{R 203 represented} by the other cation represented by the general formula (ZIA). At least one divalent cation of a structure bonded by a single bond or a linking group, etc.

First, the cation (ZI-11) will be described. The cation (ZI-11) is a cation in which at least one of R ₂₀₁ to R ₂₀₃ in the above general formula (ZIA) is an aryl group, that is, an aryl percolium cation. In the aryl cobaltium cation, 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 remainder may be alkyl or cycloalkyl. As the aryl columium cation, for example, a triaryl cobaltium cation, a diarylalkyl columium cation, an aryl dialkyl columium cation, a diarylcycloalkyl columium cation, and an aryl bicycloalkyl columium cation .

As the aryl group contained in the aryl perium cation, 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 cobaltium cation 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 peradium cation needs to 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 (such as , carbon number 6-14), alkoxy group (for example, carbon number 1-15), halogen atom, hydroxyl, lactone ring group or phenylthio group as substituents. As a lactone ring group, the group which removed the hydrogen atom from the structure represented by any one of (KA-1-1)-(KA-1-17) mentioned above is mentioned, for example.

Next, the cation (ZI-12) will be described. R ₂₀₁ to R ₂₀₃ in the cationic (ZI-12)-based formula (ZIA) each independently represent a compound having no organic group having an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom. The organic groups without an aromatic ring as R ₂₀₁ to R ₂₀₃ usually have 1 to 30 carbons, preferably 1 to 20 carbons. R ₂₀₁ to R ₂₀₃ are each independently preferably alkyl, cycloalkyl, allyl or vinyl, more preferably linear or branched 2-oxoalkyl, 2-oxocycloalkyl or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

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 having 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, the cation (ZI-13) will be described.

[chemical formula 29]

In the general formula (ZI-13), M represents an alkyl group, a cycloalkyl group or an aryl group. When it has a ring structure, the above ring structure may contain oxygen atoms, sulfur atoms, ester bonds, amide bonds and carbon-carbon double bonds at least one of the R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R _1c and R _2c may be bonded to form a ring. R _x and R _y each independently represent an alkyl group, a cycloalkyl group or an alkenyl group. R _x and R _y may be bonded to form a ring. In addition, at least two selected from M, R _1c , and R _2c may be bonded to form a ring structure, and a carbon-carbon double bond may be included in the ring structure.

In the general formula (ZI-13), as the alkyl group and cycloalkyl group represented by M, 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 (more preferably 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, and cyclohexyl, and norbornyl, etc. As the aryl group represented by M, 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.

The aforementioned M may further have a substituent. As this aspect, for example, benzyl group etc. are mentioned as M. In addition, when M has a ring structure, the ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.

Examples of the alkyl group, cycloalkyl group and aryl group represented by R _1c and R _2c include the same ones as those described above for M, and their preferred embodiments are also the same. Also, R _1c and R _2c may be bonded to form a ring. Examples of the halogen atom represented by R _1c and R _2c 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 M, and their preferred embodiments are also the same. As the alkenyl represented by R _x and R _y , allyl or vinyl is preferable. The aforementioned R _x and R _y may further have a substituent. As this aspect, for example, _Rx and _Ry include 2-oxoalkyl, alkoxycarbonylalkyl, and the like. 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 group and 2-oxobutyl group, 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. The ring structure formed by connecting R _x and R _y may contain oxygen atom, sulfur atom, ester bond, amide bond or carbon-carbon double bond.

In the general formula (ZI-13), M and R _1c may be bonded to form a ring structure, and the formed ring structure may contain a carbon-carbon double bond.

Among them, the above-mentioned cation (ZI-13) is preferably a cation (ZI-13A). The cation (ZI-13A) is a benzoylmethyl percolium cation represented by the following general formula (ZI-13A).

[chemical formula 30]

In the general formula (ZI-13A), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, Cycloalkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio or arylthio. R _6c and R _7c have the same meanings as R _1c and R _2c in the general formula (ZI-13), 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-13), and their preferred embodiments are also the same.

Any two or more of R _1c to R _5c , R _x and R _y may each be bonded to form a ring structure, and the ring structure may each independently contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond. In addition, R _5c and R _6c , and R _5c and R _x may each be bonded to form a ring structure, and the ring structure may each independently contain a carbon-carbon double bond. Also, R _6c and R _7c may each be bonded to form a ring structure. Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensed rings in which two or more of these rings are combined. Examples of the ring structure include rings with 3 to 10 members, rings with 4 to 8 members are preferred, and rings with 5 or 6 members are more preferred.

Examples of groups formed by bonding any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include butylene and pentylene. 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.

Next, the cation (ZI-14) will be described. The cation (ZI-14) is represented by the following general formula (ZI-14).

[chemical formula 31]

In general formula (ZI-14), 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, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have substituents. When there are multiple R ₁₄ , each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a monocyclic or Alkoxy group of polycyclic cycloalkyl skeleton. These groups may have substituents. 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, heteroatoms such as oxygen atoms or nitrogen atoms may be contained 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-14), 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, the general formula (ZIIA) will be described. In the general formula (ZIIA), R ₂₀₄ and R ₂₀₅ each independently represent an aryl group, an alkyl group or a cycloalkyl group. As the aryl group for _R204 and _R205 , phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group of R ₂₀₄ and R ₂₀₅ may be an aryl group 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 _R204 and _R205 , a straight chain alkyl group with 1 to 10 carbons or a branched chain alkyl group with 3 to 10 carbons (for example, methyl, ethyl, propyl, butyl and pentyl) or cycloalkyl having 3 to 10 carbons (for example, cyclopentyl, cyclohexyl and norbornyl) are preferred.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ 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), ), aryl group (for example, carbon number 6-15), alkoxy group (for example, carbon number 1-15), halogen atom, hydroxyl group, lactone ring group and phenylthio group, etc. Examples of the lactone ring group include groups obtained by removing a hydrogen atom from the structure represented by any one of the above (KA-1-1) to (KA-1-17).

Preferred examples of M ^m+ (cations) in the general formula (1) are shown below, but the present invention is not limited thereto. Me represents a methyl group.

[chemical formula 32]

[chemical formula 33]

Hereinafter, although the preferable example of the anion part in General formula (1) is shown, this invention is not limited to these. Me represents a methyl group.

[chemical formula 34]

[chemical formula 35]

The above-mentioned compound (A) is preferably represented by the following general formula (2).

[chemical formula 36]

In the general formula (2), R ₁ and R ₂ each independently represent a group represented by any one of the above general formulas (R-1) to (R-3). R ₃ to R ₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₃ to R ₅ represents a group represented by the above general formula (R-4). R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring.

Specific examples of R ₁ to R ₅ in the general formula (2) are the same as the specific examples of R ₁ to R ₅ in the above general formula (1), respectively. Specific examples of R ₁₀₁ to R ₁₀₃ in general formula (2) are the same as specific examples of R ₂₀₁ to R ₂₀₃ in general formula (ZIA) above.

The compound represented by the above general formula (2) is preferably represented by the following general formula (3).

[chemical formula 37]

In the general formula (3), R ₁ and R ₂ each independently represent a group represented by any one of the above general formulas (R-1) to (R-3). R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. A represents a single bond or a linking group of (n+1) valence. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.

R ₁ to R ₃ and R ₅ in the general formula (3) are the same as R ₁ to R ₃ and R ₅ in the above general formula (1), respectively. A, Y, and n in the general formula (3) are respectively the same as A, Y, and n in the above-mentioned general formula (R-4). R ₁₀₁ to R ₁₀₃ in the general formula (3) are the same as R ₁₀₁ to R ₁₀₃ in the above general formula (2), respectively.

In the above general formula (R-1) in the above general formula (3), at least one of R ₆ to R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ And form a ring, in the above general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form a ring, in the above general formula (R-3) , At least one of R ₁₉ to R ₂₁ is preferably bonded to at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ to form a ring.

In the above general formula (R-1), the ring system formed by bonding at least one of R ₆ to R ₈ with at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ and the general formula (3) The carbon atoms bonded by the benzenesulfonic acid anion constitute a ring member. In the above general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form a ring system bonded to the benzenesulfonic acid anion of the general formula (3) The carbon atoms form the ring members. In the above general formula (R-3), the ring system formed by bonding at least one of R ₁₉ to R ₂₁ with at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ is the same as the general formula (3) The carbon atoms bonded by the benzenesulfonic acid anion constitute a ring member.

The rings formed in the above general formulas (R-1), (R-2) and (R-3) are not particularly limited, and include hydrocarbon rings (for example, aliphatic hydrocarbon rings), heterocycles and 2 A polycyclic condensed ring formed by combining more than one of these rings. The ring structure (ring structure of a single ring constituting the polycyclic condensed ring) includes 3 to 10 membered rings, preferably 4 to 8 membered rings, more preferably 5 or 6 membered rings.

In the above general formula (R-1) in the above general formula (3), at least one of R ₆ to R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ In the above general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form a ring, and in the above general formula (R- 3), in the ring formed by bonding at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ , the number of carbon atoms constituting the ring members is 5-10 is better. The above-mentioned ring may be monocyclic or polycyclic. When polycyclic, the number of carbon atoms constituting the ring members of the polycyclic ring is preferably 5-10.

In the above general formula (R-1) in the above general formula (3), below, at least one of R ₆ to R ₈ and at least one of R ₉ and R ₁₀ or R ₁₁ to R ₁₃ are described below. A ring formed by at least one bond, a ring formed by bonding at least one of R ₁₄ to R ₁₆ to at least one of R 17 and R 18 in the above general formula (R-2), and a ring formed by bonding to at least one of R ₁₇ and R ₁₈ in the above general formula (R-2), In (R-3), at least one of R ₁₉ to R ₂₁ is a specific example of a ring formed by bonding at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ , but the present invention does not include Not limited to these. * represents a bond with the benzenesulfonic acid anion in the general formula (3).

[chemical formula 38]

The above-mentioned compound (A) is preferably represented by the following general formula (4).

[chemical formula 39]

In the general formula (4), R ₃₁ to R ₄₀ each independently represent a hydrogen atom or a substituent. At least two of R ₃₁ to R ₄₀ may be bonded to each other to form a ring. R ₄₁ to R ₅₀ each independently represent a hydrogen atom or a substituent. At least two of R ₄₁ to R ₅₀ may be bonded to each other to form a ring. R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. A represents a single bond or a linking group of (n+1) valence. n represents an integer of 1 or more. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.

Specific examples of substituents for R ₃₁ to R ₅₀ are the same as specific examples of substituents for R ₆ to R ₂₇ described above. Specific examples of the ring formed by at least two of R ₃₁ to R ₄₀ being bonded to each other and specific examples of the ring formed by bonding at least two of R ₆ to R ₁₃ in the above general formula (R-1) Example is the same. Specific examples of the ring formed by at least two of R ₄₁ to R ₅₀ being bonded to each other and specific examples of the ring formed by bonding at least two of R ₆ to R ₁₃ in the above general formula (R-1) Example is the same.

Specific examples of R ₃ and R ₅ in the general formula (4) are the same as the specific examples of R ₃ and R ₅ in the above general formula (1), respectively. Specific examples of A, Y, and n in the general formula (4) are the same as the specific examples of A, Y, and n in the above-mentioned general formula (R-4), respectively. Specific examples of R ₁₀₁ to R ₁₀₃ in general formula (4) are the same as specific examples of R ₁₀₁ to R ₁₀₃ in general formula (2) above.

The compound represented by the above general formula (4) is preferably represented by the following general formula (5).

[chemical formula 40]

In the general formula (5), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. A represents a single bond or a linking group of (n+1) valence. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.

Specific examples of R ₃ and R ₅ in the general formula (5) are the same as the specific examples of R ₃ and R ₅ in the above general formula (1), respectively. Specific examples of A, Y, and n in the general formula (5) are the same as the specific examples of A, Y, and n in the above general formula (R-4), respectively. Specific examples of R ₁₀₁ to R ₁₀₃ in general formula (5) are the same as specific examples of R ₁₀₁ to R ₁₀₃ in general formula (2) above.

The A-series aromatic groups in the above general formulas are preferred. When the A is an aromatic group, since the molecular weight of the compound (A) becomes larger, excessive acid diffusivity of the acid generated in the exposed part of the compound (A) to the unexposed part is suppressed and the resolving power becomes higher , so it is better.

The above compound (A) is preferably represented by the following general formula (6).

[chemical formula 41]

In the general formula (6), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. R ₅₁ to R ₅₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₅₁ to R ₅₅ represents a group represented by the following general formula (R-5).

[chemical formula 42]

In general formula (R-5), B represents a single bond or a (n+1) valence linking group. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different. * represents a bond to the benzene ring in the general formula (6).

Specific examples of R ₃ and R ₅ in the general formula (6) are the same as the specific examples of R ₃ and R ₅ in the above general formula (1), respectively. Specific examples of R ₁₀₁ to R ₁₀₃ in general formula (6) are the same as specific examples of R ₁₀₁ to R ₁₀₃ in general formula (2) above. Specific examples of substituents for R ₅₁ to R ₅₅ are the same as specific examples of substituents for R ₆ to R ₂₇ described above.

As the (n+1)valent linking group of B, for example, a divalent linking group is described below. It does not specifically limit as a divalent linking group, For example, an alkylene group, an aromatic group, or these combinations are mentioned. The alkylene group is not particularly limited, but a linear or branched alkylene group is preferred, and an alkylene group having 1 to 6 carbon atoms is further preferred. Specific examples include methylene and the like. The aromatic group may be an aryl group, an aralkyl group, a heterocyclic group, and the like. Specific examples of the aryl group having 6 to 15 carbon atoms include phenyl, tolyl, naphthyl, anthracenyl and the like. As the aralkyl group, an aralkyl group having 6 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 12 carbon atoms is more preferable. Specifically, benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, etc. are mentioned. As the heterocyclic group, a heterocyclic group having 6 to 20 carbon atoms is preferable, and a heterocyclic group having 6 to 12 carbon atoms is more preferable. For example, thiophene and furan can be mentioned.

The above-mentioned divalent linking group may further have a substituent. Specific examples of further substituents are the same as the specific examples of substituents for R ₆ to R ₂₇ described above. As the (n+1)-valent linking group of B, for example, a group obtained by removing (n-1) hydrogen atoms from a divalent linking group can be mentioned.

Y and n in the general formula (6) are the same as Y and n in the above general formula (R-4), respectively.

In the above general formula (6), B is preferably a single bond or a methylene group.

Y in each of the above general formulas is hydroxyl, carboxyl, a group having a carbonyl bond, acyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, aryloxycarbonyl, alkoxycarbonyl, carboxylate A group or an imide group is preferred.

Specific examples of the group having a carbonyl bond of Y include, for example, an alkylcarbonyl group, an arylcarbonyl group, and the like. Examples of the alkyl group in the alkylcarbonyl group include the same ones as the alkyl groups for R ₆ to R ₂₇ . Examples of the aryl group in the arylcarbonyl group include the same ones as the aryl groups for R ₆ to R ₂₇ . The group having a carbonyl bond is a group in which a carbonyl bond and an ether bond are not adjacent to each other.

The carbon number of the acyl group in the acyloxy group of Y is preferably 1-10, more preferably 1-6. The carbon number of the alkoxy group in the alkoxycarbonyloxy group as Y is preferably 1-10, more preferably 1-6. The carbon number of the aryl group in the aryloxycarbonyloxy group of Y is preferably 6-20, more preferably 6-12. The carbon number of the aryl group in the aryloxycarbonyl group of Y is preferably 6-20, more preferably 6-12. The carbon number of the alkoxy group in the alkoxycarbonyl group of Y is preferably 6-10, more preferably 1-6. The imide group as Y is a group obtained by removing one hydrogen atom from imide.

Alkylcarbonyl group, arylcarbonyl group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, carboxyl group as a group having a carbonyl bond as Y The group and the imide group may further have a substituent. As further substituents, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; more than one combination. Alkyl group; alkenyl group; cycloalkyl group; aryl group _; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom and silicon atom; In the specific examples of substituents in ₂₇ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and two or more of these the same combination.

Y in each of the above general formulas preferably represents a hydroxyl group, a carboxyl group or an alkoxycarbonyl group.

The pKa of the acid generated by the above-mentioned compound (A) is preferably -10 or more and 5 or less. pKa (acid dissociation constant) represents the pKa in an aqueous solution, and is defined by Chemical Handbook (II) (revised 4th edition, 1993, edited by the Chemical Society of Japan, Maruzen.Inc.). The lower the pKa value, the greater the acid strength. Specifically, pKa in an aqueous solution can be actually measured by measuring an acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the following packaged software 1 can be used to obtain the value based on the database of Hammett's substituent constants and known literature values by calculation. All the pKa values described in this specification represent the values obtained by calculation using the packaged software. Package software 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

Preferred examples of the compound (A) are shown below, but the present invention is not limited thereto. Me represents a methyl group.

[chemical formula 43]

[chemical formula 44]

[chemical formula 45]

[chemical formula 46]

The polymer (A) may be used alone or in combination of two or more. In the composition of the present invention, the content of the compound (B) (total when there are plural types) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, based on the total solid content of the composition. 1-20 mass % is still more preferable, and 1-15 mass % is especially preferable.

[(B) Resin that decomposes by the action of acid and has increased solubility in alkaline developer] (B) The resin (it is also called "resin (B)") which decomposes by the action of an acid and increases the solubility to an alkali developing solution is demonstrated. Examples of the resin (B) include resins (hereinafter also referred to as "acid-decomposable resins") having groups (hereinafter also referred to as "acid-decomposable groups") that are decomposed by the action of an acid to increase their polarity. "). Since the above-mentioned acid-decomposable resin has an acid-decomposable group, it decomposes by the action of an acid, and its solubility in an alkali developing solution increases.

The resin (B) preferably contains a repeating unit having an acid-decomposable group.

As the resin (B), known resins can be suitably used. For example, paragraphs [0055] to [0191] of U.S. Patent Application Publication No. 2016/0274458A1 specification, paragraphs [0035] to [0085] of U.S. Patent Application Publication No. 2015/0004544A1 specification, U.S. Patent Application Publication 2016 The known resin disclosed in paragraphs [0045] to [0090] of specification No. 0147150A1 is used as the resin (B).

The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) decomposed by the action of an acid. Examples of polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonyl imide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups , (Alkylsulfonyl)(Alkylcarbonyl)imide, Bis(Alkylcarbonyl)methylene, Bis(Alkylcarbonyl)imide, Bis(Alkylsulfonyl)methylene , bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene, and tri(alkylsulfonyl)methylene (typically, at 2.38% by mass tetrahydroxide dissociated groups in methylammonium aqueous solution) and alcoholic hydroxyl groups, etc.

In addition, the alcoholic hydroxyl group refers to the hydroxyl group bonded to the hydrocarbon group, which is a hydroxyl group other than the hydroxyl group (phenolic hydroxyl group) directly bonded to the aromatic ring. Alcohol groups (eg, hexafluoroisopropanol, etc.) are excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20 is preferable.

Among them, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group (preferably hexafluoroisopropanol group) or sulfonic acid group are preferred as the polar group.

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

In formula (Y1) and formula (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). In addition, when Rx ₁ to Rx ₃ When all of Rx 1 to Rx 3 are alkyl groups (straight chain or branched chain), at least two of Rx ₁ to Rx ₃ are preferably methyl groups. Among them, Rx ₁ to Rx ₃ each independently represent a straight-chain or branched alkyl group is preferable, and Rx ₁ to Rx ₃ each independently represent a straight-chain alkyl group is more preferable. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic or polycyclic ring. As the alkyl group of 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 and tert-butyl group is preferable. Cycloalkyl groups for Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic groups such as norbornyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl Cycloalkyl groups are preferred. Cycloalkyl groups formed as two bonds of Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecanyl, and tetracyclododecyl , and polycyclic cycloalkyl groups such as adamantyl are preferred, and monocyclic cycloalkyl groups having 5 to 6 carbon atoms are 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 or ethyl group, and Rx ₂ and Rx ₃ are bonded to form the aforementioned cycloalkyl group, which is 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 also be bonded to each other to form a ring. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. R ₃₆ is also preferably a hydrogen atom.

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

[chemical formula 47]

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). D represents a single bond or a divalent linking group. Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group that may contain heteroatoms, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group that combines these ( For example, groups combining alkyl and cycloalkyl). Regarding an alkyl group and a cycloalkyl group, for example, one of the methylene groups may be substituted by 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, cycloalkyl group, 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, since Tg (glass transition temperature) or activation energy is increased, film strength can be secured 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.

The resin (B) preferably has an acetal structure. The acid-decomposable group preferably has an acetal structure. The acetal structure is, for example, a structure in which a polar group such as a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group is protected by a group represented by the above formula (Y3).

As the repeating unit having an acid-decomposable group, a repeating unit represented by formula (A) is preferable.

[chemical formula 48]

L ₁ represents a divalent linking group, R ₁ to R ₃ each independently represent a hydrogen atom or a monovalent substituent, and R ₄ represents a group decomposed and detached by the action of an acid. L ₁ represents a divalent linking group. Examples of divalent linking groups include -CO-, -O-, -S-, -SO-, -SO ₂ -, hydrocarbon groups (e.g., alkylene, cycloalkylene, alkenylene, arylene Base, etc.) and a linking base that connects a plurality of them. Among them, -CO- and an aryl group are preferable as L ₁ . As the arylylene group, a phenylene group is preferable. The alkylene group may be linear or branched. The carbon number of the alkylene group is not particularly limited, and 1-10 is preferable, and 1-3 is more preferable.

R ₁ to R ₃ each independently represent a hydrogen atom or a monovalent substituent. As a monovalent substituent, an alkyl group, a cycloalkyl group, or a halogen atom is mentioned, for example. The alkyl group may be linear or branched. The carbon number of the alkyl group is not particularly limited, and 1-10 is preferable, and 1-3 is more preferable. The cycloalkyl group may be monocyclic or polycyclic. The carbon number of the cycloalkyl group is preferably 3-8. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ₄ represents a group decomposed by the action of an acid (leaving group). Among them, as the leaving group, groups represented by the above-mentioned formulas (Y1) to (Y4) can be mentioned, and the group represented by the above-mentioned formula (Y3) 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 alkoxy group. Carbonyl (carbon number 2-6), etc. The carbon number in the substituent is preferably 8 or less.

As the repeating unit having an acid-decomposable group, the repeating unit represented by the general formula (AI) is also preferable.

[chemical formula 49]

In the general formula (AI), Xa ₁ represents a hydrogen atom or an alkyl group. 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 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 with 5 or less carbon atoms and an acyl group with 5 or less carbon atoms, preferably an alkyl group with 3 or less carbon atoms , 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 -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group with 1 to 5 carbon atoms, and -CH ₂ -, -(CH ₂ ) ₂ - or -(CH ₂ ) ₃ - is better.

As the alkyl group of 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 and tert-butyl group is preferable. Cycloalkyl groups for Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic groups such as norbornyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl Cycloalkyl groups are 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. Regarding the cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring is substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. Regarding the repeating unit represented by 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-mentioned groups has a substituent, for example, 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 (1 to 4 carbon atoms) can be mentioned. 2~6) etc. as substituents. The carbon number in the substituent is preferably 8 or less.

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

The resin (B) may contain one kind of repeating unit having an acid-decomposable group alone, or may contain two or more kinds in combination.

The content of the repeating unit having an acid-decomposable group contained in the resin (B) relative to all the repeating units of the resin (B) (the total number of repeating units having an acid-decomposable group exists) is 10 to 90 Mole% is preferable, 20-80 mol% is more preferable, and 30-70 mol% is still more preferable.

(repeating unit with lactone or sultone group) The resin (B) may further contain repeating units having a lactone group or sultone. As the lactone group or the sultone group, any group can be used as long as it has a lactone structure or a sultone structure, but it is preferably a 5- to 7-membered cyclic lactone structure or a 5- to 7-membered cyclic sultone group. A group with an ester structure, which forms a bicyclic structure or a spiro ring structure on a 5- to 7-membered cyclic lactone structure, and has other ring structures or forms a bicyclic structure on a 5- to 7-membered cyclic sultone structure, or In the form of spiro ring structure, it is more preferable that the condensed ring has other ring structures. It is more preferable to have a repeating unit, and the repeating unit has: a group having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21); or having the following general formula (SL1 A group with a sultone structure represented by any one of -1) to (SL1-3). In addition, a group having a lactone structure or a sultone structure may be directly bonded to the main chain. As a preferred structure, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-6), general formula (LC1-13) and general formula (LC1- 14) The groups represented are preferred.

[chemical formula 50]

The lactone moiety or the sultone moiety may have a substituent (Rb ₂ ). Examples of preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbons, cycloalkyl groups having 4 to 7 carbons, alkoxy groups having 1 to 8 carbons, and alkyl groups having 1 to 8 carbons. Oxycarbonyl group, carboxyl group, halogen atom, hydroxyl group, cyano group, acid decomposable group, etc. n2 represents an integer of 0-4. When n2 is 2 or more, a plurality of Rb ₂ may be different, and a plurality of Rb ₂ may be bonded to each other to form a ring.

Examples of the repeating unit including a group having a lactone structure or a sultone structure include repeating units represented by the following general formula (AI).

[chemical formula 51]

In the general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Examples of preferable substituents that the alkyl group of Rb ₀ may have include hydroxyl groups and halogen atoms. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group combining these. Among them, a single bond or a linking group represented by -Ab ₁ -CO ₂ - is preferred. Ab ₁ is straight-chain or branched alkylene or monocyclic or polycyclic cycloalkylene, methylene, ethylidene, cyclohexylene, adamantyl or norbornyl is preferred . V represents a group having a lactone structure or a sultone structure. A group having a lactone structure or a sultone structure as V, represented by any one of the general formulas (LC1-1) to (LC1-21), and the general formulas (SL1-1) to (SL1-3) group is preferred.

The repeating unit including a group having a lactone structure or a sultone structure usually has an optical isomer, but any optical isomer can be used. Also, one type of optical isomer may be used alone, or a plurality of optical isomers may be used in combination. When mainly using one optical isomer, its optical purity (ee) is preferably 90 or higher, more preferably 95 or higher.

Specific examples of the repeating unit including a group having a lactone structure or a sultone structure are given below, but the present invention is not limited thereto. In addition, Rx in the formula represents H, CH ₃ , CH ₂ OH or CF ₃ .

[chemical formula 52]

[chemical formula 53]

The content of repeating units having lactone groups or sultone groups is preferably 1-60 mol%, more preferably 5-50 mol%, 10-40 mol% relative to all repeating units in the resin (A). % is further preferred.

(repeating units with acid groups) Resin (B) may contain repeating units having acid groups. As the acid group, an acid group having an acid dissociation constant (pKa) of 13 or less is preferable. The pKa is the same as the pKa of the acid of the above-mentioned compound (A) generated by irradiation with actinic rays or radiation.

As the repeating unit having an acid group, a repeating unit represented by formula (B) is preferable.

[chemical formula 54]

R ₃ represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, a group represented by -L ₄ -R ₈ is preferable. L ₄ represents a single bond or an ester group. R ₈ may include an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof.

R ₄ and R ₅ each independently represent a hydrogen atom, a halogen atom or an alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

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

As the repeating unit having an acid group, a repeating unit represented by the following general formula (I) is also preferable.

[chemical formula 55]

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

As the alkyl group of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I), methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, hexyl, 2-ethylhexyl, An alkyl group having 20 or less carbon atoms, such as an octyl group or a dodecyl group, is preferable, an alkyl group having 8 or less carbon atoms is more preferable, and an alkyl group having 3 or less carbon atoms is still more preferable.

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

Examples of preferable substituents in the above-mentioned groups include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amido groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, Alkoxy, thioether, acyl, acyloxy, alkoxycarbonyl, cyano and nitro. The carbon number of the substituent is preferably 8 or less.

Ar ₄ represents a (n+1)-valent aromatic ring group. When n is 1, the divalent aromatic ring group may have a substituent, for example, an arylylene group having 6 to 18 carbon atoms such as phenylene, cresyl, naphthyl, and anthracenyl, or a thiophene ring , furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, three well rings, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring, etc. The aromatic ring group is preferred.

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

Examples of substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include: R in the general formula (I) ₄₁ Alkoxy groups such as alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy listed in R ₄₂ and R ₄₃ ; aryl groups such as phenyl; wait. Examples of the alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ include methyl, ethyl, propyl, isopropyl, n-butyl, and An alkyl group having at most 20 carbons, such as dibutyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, preferably an alkyl group having at most 8 carbons. As X ₄ , a single bond, -COO- or -CONH- is preferred, and a single bond or -COO- is more preferred.

As the alkylene group in _L4 , an alkylene group having 1 to 8 carbon atoms such as methylene, ethylidene, propylidene, butyl, hexylene, and octylene is preferable. As Ar ₄ , an aromatic ring group having 6 to 18 carbon atoms is preferable, and a phenyl ring group, a naphthyl ring group, and a biphenylene ring group are more preferable. The repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar ₄ is preferably a phenyl ring group.

As the repeating unit represented by the general formula (I), a repeating unit represented by the following general formula (1) is preferable.

[chemical formula 56]

In general formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group. When plural, they may be the same or different. When there are plural Rs, they may jointly form a ring. As R, a hydrogen atom is preferable. a represents an integer of 1-3. b represents an integer of 0 to (3-a).

Specific examples of the repeating unit represented by the general formula (I) are shown below, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

[chemical formula 57]

[chemical formula 58]

[chemical formula 59]

In addition, among the above-mentioned repeating units, the repeating units described in detail below are preferable. In the formula, R represents a hydrogen atom or a methyl group, and a represents 1, 2 or 3.

[chemical formula 60]

[chemical formula 61]

Relative to all the repeating units in the resin (B), the content of repeating units having acid groups is preferably 10-80 mol%, more preferably 15-75 mol%, and further more preferably 20-70 mol%. good.

The resin (B) may have various repeating units in addition to the above-mentioned repeating structural units for the purpose of adjusting dry etching resistance, standard developer compatibility, substrate adhesion, resist profile, resolving power, heat resistance, and sensitivity.

Resin (B) can be synthesize|combined by a conventional method (for example, radical polymerization). As a general synthesis method, for example, (1) a blanket polymerization method of polymerizing by dissolving monomer species and an initiator in a solvent and heating; The dropwise polymerization method in which the solution of the body type and the initiator is added dropwise to the heating solvent, etc.

The weight average molecular weight (Mw) of the resin (B) is preferably 1,000-200,000, more preferably 2,000-30,000, and still more preferably 3,000-25,000. The degree of dispersion (Mw/Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and still more preferably 1.1 to 2.0.

Resin (B) may be used individually by 1 type, and may use 2 or more types together. In the composition of the present invention, the content of the resin (B) is usually 20% by mass or more relative to the total solid content, preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass or more. Further better. The upper limit is not particularly limited, but is preferably at most 99.5% by mass, more preferably at most 99% by mass, and still more preferably at most 98% by mass. In addition, the total solid content of the composition of the present invention represents other components (components that can constitute an actinic radiation-sensitive or radiation-sensitive film) other than the solvent.

[(A') A compound that generates an acid by irradiation with actinic rays or radiation other than the above-mentioned compound (A)] The composition of the present invention may contain a compound other than the compound (A) that generates an acid upon irradiation with actinic rays or radiation within a range that does not impair the effects of the present invention.

[Acid Diffusion Control Agent] The composition of the present invention preferably contains an acid diffusion controller. The acid diffusion control agent functions as a quencher that traps acid generated from a photoacid generator or the like during exposure, and suppresses the reaction of the acid-decomposable resin in the unexposed portion due to excess generated acid. For example, basic compounds (DA), basic compounds (DB) whose alkalinity is reduced or disappeared by irradiation with actinic rays or radiation, onium salts (DC) which become relatively weak acids with respect to acid generators, nitrogen-containing Atoms and low-molecular-weight compounds (DD) with groups detached by the action of acids, or onium salt compounds (DE) with nitrogen atoms in the cationic portion, are used as acid diffusion control agents. In the composition of the present invention, known acid diffusion controllers can be appropriately used. For example, paragraphs [0627] to [0664] of U.S. Patent Application Publication No. 2016/0070167A1 specification, paragraphs [0095] to [0187] of U.S. Patent Application Publication No. 2015/0004544A1 specification, U.S. Patent Application Publication 2016 The known compounds disclosed in paragraphs [0403] to [0423] of specification No. /0237190A1 and paragraphs [0259] to [0328] of specification US Patent Application Publication No. 2016/0274458A1 are used as acid diffusion control agents.

As the basic compound (DA), a compound having a structure represented by the following general formulas (A) to (E) is preferable.

[chemical formula 62]

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 carbon atoms.

The alkyl groups in the general formulas (A) and (E) may have a substituent or may be unsubstituted. Regarding the above-mentioned alkyl group, the alkyl group having a substituent is preferably 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. The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

As basic compounds (DA), thiazole, benzothiazole, oxazole, benzoxazole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperwell, aminomorphine, aminoalkyl Portoline, piperidine, or compounds with these structures are preferred, with thiazole structure, benzothiazole structure, oxazole structure, benzoxazole structure, imidazole structure, diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives with hydroxyl and/or ether bond, or aniline derivatives with hydroxyl and/or ether bond, etc. good.

A basic compound (DB) (hereinafter also referred to as "compound (DB)") whose alkalinity is reduced or disappeared by irradiation with actinic rays or radiation, has a proton-accepting functional group and is A compound whose proton-accepting property decreases, disappears, or changes from proton-accepting to acidic after being decomposed by radiation or radiation exposure.

The proton-accepting functional group refers to a functional group having a group or electrons capable of electrostatically interacting with protons, such as a functional group having a macrocyclic structure such as cyclic polyether, or a functional group containing The functional group of the nitrogen atom that acts on the unshared electron pair. The nitrogen atom having an unshared electron pair that does not contribute to π-conjugation means, for example, a nitrogen atom having a partial structure represented by the following formula.

[chemical formula 63]

Preferable partial structures of the proton accepting functional group include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyridine structure.

Compound (DB) yields a compound whose proton accepting property decreases, disappears, or changes from proton accepting property to acidity when decomposed by irradiation of actinic rays or radiation. Among them, the reduction or disappearance of proton accepting properties or the change from proton accepting properties to acidity refers to the change of proton accepting properties caused by the addition of protons to proton accepting functional groups. When the compound (DB) of the proton-accepting functional group and the proton adduct are generated from the proton, the equilibrium constant in the chemical equilibrium thereof decreases. Proton accepting properties can be confirmed by performing pH measurements.

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

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen.Inc.). The lower the value representing the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the following packaged software 1 can be used to obtain the value based on the database of Hammett's substituent constants and known literature values by calculation. All the pKa values described in this specification represent the values obtained by calculation using the packaged software.

Package software 1: Advanced Chemistry Development (ACD/Labs) software V8.14 supports Solaris system (1994-2007ACD/Labs).

In the composition of the present invention, an onium salt (DC) which is a relatively weak acid relative to the photoacid generator can be used as an acid diffusion control agent. When a photoacid generator and an onium salt that generates an acid that is a relatively weak acid relative to the acid generated by the photoacid generator are used in combination, if the acid generated by the photoacid generator is Collision with an onium salt with an unreacted weak acid anion releases the weak acid by salt exchange to produce an onium salt with a strong acid anion. In this process the strong acid is exchanged for a weaker acid with lower catalytic energy, thus visually inactivating the acid and enabling control of acid diffusion.

Compounds represented by the following general formulas (d1-1) to (d1-3) are preferable as onium salts that are relatively weak acids with respect to the photoacid generator.

[chemical formula 64]

In the formula, R ⁵¹ is a hydrocarbon group that may have a substituent, Z ^2c is a hydrocarbon group with 1 to 30 carbons that may have a substituent (wherein, the carbon adjacent to S is not substituted by a fluorine atom), R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene or arylylene group, Rf is a hydrocarbon group containing fluorine atoms, and M ⁺ are independently ammonium cations, percite cations or iodonium cations.

Preferable examples of the peronium cation or the odonium cation represented by M ⁺ include the percolium cation exemplified by the general formula (ZI) and the odonium cation exemplified by the general formula (ZII).

The onium salt (DC) which becomes a relatively weak acid relative to the photoacid generator may also be a compound having a cationic site and an anionic site in the same molecule and the cationic site and the anionic site are linked by a covalent bond (hereinafter also referred to as "compound (DCA)".). As the compound (DCA), a compound represented by any one of the following general formulas (C-1) to (C-3) is preferable.

[chemical formula 65]

In the general formulas (C-1) to (C-3), R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms. L ₁ represents a divalent linking group or a single bond connecting the cation site and the anion site. -X¯ represents an anion site selected from -COO¯, -SO ₃ ¯, -SO ₂ ¯ and -N¯-R ₄ . R ₄ represents carbonyl (-C(=O)-), sulfonyl (-S(=O) ₂ -), and sulfinyl (-S(=O) -) at least one 1-valent substituent. R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be bonded to each other to form a ring structure. In addition, in the general formula (C-3), two of R ₁ to R ₃ may together represent one divalent substituent, and may be bonded to an N atom via a double bond.

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

Examples of L ₁ of the divalent linking group include linear or branched alkylene groups, cycloalkylene groups, arylylene groups, carbonyl groups, ether linkages, ester linkages, amide linkages, and urethanes. bond, urea bond, and a combination of two or more of these, etc. L ₁ is preferably an alkylene group, an arylylene group, an ether bond, an ester bond, or a combination of two or more of these.

A low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid (hereinafter, also referred to as "compound (DD)") has a group detached by the action of an acid on the nitrogen atom. Amine derivatives of the group are preferred. As the group detached by the action of acid, acetal group, carbonate group, carbamate group, tertiary ester group, tertiary hydroxyl group or half amine acetal ether group are preferred, carbamate Group or half amine acetal ether group is more preferred. The molecular weight of the compound (DD) is preferably from 100 to 1000, more preferably from 100 to 700, and still more preferably from 100 to 500. Compound (DD) may also 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 formula 66]

In the general formula (d-1), R _b independently represent a hydrogen atom, an alkyl group (preferably having 1 to 10 carbons), a cycloalkyl group (preferably having 3 to 30 carbons), an aryl group (preferably C3-30), aralkyl (preferably C1-10) or alkoxyalkyl (preferably C1-10). R _b may be bonded to each other to form a ring. The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R _b can be independently replaced by functional groups such as hydroxyl group, cyano group, amino group, pyrrolidinyl group, piperidinyl group, porphyrinyl group, and bridged oxygen group. , alkoxy, halogen atom substitution. The same applies to the alkoxyalkyl group represented by R _b .

As R _b , a linear or branched alkyl group, cycloalkyl group or aryl group is preferred, and a linear or branched alkyl group or cycloalkyl group is more preferred. Examples of the ring formed by linking two R _b to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof. Specific structures of the group represented by the general formula (d-1) include, but are not limited to, structures disclosed in paragraph [0466] of US Patent Publication No. US2012/0135348A1.

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

[chemical formula 67]

In general formula (6), l represents the integer of 0-2, m represents the integer of 1-3, and satisfies l+m=3. R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two R _a can be the same or different, and the two R _a can also be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain heteroatoms other than the nitrogen atom in the formula. R _b has the same meaning as R _b 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 R _a can be independently substituted by the same group as the aforementioned group as the following group, the group being The alkyl group, cycloalkyl group, aryl group, and aralkyl group of R _b may be substituted.

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 above-mentioned R a include the same groups as those described above for R _b . Specific examples of the particularly preferred 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.

The onium salt compound (DE) (hereinafter also referred to as "compound (DE)") having a nitrogen atom in the cationic portion is preferably a compound having a basic site containing a nitrogen atom in the cationic portion. The basic part is preferably an amine group, more preferably an aliphatic amine group. It is further preferred that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Also, from the viewpoint of increasing the basicity, it is preferable that an electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly bonded to a nitrogen atom. Preferable specific examples of the compound (DE) include compounds disclosed in paragraph [0203] of US Patent Application Publication No. 2015/0309408A1, but are not limited thereto.

Preferred examples of acid diffusion controllers are shown below. Me represents a methyl group.

[chemical formula 68]

[chemical formula 69]

[chemical formula 70]

[chemical formula 71]

[chemical formula 72]

In the composition of the present invention, the acid diffusion controller may be used alone or in combination of two or more. The content of the acid diffusion controller in the composition of the present invention (total when there are plural kinds) is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total solid content of the composition.

[solvent] It is preferable that the composition of the present invention contains a solvent. In the composition of the present invention, known resist solvents can be preferably used. For example, paragraphs [0665] to [0670] of U.S. Patent Application Publication No. 2016/0070167A1 specification, paragraphs [0210] to [0235] of U.S. Patent Application Publication No. 2015/0004544A1 specification, and U.S. 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, alkyl alkoxypropionate Esters, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and pyruvic acid Organic solvents such as alkyl esters.

As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in its structure and a solvent not having a hydroxyl group can be used. As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-mentioned exemplified compounds can be appropriately selected. As a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or alkyl lactate, etc. are preferred, and propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate are more preferred. In addition, solvents that do not have a hydroxyl group include alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound that may have a ring, cyclic lactone, or alkyl acetate. Among them, propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetyloxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyl Lactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone or 2- Heptanone is further preferred. 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 containing two or more kinds of propylene glycol monomethyl ether acetate.

[Surfactant] The composition of the present invention may further contain a surfactant. By containing the surfactant, in the case of using an exposure light source with a wavelength of 250nm or less, especially 220nm or less, it is possible to form a pattern with good sensitivity and resolution and less adhesion and development defects. As the surfactant, it is particularly preferable to use a fluorine-based and/or silicon-based surfactant. Examples of the fluorine-based and/or silicon-based surfactant include those described in [0276] of US Patent Application Publication No. 2008/0248425. Also, Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); Megaface F171, F173, F176, F189, F113, F110, F177, F120 can also be used or R08 (manufactured by DIC CORPORATION); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by ASAHI GLASS CO., LTD.); TroySol S-366 (manufactured by Troy Chemical Industries Inc.); GF- 300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.), Surflon S-393 (manufactured by SEIMI CHEMICAL CO., LTD.); EftopEF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco); PF636, PF656, PF6320, or PF6520 (manufactured by OMNOVA Solutions Inc.); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, or 222D (manufactured by Neos Corporation). In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition, as the surfactant, in addition to the known ones shown above, fluorofatty acids produced by short-chain polymerization (also called short-chain polymer method) or oligomerization method (also called oligomer method) can also be used. family of compounds to synthesize. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can be used as a surfactant. The fluoroaliphatic compound can be synthesized by, for example, the method described in JP-A-2002-090991. In addition, surfactants other than the fluorine-based and/or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 can also be used.

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

When the composition of the present invention contains a surfactant, its content is based on the total solid content of the composition, preferably 0-2% by mass, more preferably 0.0001-2% by mass, further preferably 0.0005-1% by mass %.

(other additives) The composition of the present invention may suitably contain, in addition to the components described above, carboxylic acids, carboxylate onium salts, dissolution-inhibiting compounds with a molecular weight of 3000 or less described in Proceeding of SPIE, 2724, 355 (1996), dyes, plastics, etc. Chemicals, photosensitizers, light absorbers, antioxidants, etc.

In particular, carboxylic acids can also be preferably used in order to improve performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.

When the composition of the present invention contains a carboxylic acid, the content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 3% by mass relative to the total solid content of the composition. %.

From the standpoint of improving resolution, the actinic radiation-sensitive or radiation-sensitive resin composition in the present invention is preferably used with a film thickness of 10 to 250 nm, more preferably used with a film thickness of 20 to 200 nm. More preferably, it is preferably used with a film thickness of 30 to 100 nm. Such a film thickness can be obtained by setting the solid content concentration in the composition within an appropriate range to obtain an appropriate viscosity and improve applicability and film-forming properties.

The solid content concentration of the actinic radiation-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, further preferably 2.0 to 5.3% by mass. By making the solid content concentration into the above-mentioned range, the resist solution can be uniformly applied on the substrate, and a resist pattern excellent in line width roughness can be formed. The solid content concentration refers to the mass percentage of the mass of other components except the solvent relative to the total mass of the actinic radiation-sensitive or radiation-sensitive resin composition.

[use] The 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 composition of the present invention relates to a semiconductor manufacturing process such as an IC (Integrated Circuit), manufacturing a circuit substrate such as a liquid crystal or a thermal head, manufacturing a mold structure for imprinting, and other Actinic radiation-sensitive or radiation-sensitive resin compositions used in photolithography processing steps or in the manufacture of lithographic printing plates or acid-curable 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) and the like. In addition, the present invention relates to an actinic radiation-sensitive or radiation-sensitive resin composition for manufacturing photomasks.

[Actinic radiation-sensitive or radiation-sensitive film] The present invention also relates to an actinic radiation-sensitive or radiation-sensitive film (preferably a resist film) formed from the actinic radiation-sensitive or radiation-sensitive composition of the present invention. Such a film is formed, for example, by applying the composition of the present invention to a support such as a substrate. The thickness of the film is preferably 0.02 to 0.1 μm. As the method of coating on the substrate, it is coated on the substrate by appropriate coating methods such as spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, etc., but spin coating is better, and its rotation speed is 1000~ 3000rpm (rotations per minute) is better. The coated film is formed into a thin film by prebaking at 60-150° C. for 1-20 minutes, preferably at 80-120° C. for 1-10 minutes. For example, in the case of semiconductor wafers, silicon wafers can be used for the substrate to be processed and the material constituting the outermost layer. Examples of materials for the outermost layer include Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflection film, etc.

Before forming the resist film, an antireflection film may be precoated on the substrate. As the antireflection film, any of inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and organic film types composed of light absorbers and polymer materials can be used. In addition, commercially available organic antireflection films such as DUV30 series and DUV-40 series manufactured by Brewer Science, Inc., AR-2, AR-3, and AR-5 manufactured by Shipley Japan, Ltd. can also be used as the organic antireflection film. Reflective film.

In addition, in the pattern forming method of the present invention, a top coat layer may be formed on the upper layer of the resist film. It is preferable that the top coat layer can be evenly applied to the upper layer of the resist film without being mixed with the resist film. The top coat is not particularly limited, and a previously known top coat can be formed by a previously known method. For example, the top coat can be formed based on the description in paragraphs 0072 to 0082 of JP-A-2014-059543 . For example, it is preferable to form a top coat layer containing a basic compound as described in JP 2013-061648 A on a resist film. Specific examples of the basic compound that the top coat layer may contain are the same as those described above for the acid diffusion inhibitor. Also, it is preferable that the top coat layer contains a compound containing at least one group or bond selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond, and ester bond.

Also, it is preferable that the top coat layer contains a resin. The resin that can be contained as the top coat layer is not particularly limited, and the same hydrophobic resin that can be contained in the actinic radiation-sensitive or radiation-sensitive composition can be used. For hydrophobic resins, refer to [0017] to [0023] of JP-A-2013-061647 (corresponding to [0017]-[0023] of U.S. Laid-Open Patent Publication No. 2013/244438) and JP-A-2014-056194 The descriptions in [0016] to [0165] of the publication are incorporated into the description of the present application. It is preferable that the top coat comprises a resin containing a repeating unit having an aromatic ring. By including a repeating unit having an aromatic ring, especially during electron beam or EUV exposure, the generation efficiency of secondary electrons and the acid generation efficiency from compounds that generate acid by actinic rays or radiation are improved, and pattern formation can be expected The effect of high sensitivity and high resolution at the same time.

When the top coat layer includes a plurality of resins, it is preferable to include at least one resin (XA) having fluorine atoms and/or silicon atoms. The top coat composition preferably includes at least one resin (XA) having fluorine atoms and/or silicon atoms, and resin (XB) having a lower content of fluorine atoms and/or silicon atoms than the resin (XA). Thereby, since the resin (XA) is localized on the surface of the top coat film when the top coat film is formed, it is possible to improve performance such as developing characteristics and immersion liquid followability.

In addition, the top coat layer may contain an acid generator and a crosslinking agent.

Typically, the top coat layer is formed from a composition for forming a top coat layer. Regarding the composition for forming a top coat layer, it is preferable to dissolve each component in a solvent and perform filter filtration. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon with a pore size of 0.1 μm or less, more preferably 0.05 μm or less, further 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 filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. Regarding filter filtration, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-062667 (Japanese Patent Application Laid-Open No. 2002-062667 ), filtration can be performed by performing circulation or by connecting a plurality of filters in series or in parallel. In addition, the composition may be filtered multiple times. In addition, the composition may be degassed before and after filtering with a filter. It is preferable that the composition for forming a top coat layer does not contain impurities such as metals. The content of the metal component contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less, and is particularly preferably substantially free (below the detection limit of the measuring device). In order to reduce the content of metal impurities in the resist composition (for example, at the mass ppm level), the raw materials (resin, photoacid generator, etc.) It is also preferable to perform part or all glass lining (lining) on the inside of the device. Such a method is described, for example, in Chemical Industry Daily on December 21, 2017.

When the exposure described later is immersion exposure, the top coat layer is disposed between the resist film and the immersion liquid, and also functions as a layer that does not directly contact the resist film and the immersion liquid. In this case, the preferred characteristics of the top coat layer (top coat layer forming composition) are coating suitability to resist film, radiation, especially transparency to 193 nm, and liquid immersion liquid ( preferably water) insoluble. In addition, it is preferable that the top coat layer can be further uniformly applied to the surface of the resist film without being mixed with the resist film. In addition, in order to uniformly coat the composition for topcoat layer formation on the surface of the resist film without dissolving the resist film, it is preferable that the composition for topcoat layer formation contains a solvent that does not dissolve the resist film. good. As the solvent that does not dissolve the resist film, it is more preferable to use a solvent having a different component from the developer containing an organic solvent (organic developer) described in detail below.

The coating method of the composition for forming a top coat layer is not particularly limited, and conventionally known spin coating methods, spray coating methods, roll coating methods, dipping methods, and the like can be used.

The film thickness of the top coat layer is not particularly limited, but from the viewpoint of transparency to the exposure light source, it is usually 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, further preferably 30 nm to 100 nm thickness is formed. After the top coat is formed, the substrate is heated (PB) as needed. From an analytical point of view, it is preferable that the refractive index of the top coat layer is close to that of the resist film. Preferably the top coat is insoluble in the immersion liquid, more preferably insoluble in water. With regard to the receding contact angle of the top coat, from the viewpoint of the followability of the immersion liquid, the receding contact angle (23° C.) of the immersion liquid relative to the top coat is preferably 50 to 100 degrees, and 80 to 100 degrees is better. In liquid immersion exposure, considering that the liquid immersion liquid needs to move on the wafer following the movement of the exposure head scanning the wafer at high speed to form the exposure pattern, compared to the liquid immersion liquid of the top coat in the dynamic state The contact angle becomes important, and in order to obtain better resist performance, it is better to have a receding contact angle in the above range.

When peeling off the top coat layer, an organic developer may be used, or a peeling agent may be used alone. As a stripping agent, a solvent with little penetration into a resist film is preferable. From the viewpoint that the peeling of the top coat layer can be performed simultaneously with the development of the resist film, it is preferable that the top coat layer can be peeled off with an organic developer. The organic developing solution used for the peeling is not particularly limited as long as it can dissolve and remove the low-exposed portion of the resist film.

From the viewpoint of peeling with an organic developer, the dissolution rate of the top coat layer with respect to the organic developer is preferably 1 to 300 nm/sec, more preferably 10 to 100 nm/sec. Here, the dissolution rate of the organic developer for the top coat refers to the rate of decrease in film thickness when exposed to a developer after forming the top coat film. The speed of butyl ester. By setting the dissolution rate of the organic developer for the top coat layer to 1/sec or more, preferably 10 nm/sec or more, there is an effect of reducing the occurrence of development defects after developing the resist film. Also, by setting it to 300nm/sec or less, preferably 100nm/sec, the line edge roughness of the pattern after developing the resist film is probably due to the influence of the reduction of exposure unevenness during liquid immersion exposure become better. The top coat layer can be removed using other well-known developing solutions, for example, an aqueous alkali solution or the like. As the alkaline aqueous solution that can be used, specifically, an aqueous solution of tetramethylammonium hydroxide is mentioned.

[Pattern Formation Method] The present invention also relates to a pattern forming method comprising a resist film forming step of forming a resist film using the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention, an exposing step of exposing the resist film, and a developing step of developing the exposed resist film using a developing solution. In the present invention, the above-mentioned exposure is preferably performed using electron beams, ArF excimer lasers, or extreme ultraviolet rays, and more preferably performed using electron beams or extreme ultraviolet rays.

In the manufacture of precision integrated circuit elements, etc., regarding the exposure (patterning step) on the resist film, first, ArF excimer laser, electron beam or extreme ultraviolet rays are patterned on the resist film of the present invention. (EUV) irradiation is preferred. Regarding the exposure amount, in the case of an ArF excimer laser, it is about 1 to 100 mJ/cm ² , preferably about 20 to 60 mJ/cm ² , and in the case of an electron beam, it is about 0.1 to 20 μC/cm ² , preferably about 3 to 10 μC/cm ² , and in the case of extreme ultraviolet light, about 0.1 to 20 mJ/cm ² , preferably about 3 to 15 mJ/cm ² for exposure. Next, on a heating plate, preferably at 60 to 150°C for 5 seconds to 20 minutes, more preferably at 80 to 120°C for 15 seconds to 10 minutes, even more preferably at 80 to 120°C Then, post-exposure heating (post-exposure baking) is performed for 1 to 10 minutes, followed by developing, rinsing, and drying to form a pattern. Here, post-exposure heating is appropriately adjusted by the acid decomposability of the repeating unit having the acid decomposable group in the resin (A). When the acid decomposability is low, the heating temperature after exposure is preferably 110° C. or higher, and the heating time is preferably 45 seconds or longer. The developer can be selected appropriately, and it is preferable to use a developer containing an alkali developer (represented by an aqueous alkali solution) or an organic solvent (also called an organic developer). When the developing solution is an alkaline aqueous solution, use a 0.1 to 5% by mass, preferably 2 to 3% by mass aqueous alkaline solution of tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), etc., and utilize The image development is performed for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by conventional methods such as a dip method, a paddle method, and a spray method. An appropriate amount of alcohols and/or surfactants can be added to the alkaline developer. In this way, in the formation of the negative pattern, the film of the exposed part is not easily dissolved in the developer solution by dissolving the film of the unexposed part, and, in the formation of the positive pattern, the film of the exposed part is dissolved, and The film of the unexposed portion is less likely to dissolve in a developer, thereby forming a target pattern on the substrate.

When the pattern forming method of the present invention has a step of developing using an alkali developing solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc. can be used as the alkali developing solution. Inorganic bases, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanolamine Alcohol amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide Ammonium Hydroxide, Ethyltrimethylammonium Hydroxide, Butyltrimethylammonium Hydroxide, Methyltripentylammonium Hydroxide, Dibutyldipentylammonium Hydroxide, Tetraalkylammonium Hydroxide, Trimethylammonium Hydroxide Phenyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, triethyl benzyl ammonium hydroxide, dimethyl bis(2-hydroxyhexadecyl) ammonium hydroxide and other quaternary ammonium salts, pyrrole, piperidine Alkaline aqueous solutions such as cyclic amines, etc. It can also be used by adding an appropriate amount of alcohols and surfactants to the above-mentioned alkaline aqueous solution. The alkali concentration of an alkaline developer is normally 0.1-20 mass %. The pH of the alkaline developing solution is usually 10.0 to 15.0. In particular, it is desirable to be a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

Pure water can also be used as a rinsing liquid in the rinsing process performed after alkali image development, and it can add and use an appropriate amount of surfactant. In addition, after the development treatment or the rinse treatment, it is possible to perform a process of removing the developing solution or the rinse solution adhering to the pattern with a supercritical fluid.

When the pattern forming method of the present invention has a step of developing using a developer containing an organic solvent, as the developer in the above step (hereinafter, also referred to as an organic developer), a ketone solvent, an ester solvent, Polar solvents such as alcohol-based solvents, amide-based solvents, and ether-based solvents, and hydrocarbon-based solvents.

In the present invention, an ester solvent refers to a solvent having an ester group in the molecule, a ketone solvent refers to a solvent having a ketone group in the molecule, an alcohol solvent refers to a solvent having an alcoholic hydroxyl group in the molecule, and an amide solvent refers to a solvent having an alcoholic hydroxyl group in the molecule. A solvent refers to a solvent having an amide group in the molecule, and an ether solvent refers to a solvent having an ether bond in the molecule. Among these, there are also solvents having a plurality of types of the above-mentioned functional groups in one molecule, but in this case, it is applicable to any solvent type including the functional group having the solvent. For example, diethylene glycol monomethyl ether is any one of alcohol-based solvents and ether-based solvents corresponding to the above classification. Also, the hydrocarbon-based solvent refers to a hydrocarbon solvent having no substituent. In particular, a developer containing at least one solvent selected from ketone-based solvents, ester-based solvents, alcohol-based solvents, and ether-based solvents is preferable.

From the viewpoint of being able to suppress the swelling of the resist film, a developer having at least 7 carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a heteroatom number of Ester-based solvents below 2 are preferred. The hetero atom of the above-mentioned ester-based solvent is an atom other than a carbon atom and a hydrogen atom, for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc. are mentioned. The number of heteroatoms is preferably 2 or less. Preferred examples of ester-based solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isopentyl acetate, 2-methylbutyl acetate, and 1-methylbutyl acetate. , hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, isobutyl isobutyrate, etc. It is particularly preferable to use isoamyl acetate or isobutyl isobutyrate.

The developer may use a mixed solvent of the ester solvent and the hydrocarbon solvent or a mixed solvent of the ketone solvent and the hydrocarbon solvent instead of the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms. In this case, swelling of the resist film is also effectively suppressed. When an ester-based solvent and a hydrocarbon-based solvent are used in combination, it is preferable to use isoamyl acetate as the ester-based solvent. Also, from the viewpoint of adjusting the solubility of the resist film, as the hydrocarbon solvent, a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) is used. better. As the ketone solvent, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1 -hexanone, 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl Isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetylmethanol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, etc., use diisobutyl Ketones, 2,5-dimethyl-4-hexanone are particularly preferred. Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate ), propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionic acid ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, lactic acid Butyl ester, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, etc. Examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, 4-methyl-2-pentanol, tertiary butanol, isobutanol, Alcohols such as n-hexanol, n-heptanol, n-octanol, and n-decyl alcohol; or glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, Glycol ether solvents such as ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethyl butanol. Examples of ether solvents include anisole, dioxane, tetrahydrofuran, and the like in addition to the above-mentioned glycol ether solvents. As an amide-based solvent, for example, N-methyl-2-pyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, hexamethylphosphoramide, Triamine, 1,3-dimethyl-2-imidazolidinone, etc. Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane. In addition, the aliphatic hydrocarbon solvent used as the hydrocarbon solvent may be a mixture of compounds having the same carbon number but different structures. For example, when decane is used as an aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, iso Octane and the like may be contained in the aliphatic hydrocarbon solvent. In addition, the above-mentioned compounds having the same carbon number and different structures may contain one type, or may contain plural types as described above. The above-mentioned solvents may be mixed in plural, and may be used in admixture with solvents other than the above-mentioned ones or water. Among them, in order to fully exert the effect of the present invention, the water content of the entire developer is preferably less than 10% by mass, and it is more preferably substantially free of water. The concentration of the organic solvent in the organic developer (combined when a plurality of them are mixed) is preferably at least 50% by mass, more preferably 50 to 100% by mass, further preferably 85 to 100% by mass, still more preferably 90% by mass. ~100% by mass, particularly preferably 95% to 100% by mass. It is most preferable that it consists substantially only of an organic solvent. In addition, the case where it consists substantially only of an organic solvent means the case where a trace amount of surfactant, antioxidant, stabilizer, antifoaming agent, etc. are included. In particular, an organic developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents is preferred.

The vapor pressure of the organic developer is preferably at most 5 kPa at 20° C., more preferably at most 3 kPa, and most preferably at most 2 kPa. By setting the vapor pressure of the organic developer to 5 kPa or less, the evaporation of the developer on the substrate or in the developer cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the size of the wafer in the surface Uniformity is improved. Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), and 4-heptanone , 2-hexanone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenylacetone, methyl isobutyl ketone and other ketone solvents; butyl acetate, amyl acetate, isoamyl acetate, acetic acid Amyl ester, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropane Ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Ester solvents; n-propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, n-decyl alcohol and other alcohol solvents; Glycol, diethylene glycol, triethylene glycol and other glycol-based solvents or, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl Glycol ether solvents such as oxymethyl butanol; ether solvents such as tetrahydrofuran; N-methyl-2-pyrrolidone, N,N'-dimethylacetamide, N,N'-dimethyl Amide-based solvents of formamide; aromatic hydrocarbon-based solvents such as toluene and xylene; aliphatic hydrocarbon-based solvents such as octane and decane. Specific examples having a vapor pressure of 2 kPa or less in an especially preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2 - Ketone solvents such as hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetic acid ester, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl -3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate and other ester solvents; n-butanol, secondary butanol, tertiary butanol, isobutanol, n-hexanol, n-butanol Alcohol-based solvents such as heptanol, n-octanol, and n-decyl alcohol; diol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and ethylene glycol Monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol and other glycol ether solvents; N-methyl-2-pyrrolidone, N,N '-Dimethylacetamide, N,N'-dimethylformamide amide-based solvents; xylene and other aromatic hydrocarbon-based solvents; octane, decane, undecane and other aliphatic hydrocarbon-based solvents.

The organic developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as the specific examples and preferred examples of the basic compound that can be contained in the above-mentioned actinic radiation or radiation sensitive composition.

An appropriate amount of surfactant can be added to the organic developer as needed. The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and/or silicon-based surfactants and the like can be used. As such fluorine and/or silicon-based surfactants, for example, JP-A-62-036663, JP-A-61-226746, JP-A-61-226745, JP-A JP-A-62-170950, JP-A-63-034540, JP-7-230165, JP-8-062834, JP-9-054432, JP-9- Publication No. 005988, US Patent No. 5405720, US Patent No. 5360692, US Patent No. 5529881, US Patent No. 5296330, US Patent No. 5436098, US Patent No. 5576143, US Patent No. 5294511 No. specification, US Pat. No. 5,824,451 specification described in the surfactant, preferably non-ionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is more preferable to use a fluorine-type surfactant or a silicon-type surfactant. The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0001 to 1% by mass, particularly preferably 0.0001 to 0.1% by mass, relative to the total amount of the developer.

As a developing method, for example, the following methods can be applied: a method of immersing the substrate in a tank filled with a developer solution for a constant time (dipping method), a method of developing by stacking a developer solution on the surface of the substrate by surface tension and standing still for a constant time (paddle method), method of spraying developer on the substrate surface (spray method), method of continuously spraying developer while scanning the developer spray nozzle at a constant speed on a substrate rotating at a constant speed (dynamic distribution law), etc. When the above-mentioned various developing methods include the step of spraying the developing solution from the developing nozzle of the developing device toward the resist film, the spraying pressure of the sprayed developing solution (the flow rate per unit area of the sprayed developing solution) is preferably 2 mL /sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, further preferably 1 mL/sec/mm ² or less. The lower limit of the flow rate is not limited by the characteristics, but considering the throughput, it is preferably 0.2mL/sec/mm ² or more. By setting the spraying pressure of the sprayed developing solution within the above-mentioned range, it is possible to remarkably reduce pattern defects derived from resist residue after development. The details of this mechanism are unclear, but it is thought that by setting the injection pressure within the above range, the pressure applied by the developer to the resist film is reduced, and the resist film/pattern is suppressed from being unintentionally cut or collapsed. . In addition, the spray pressure (mL/sec/mm ² ) of the developer is a value at the outlet of the developing nozzle in the developing device.

As a method of adjusting the injection pressure of the developer, for example, a method of adjusting the injection pressure with a pump or the like, a method of adjusting the pressure by supplying it from a pressurized tank, and changing it, etc., can be mentioned.

In addition, after the step of developing using a developer containing an organic solvent, a step of replacing it with another solvent and stopping the development may be performed.

The step of washing with a rinse solution may be included after the step of developing with a developer containing an organic solvent, but the step of washing with a rinse solution may not be included from the viewpoint of throughput (productivity), amount of rinse solution, etc. .

The rinsing solution used in the rinsing step after the step of developing using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. As the rinsing solution, it is preferable to use a rinsing solution 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. 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 as those described in the developer containing an organic solvent. In particular, Preferable examples include butyl acetate and methyl isobutyl carbinol. Preferably, after the step of developing using a developer containing an organic solvent, it is more preferable to use a rinse solution containing at least one organic solvent selected from the group consisting of ester solvents, alcohol solvents, and hydrocarbon solvents. The washing step is more preferably a washing step using a rinse solution containing an alcohol-based solvent or a hydrocarbon-based solvent.

As the organic solvent contained in the rinsing liquid, it is preferable to use a hydrocarbon-based solvent among the organic solvents, and it is more preferable to use an aliphatic hydrocarbon-based solvent. As the aliphatic hydrocarbon solvent used in the rinsing liquid, from the viewpoint of further enhancing its effect, aliphatic hydrocarbon solvents with 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane , dodecane, hexadecane, etc.) are preferred, aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred. In addition, the upper limit of the number of carbon atoms of the aliphatic hydrocarbon-based solvent is not particularly limited, for example, 16 or less, preferably 14 or less, more preferably 12 or less. Among the above-mentioned aliphatic hydrocarbon solvents, decane, undecane, and dodecane are particularly preferable, and undecane is most preferable. By using a hydrocarbon-based solvent (especially an aliphatic hydrocarbon-based solvent) as an organic solvent contained in the rinse solution in this way, the developer solution that permeates the resist film slightly after development is washed away, thereby further developing swelling. The effect of suppressing and suppressing pattern collapse can be obtained.

The above-mentioned components may be mixed in plural, and may be used in admixture with organic solvents other than the above-mentioned ones.

The water content in the flushing liquid is preferably at most 10% by mass, more preferably at most 5% by mass, and most preferably at most 3% by mass. Favorable image development characteristics can be acquired by making water content into 10 mass % or less.

Regarding the vapor pressure of the rinse solution used after the step of developing with a developer containing an organic solvent, at 20°C, it is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa Above and below 3kPa is the best. By setting the vapor pressure of the rinsing liquid to 0.05kPa to 5kPa, the temperature uniformity in the wafer surface is improved, and the swelling caused by the penetration of the rinsing liquid is suppressed, and the dimensional uniformity in the wafer surface is improved. .

It can also be used by adding an appropriate amount of surfactant to the rinse solution.

In the rinsing step, the wafer is cleaned using a rinsing solution containing the above-mentioned organic solvent, and the wafer is developed using a developing solution containing an organic solvent. The method of cleaning treatment is not particularly limited, for example, the following methods can be applied: the method of continuously spraying the rinse solution on the substrate rotating at a constant speed (spin coating method), immersing the substrate in a tank filled with the rinse solution for a constant time The method (dipping method), the method of spraying the rinse solution on the substrate surface (spray method), etc., wherein the spin coating method is used for cleaning treatment, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm and the rinse solution is sprayed from the substrate. Removal is better. In addition, it is also preferable to include a heating step (Post Bake) after the rinsing step. The developer and rinse solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually carried out at 40 to 160°C, preferably at 70 to 95°C, for usually 10 seconds to 3 minutes, preferably for 30 seconds to 90 seconds.

When there is no step of washing with a rinse solution, for example, the development treatment method described in paragraphs [0014] to [0086] of JP 2015-216403 can be used.

Moreover, the pattern formation method of this invention may have the image development process using an organic developer, and the image development process using an alkali developer. The portion with weak exposure intensity is removed by development using an organic developer, and the portion with strong exposure intensity is also removed by development using an alkali developer. Since pattern formation can be performed without dissolving only the region of intermediate exposure intensity by performing multiple development steps of multiple development in this way, it is possible to form a finer pattern than usual (same as JP-A 2008 -292975 Bulletin No. [0077] the same mechanism).

Various materials used in the actinic radiation or radiation sensitive composition of the present invention and the pattern forming method of the present invention (for example, resist solvent, developing solution, rinse solution, antireflection film forming composition, top coat Layer-forming composition, etc.) preferably do not contain impurities such as metals, metal salts containing halogens, acids, bases, components containing sulfur atoms or phosphorus atoms. Here, examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The content of impurities contained in these materials is preferably 1ppm or less, more preferably 1ppb or less, further preferably 100ppt (parts per trillion: parts per trillion) or less, particularly preferably 10ppt or less, and substantially does not contain (Below the detection limit of the measuring device) is the best. As a method of removing impurities such as metals from various materials, for example, filtration using a filter can be mentioned. The pore size of the filter is preferably at most 10 nm, more preferably at most 5 nm, and still more preferably at most 3 nm. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. Filters may be composite materials combining these materials with ion exchange media. Filters can also be pre-cleaned with organic solvents. In the filter filtering step, a plurality of types of filters may be connected in series or in parallel and used. When using multiple types of filters, filters with different pore diameters and/or materials can also be used in combination. In addition, various materials may be filtered multiple times, and the step of performing multiple times of filtration may also be a circulating filtration step. In addition, as a method of reducing impurities such as metals contained in various materials, the following methods can be mentioned: selecting raw materials with low metal content as raw materials constituting various materials, filtering the raw materials constituting various materials, A method such as distillation under conditions where contamination is suppressed as much as possible by lining with TEFLON (registered trademark). Preferable conditions in filter filtration of the raw materials constituting each material are the same as those described above. In addition to filter filtration, impurities can also be removed using an adsorbent, and filter filtration and adsorbent can also be used in combination. As the adsorbent, known adsorbents can be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In addition, as a method of reducing impurities such as metals contained in the organic treatment liquid of the present invention, the following methods can be mentioned: selecting raw materials with low metal content as raw materials constituting various materials, and filtering the raw materials constituting various materials. , Distillation is carried out under conditions such as lining the device with TEFLON (registered trademark) to suppress contamination as much as possible. Preferable conditions for filter filtration of the raw materials constituting the various materials are the same as those described above. In addition to filter filtration, it is also possible to remove impurities using adsorption materials, and it is also possible to use filter filtration and adsorption materials in combination. As the adsorbent, known adsorbents can be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

[storage container] As an organic solvent (also referred to as "organic processing liquid") that can be applied to the developer and rinse liquid, an organic processing liquid for pattern formation that has a container, a chemically amplified type or a non-chemically amplified resist film is used. Those stored in storage containers are the best. As the storage container, for example, the inner wall of the storage part in contact with the organic treatment liquid is made of a resin different from any one of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or is made of antirust/ A storage container for an organic treatment liquid for patterning a resist film formed of a metal formed by metal elution prevention treatment is preferable. A predetermined organic solvent used as an organic treatment liquid for patterning a resist film is stored in the storage portion of the storage container, and what is discharged from the storage portion can be used when patterning the resist film.

When the storage container further has a sealing portion for sealing the storage portion, the sealing portion is also made of a resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferable to form it from a resin, or a metal that has been treated to prevent rust/metal elution.

Here, the sealing part means a member capable of blocking the housing part and the outside air, and packing, an O-ring, etc. can be mentioned preferably.

The resin different from one or more resins selected from the group consisting of polyethylene resins, polypropylene resins, and polyethylene-polypropylene resins is preferably a perfluororesin.

Examples of perfluororesins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene Ethylene-ethylene copolymer resin (ETFE), chlorotrifluoroethylene-ethylene copolymer resin (ECTFE), vinylidene chloride resin (PVDF), chlorotrifluoroethylene copolymer resin (PCTFE), vinyl fluoride resin (PVF), etc. .

Particularly preferred perfluororesins include tetrafluoroethylene resins, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resins, and tetrafluoroethylene-hexafluoropropylene copolymer resins.

Examples of metals in metals subjected to rust prevention/metal elution prevention treatment include carbon steel, alloy steel, nickel-chromium steel, nickel-chromium-molybdenum steel, chromium steel, chromium-molybdenum steel, manganese steel, and the like.

As anti-rust/metal elution prevention treatment, it is better to apply coating technology.

In the coating technology, it is roughly divided into three types: metal coating (various electroplating), inorganic coating (various chemical treatments, glass, cement, ceramics, etc.) and organic coating (anti-rust oil, paint, rubber, plastic) .

As a preferred coating technology, surface treatment by anti-rust oil, anti-rust agent, preservative, chelating compound, peelable plastic, and lining agent can be mentioned.

Among them, various chromates, nitrites, silicates, phosphates, oleic acid, dimer acid, naphthenic acid and other carboxylic acids, carboxylic acid metal soaps, sulfonates, amine salts, esters (glycerin of higher fatty acids) ester or phosphate) and other preservatives; chelating compounds such as ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid and fluororesin lining are relatively good. Especially good for phosphate treatment and fluororesin lining.

In addition, compared with direct coating treatment, although it does not directly prevent rust, as a treatment method for extending the antirust period by coating treatment, it is also more effective to use "pretreatment" which is the stage before applying antirust treatment. good.

As a specific example of such a pretreatment, a treatment for removing various corrosion factors such as chlorides and sulfates present on the metal surface by washing or polishing can be preferably mentioned.

As a storage container, the following can be mentioned specifically.

･FluoroPure PFA composite cartridge manufactured by Entegris, Inc. (inner surface wetted with liquid; PFA resin lining) ･Steel cans manufactured by JFE CONTAINER CO.,LTD. (inner surface in contact with liquid; zinc phosphate coating)

In addition, examples of storage containers that can be used in the present invention include those described in [0013] to [0030] of JP-A-11-021393 and [0012]-[0024] of JP-A-10-045961. container.

The organic treatment liquid of the present invention can also add conductive compounds to prevent electrostatic charging and subsequent failure of chemical piping or various components (filters, O-rings, hoses, etc.) accompanied by electrostatic discharge. The conductive compound is not particularly limited, for example, methanol is mentioned. The addition amount is not particularly limited, but is preferably 10% by mass or less, and more preferably 5% by mass or less, from the viewpoint of maintaining good image development characteristics. For chemical piping components, various piping coated with SUS (stainless steel) or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) with antistatic treatment can be used. Similarly, for a filter or an O-ring, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used.

In addition, generally, the developing solution and the rinse solution are stored in a waste liquid tank through piping after use. At this time, if a hydrocarbon-based solvent is used as the rinsing solution, in order to prevent the resist dissolved in the developer from being deposited on the back surface of the wafer and the side of the pipe, etc., it is necessary to pass the solvent dissolved in the resist through the pipe again. method. As the method of passing through the pipes, after cleaning with a rinse liquid, the method of washing with a solution dissolved in a resist and flowing it over the back and side surfaces of the substrate, etc., or passing a solvent in which a resist is dissolved through a pipe and flowing in parallel A method that does not come into contact with the resist. The solvent passing through the piping is not particularly limited as long as it can dissolve the resist, for example, the organic solvents mentioned above can be used, and propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate , Propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether acetate, Propylene glycol monomethyl ether propionate, Propylene glycol monoethyl ether propionate, Ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate , propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, Acetone etc. Among them, PGMEA, PGME, and cyclohexanone can be preferably used.

[Reticle] Moreover, the present invention also relates to a photomask manufactured using the above-mentioned pattern forming method. The photomask produced by the pattern forming method described above may be a light-transmissive mask used in ArF excimer laser, etc., or a light-reflective mask used in reflective lithography using EUV light as a light source.

[Manufacturing method of electronic device] In addition, the present invention also relates to a method of manufacturing an electronic device including the above pattern forming method. The electronic device manufactured by the method for manufacturing an electronic device of the present invention can be suitably mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.) .

[compound] The present invention also relates to a compound represented by the following general formula (A).

[chemical formula 73]

In the general formula (A), R ₁ and R ₂ each independently represent a group represented by any one of the following general formulas (R-1) to (R-3). R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. A represents a single bond or a linking group of (n+1) valence. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different. M ^m+ represents a cation. m represents an integer of 1 or more.

[chemical formula 74]

In the general formulas (R-1) to (R-3), R ₆ to R ₂₇ each independently represent a hydrogen atom or a substituent. In the general formula (R-1), at least two of R ₆ to R ₁₃ may be bonded to each other to form a ring. In the general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to each other to form a ring. In the general formula (R-3), at least two of R ₁₉ to R ₂₇ may be bonded to each other to form a ring. * represents a bond to the benzene ring in the general formula (1). In the aforementioned general formula (R-1) in the aforementioned general formula (3), at least one of R ₆ to R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ and Forming a ring, in the aforementioned general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form a ring, in the aforementioned general formula (R-3), R ₁₉ At least one of R ₂₁ to R 21 is bonded to at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ to form a ring. In the aforementioned general formula (R-1) in the aforementioned general formula (3), at least one of R ₆ to R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ and The ring formed, the ring formed by bonding at least one of R ₁₄ to R ₁₆ to at least one of R ₁₇ and R ₁₈ in the aforementioned general formula (R-2), and the aforementioned general formula (R-3) , in the ring formed by bonding at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ , the number of carbon atoms constituting the ring members is 5 to 10, respectively .

Specific examples of R ₁ , R ₂ , R ₃ and R ₅ of the general formula (A) are respectively the same as R ₁ , R ₂ , R ₃ and R of the general formula (1) of the compound (A) in the composition of the present invention The specific example of ₅ is the same. The specific examples of A, Y and n in the general formula (A) are the same as the specific examples of A, Y and n in the above general formula (R-4) of the compound (A) in the composition of the present invention. The specific examples of m and M ^m+ in the general formula (A) are the same as the specific examples of m and M ^m+ in the general formula (1) of the compound (A) in the composition of the present invention.

Also, the present invention relates to a compound represented by the following general formula (3).

[chemical formula 75]

In the general formula (3), R ₁ and R ₂ each independently represent a group represented by any one of the following general formulas (R-1) to (R-3). R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. A represents a single bond or a linking group of (n+1) valence. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. n represents an integer of 1 or more. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.

[chemical formula 76]

In the general formulas (R-1) to (R-3), R ₆ to R ₂₇ each independently represent a hydrogen atom or a substituent. In the general formula (R-1), at least two of R ₆ to R ₁₃ may be bonded to each other to form a ring. In the general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to each other to form a ring. In the general formula (R-3), at least two of R ₁₉ to R ₂₇ may be bonded to each other to form a ring. * represents a bond to the benzene ring in the general formula (1). In the above general formula (R-1) in the above general formula (3), at least one of R ₆ to R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ To form a ring, in the above general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form a ring, in the above general formula (R-3) , at least one of R ₁₉ to R ₂₁ is bonded to at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ to form a ring. In the above general formula (R-1) in the above general formula (3), at least one of R ₆ to R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ In the above general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form a ring, and in the above general formula (R- 3), in the ring formed by bonding at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ , the number of carbon atoms constituting the ring members is 5 to 10.

Specific examples of R ₁ , R ₂ , R ₃ and R ₅ of the general formula (3) are respectively the same as R ₁ , R ₂ , R ₃ and R of the general formula (1) of the compound (A) in the composition of the present invention The specific example of ₅ is the same. The specific examples of A, Y and n in the general formula (3) are the same as the specific examples of A, Y and n in the above general formula (R-4) of the compound (A) in the composition of the present invention. Specific examples of R ₁₀₁ to R ₁₀₃ of the general formula (3) are the same as specific examples of R ₁₀₁ to R ₁₀₃ of the general formula (2) in the compound (A) in the composition of the present invention.

The above compound is preferably represented by the following general formula (9).

[chemical formula 77]

In the general formula (9), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. A represents a single bond or a linking group of (n+1) valence. n represents an integer of 1 or more. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.

Specific examples of R ₃ and R ₅ in the above general formula (9) are the same as specific examples of R ₃ and R ₅ in the above general formula (1) of the compound (A) in the composition of the present invention. The specific examples of A, Y and n in the general formula (9) are the same as the specific examples of A, Y and n in the above general formula (R-4) of the compound (A) in the composition of the present invention. Specific examples of R ₁₀₁ to R ₁₀₃ in the general formula (9) are the same as specific examples of R ₁₀₁ to R ₁₀₃ in the general formula (2) of the compound (A) in the composition of the present invention.

The above compound is preferably represented by the following general formula (10).

[chemical formula 78]

In the general formula (10), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent. R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent. Two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring. R ₅₁ to R ₅₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₅₁ to R ₅₅ represents a group represented by the following general formula (R-5).

[chemical formula 79]

In general formula (R-5), B represents a single bond or a (n+1) valence linking group. n represents an integer of 1 or more. Y represents a group including a polar group, a group including a group whose polarity is increased by decomposition by the action of an acid, or a group including a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer group of groups. When n represents an integer of 2 or more, a plurality of Ys may be the same or different. * represents a bond to the benzene ring in the general formula (10).

Specific examples of R ₃ and R ₅ in the above general formula (10) are the same as specific examples of R ₃ and R ₅ in the above general formula (1) of the compound (A) in the composition of the present invention. Specific examples of R ₁₀₁ to R ₁₀₃ in the general formula (10) are respectively the same as specific examples of R ₁₀₁ to R ₁₀₃ in the general formula (2) of the compound (A) in the composition of the present invention.

Specific examples of R ₅₁ to R ₅₅ in the above general formula (10) are the same as specific examples of R ₅₁ to R ₅₅ in the above general formula (6) in the compound (A) in the composition of the present invention. Specific examples of B, Y, and n in the above general formula (R-5) are the same as specific examples of B, Y, and n in the above general formula (R-5) of the compound (A) in the composition of the present invention.

Y in each of the above general formulas represents hydroxyl, carboxyl, a group with a carbonyl bond, acyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, aryloxycarbonyl, alkoxycarbonyl, carboxylate A group or an imide group is preferred. Specific examples of a group having a carbonyl bond, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or an imide group of the above-mentioned Y For example, the group having a carbonyl bond, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkyl group, etc. The oxycarbonyl, carbamoyl or imide groups are the same.

Y in each of the above general formulas preferably represents a hydroxyl group, a carboxyl group or an alkoxycarbonyl group. [Example]

Hereinafter, the present invention will be described in further detail based on examples. Materials, usage amounts, ratios, processing contents, processing procedures and the like shown in the following examples can be appropriately changed unless departing from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.

＜Resin (B)＞ The structure of the repeating unit of the resin (B) used and its content (molar ratio), weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) are shown below.

[chemical formula 80]

[chemical formula 81]

＜Photoacid generator (A)＞ <Synthesis Example 1: Synthesis of Photoacid Generator (A-1)> (Synthesis of Compound (A-1)) Compound (A-1) was synthesized according to the following scheme.

[chemical formula 82]

Under a nitrogen atmosphere, add 1 mol/L zinc chloride THF solution (90.0ml, 90.0mmol) dropwise to 1mol/L cyclohexylmagnesium bromide THF solution (90.0ml, 90.0mmol) in a water bath, at room temperature After stirring for 1 hour, 4-chloro-2,6-dibromoaniline (6.42g, 22.5mmol), tetrakis(triphenylphosphine)palladium(0) (780mg, 0.675mmol) were added, under nitrogen atmosphere, and in The reaction was carried out at 60°C for 2.5 hours. After cooling to room temperature, an aqueous ammonium chloride solution was added to the reaction solution, and the organic layer was extracted with ethyl acetate, washed again with an aqueous ammonium chloride solution, and concentrated under reduced pressure. By subjecting the concentrated residue to silica gel column chromatography (ethyl acetate:hexane=1:10), compound 1 (5.49 g, 18.8 mmol, 84% yield) was obtained as a light red powder.

Compound 1 (11.5 g, 39.4 mmol) was added to a mixed solvent of 69 ml of water, 69 ml of acetonitrile, and 46 ml of concentrated sulfuric acid, and cooled to -10°C. After cooling, an aqueous solution obtained by dissolving sodium nitrite (4.83 g, 70.1 mmol) in 41.4 ml of water was added dropwise, followed by stirring at -10°C for 30 minutes after the dropwise addition. An aqueous solution obtained by dissolving potassium iodide (22.9 g, 138 mmol) in 115 ml of water was added dropwise, and the mixture was stirred for 1 hour after returning to room temperature. 300ml of ethyl acetate was added to the reaction mixture, and an aqueous solution of sodium thiosulfate was added dropwise to decompose the remaining iodine generated in the reaction. The organic layer was extracted with ethyl acetate by liquid separation, washed with physiological saline, and concentrated under reduced pressure. Compound 2 (5.00 g, 12.4 mmol, 32% yield) was obtained as pale red crystals by subjecting the concentrated residue to silica gel column chromatography (hexane).

Add 20ml of cyclopentyl methyl ether to compound 2 (1.00g, 2.48mmol), and cool to -78°C under a nitrogen atmosphere. A 2.6 mol/L n-butyllithium hexane solution (1.14 ml, 3.00 mol) was added dropwise and stirred for 10 minutes. A solution obtained by diluting sulfonyl chloride (405 mg, 3.00 mmol) in 1.21 ml of n-hexane was added dropwise, and stirred for 1 hour after returning to room temperature. Water was added to the reaction mixture, and the organic layer was extracted with ethyl acetate by a liquid separation operation, washed with physiological saline, and concentrated under reduced pressure. 9 ml of ethanol, 1 ml of distilled water, sodium hydroxide (792 mg, 19.8 mmol) were added to the concentrated residue containing compound 3, and reacted by heating under reflux for 2 hours. After adding ethyl acetate and water to the reaction mixture, sulfuric acid was added dropwise to adjust the pH to 1-2, and several layers were extracted with ethyl acetate, washed with normal saline and concentrated under reduced pressure. By subjecting the concentrated residue to silica gel column chromatography (ethyl acetate:methanol=10:1), compound 4 (5.00 g, 12.4 mmol, 32% yield) was obtained as a white powder.

Compound 4 (36.4mg, 0.102mmol), (4‐methoxycarbonylmethyl)phenylboronic acid (27.5mg, 0.153mmol), palladium (II) acetate (3.44mg, 0.0153mmol), 2-dicyclohexyl Add phosphino-2',6'-dimethoxybiphenyl (S-Phos) (12.6mg, 0.0306mmol), potassium triphosphate (75.8mg, 0.357mmol), 1ml THF and 10μl distilled water into a 50ml three-necked flask , nitrogen substitution was performed. Under a nitrogen atmosphere, it was heated to 60° C. and stirred for 4 hours. Also, after cooling to room temperature, water was added to the reaction solution. Several layers were extracted with ethyl acetate, washed with saline and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (ethyl acetate:methanol=5:1). Add 5 ml of chloroform to the crude purified product to dissolve it, add 3 mg of activated carbon ANOX1 (manufactured by Osaka Gas Chemical Co., Ltd.) and 1.5 mg of trimercapto to three wells, and stir at room temperature for 2 hours (becoming a catalyst The palladium was adsorbed in three wells of activated carbon and trimercapto). Activated carbon ANOX1 was removed by filtration, and the chloroform organic layer was washed with a 10 wt % sodium bicarbonate aqueous solution, washed twice with a 0.1 mol/L aqueous hydrochloric acid solution, and further washed twice with ultrapure water. After vacuum distillation by the solvent, 10 ml of ethyl acetate was added for vacuum distillation to azeotrope the water for dehydration. The obtained crude product was recrystallized from ethyl acetate/methanol and dried in vacuo to obtain compound 5 (37.0 mg, 0.0773 mmol, 76% yield) as a white powder.

Compound 5 (360mg, 0.775mmol), triphenyl cobaltium bromide (266mg, 0.775mmol), 40ml ethyl acetate and 20ml distilled water were added to a 200ml three-necked flask, stirred under yellow light and at room temperature for 1 Hour. The organic layer of the reaction mixture was extracted with ethyl acetate, washed with distilled water, and concentrated under reduced pressure. Add 10ml of diisopropyl ether to the concentrated residue, stir for 30 minutes, filter the precipitated powder, and wash with diisopropyl ether to obtain compound (A-1) (500mg, 0.0695mmol, 90% yield ), which is a white powder. In addition, the ¹ H-NMR spectrum (400 MHz, CDCL3) of compound (A-1) is as follows. ¹ H-NMR (CDCl3 400 MHz) δ: 8.08 (d, J=8.5Hz, 2 H), 7.81 (d, J=8.2Hz, 6 H), 8.31-8.29 (m, 2H), 8.25-8.19 ( m, 2H), 7.73-7.67 (m, 2H), 7.71-7.58 (m, 11H), 7.40 (s, 1H), 4.35 (t, J=7.2Hz, 2H), 3.94 (s, 3H), 1.99 -1.95 (m, 4H), 1.78-1.69 (m, 6H), 1.45-1.20 (m, 10H);

Hereinafter, compounds (A-2) to (A-17) were synthesized by the same method. It was confirmed that the pKa of the acids generated by the compounds (A-1) to (A-17) was -10 or more and 5 or less. Me represents a methyl group.

[chemical formula 83]

[chemical formula 84]

[chemical formula 85]

In Comparative Examples, the following compounds (A'-1) and (A'-2) were used.

[chemical formula 86]

＜Acid diffusion control agent＞ The structure of the acid diffusion control agent used is shown below. Me represents a methyl group.

[chemical formula 87]

[chemical formula 88]

＜Surfactant＞ As surfactants, the following W-1 to W-4 were used. W-1: MEGAFACE R08 (manufactured by DIC Corporation; fluorine and silicon) W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicon-based) W-3: TroySolS-366 (manufactured by Troy Chemical Industries Inc.; fluorine-based) W-4: PF6320 (manufactured by OMNOVA SOLUTIONS INC.; fluorine-based)

<Solvent> The solvents used are shown below. S-1: Propylene Glycol Monomethyl Ether Acetate (PGMEA) S-2: Propylene Glycol Monomethyl Ether (PGME) S-3: Ethyl Lactate (EL) S-4: Ethyl 3-ethoxypropionate (EEP) S-5: 2-Heptanone (MAK) S-6: Methyl 3-methoxypropionate (MMP) S-7: 3-methoxybutyl acetate

[Preparation and application of coating solution of resist composition] (1) Preparation of support body An 8-inch wafer on which Cr oxynitride was vapor-deposited was prepared. (2) Preparation of resist composition The components shown in Table 1 were dissolved in the solvents shown in the same table, and a solution was prepared at the solid content (solid content concentration) shown in the same table, and filtered through polyethylene having a pore size of 0.03 μm This was filtered through a filter to prepare a resist composition. (3) Preparation of resist film The resist composition was coated on the above-mentioned 8-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron Limited, and dried on a heating plate at 120° C. for 600 seconds to obtain a resist composition with a film thickness of 100 nm. etchant film. That is, a resist-coated wafer was obtained.

[EB exposure and development] (4) Fabrication of photoresist patterns The resist film obtained in the above (3) was subjected to pattern irradiation using an electron beam drawing apparatus (manufactured by Advantest Co., Ltd.; F7000S, acceleration voltage 50 KeV). After irradiation, it was heated on a hot plate at 100° C. for 600 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried.

[evaluate] (5) Evaluation of resist pattern The obtained pattern was evaluated with respect to resolution and development defects by the following method. The results are shown in Table 2 below.

The irradiation energy when analyzing a 1:1 line-space pattern with a line width of 50nm is taken as the sensitivity (Eop).

＜L/S resolution＞ The limit resolution (minimum line width at which line and space (line: pitch = 1:1) are separated and analyzed) under the exposure amount that shows the above sensitivity (Eop) is taken as the resolution (nm).

＜Isolated space pattern (IS) resolution＞ Find the limit resolution (minimum space width for separate analysis of line and space) in an isolated space (line:spacing = 100:1) at the above sensitivity (Eop). And, let this value be "isolated spatial pattern resolving power (nm)". Indicates that the smaller the value, the better the performance.

<Development defects> Using the defect inspection device KLA2360 (product name) manufactured by KLA-Tencor Corporation, set the pixel size of the defect inspection device for a 1:1 line-and-space pattern with a line width of 50 nm formed at the above sensitivity (Eop) 0.16μm, and set the threshold to 20, detect the defects (number/cm ² ) extracted from the difference generated by comparing the superposition of the image and the pixel unit, and calculate the number of defects per unit area (number/cm ² ). Then, the development defects were classified and extracted from all the defects by performing defect inspection, and the number of development defects per unit area (number/cm ² ) was calculated. A value of less than 0.5 was defined as A, a value of 0.5 or more and less than 1.0 was defined as B, a value of 1.0 or more and less than 5.0 was defined as C, and a value of 5.0 or greater was defined as D. Indicates that the smaller the value, the better the performance. In addition, in the following Table 1, the content (mass %) of each component other than the solvent represents the content ratio with respect to the total solid content. In addition, the content ratio (mass %) of all the solvents with respect to the solvent used is described in the following Table 1.

[Table 1] Table 1

[Table 2] Table 1 (continued)

[Table 3] Table 2

[Table 4] Table 2 (continued)

As can be seen from the results in Table 2, the pattern obtained by the pattern forming method of the present invention has excellent resolution and development defects are suppressed.

[Extreme Ultraviolet (EUV) Exposure] (4) Fabrication of photoresist patterns The above (3 ) was subjected to pattern exposure on the resist film-coated wafer obtained in . After the exposure, it was heated on a hot plate at 100° C. for 90 seconds, then immersed in a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with water for 30 seconds. Then, the wafer was rotated at 4000 rpm for 30 seconds, and then baked and dried at 95° C. for 60 seconds.

[evaluate] (5) Evaluation of resist pattern The obtained pattern was evaluated by the following method about resolution and image development defect. The results are shown in Table 3 below.

The irradiation energy when analyzing a 1:1 line-space pattern with a line width of 50 nm was defined as the sensitivity (Eop).

＜L/S resolution＞ The limit resolving power (minimum line width at which line and space (line: pitch = 1:1) are separated and analyzed) at the exposure level that shows the above sensitivity (Eop) is defined as the resolving power (nm).

＜Isolated space pattern (IS) resolution＞ Find the limit resolution (minimum space width for separate analysis of line and space) in an isolated space (line:spacing = 100:1) at the above sensitivity (Eop). And, let this value be "isolated space pattern resolving power (nm)". Indicates that the smaller the value, the better the performance.

<Defects in development> Using defect inspection device KLA2360 (product name) manufactured by KLA-Tencor Corporation, for a 1:1 line-and-space pattern with a line width of 50nm formed at the above sensitivity (Eop), set the pixel size of the defect inspection device to 0.16μm, and set the threshold to 20, detect the defects (number/cm ² ) extracted from the difference generated by comparing the superposition of the image and the pixel unit, and calculate the number of defects per unit area (number/cm ² ) . Then, the development defects were classified and extracted from all the defects by performing defect inspection, and the number of development defects per unit area (number/cm ² ) was calculated. A value of less than 0.5 was defined as A, a value of 0.5 or more and less than 1.0 was defined as B, a value of 1.0 or more and less than 5.0 was defined as C, and a value of 5.0 or greater was defined as D. Indicates that the smaller the value, the better the performance.

[Table 5] Table 3

[Table 6] Table 3 (continued)

As can be seen from the results in Table 3, the pattern obtained by the pattern forming method of the present invention has excellent resolution and development defects are suppressed. [Industrial availability]

According to the present invention, it is possible to provide an actinic radiation-sensitive or radiation-sensitive resin composition capable of achieving both high resolution improvement and development defect reduction. According to the present invention, it is possible to provide an actinic radiation-sensitive or radiation-sensitive film using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition, a method for forming a pattern, a photomask, a method for producing an electronic device, and a compound.

Although this invention was demonstrated in detail with reference to the specific embodiment, it is clear for those skilled in the art that various changes and modifications can be added without departing from the spirit and range of this invention. This application claims to be based on the Japanese patent application (Japanese Patent Application No. 2018-164085) filed on September 1, 2018 and the Japanese patent application (Japanese Patent Application No. 2018-248643) filed on December 28, 2018, and its contents are incorporated by reference enter here.

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Claims (23)

An actinic radiation-sensitive or radiation-sensitive resin composition, which contains the following (A), wherein (A) is a compound that generates an acid upon irradiation with actinic rays or radiation and is a compound represented by general formula (1) ,

In the general formula (1), R ₁ and R ₂ each independently represent a group represented by any one of the following general formula (R-1) ~ general formula (R-3), R ₃ ~ R ₅ are independently represents a hydrogen atom or a substituent, at least one of R ₃ to R ₅ represents a group represented by the following general formula (R-4), M ^m+ represents a cation, m represents an integer of 1 or more,

In general formula (R-1) ~ general formula (R-3), R ₆ ~ R ₂₇ independently represent a hydrogen atom or a substituent, in general formula (R-1), at least 2 of R ₆ ~ R ₁₃ may be bonded to each other to form a ring, in general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to each other to form a ring, in general formula (R-3), R ₁₉ to R ₂₇ At least two of them can be bonded to each other to form a ring, * represents the bond with the benzene ring in the general formula (1), *-A-(Y)n (R-4) the general formula (R-4) Among them, A represents an aromatic group with a valence of (n+1), and Y represents a group containing a polar group, a group containing a group whose polarity is increased by decomposition by the action of an acid, or a group containing a group that is decomposed by an alkaline developer. It is a group that decomposes and increases the solubility in alkali developing solution. n represents an integer of 1 or more. When n represents an integer of 2 or more, the plural Ys can be the same or different. * means the same as the general The bonding bond of the benzene ring in formula (1). The actinic radiation-sensitive or radiation-sensitive resin composition as described in claim 1, wherein the compound (A) is represented by the following general formula (2),

In general formula (2), R ₁ and R ₂ each independently represent a group represented by any one of the above-mentioned general formula (R-1) ~ general formula (R-3), R ₃ ~ R ₅ are independently Represents a hydrogen atom or a substituent, at least one of R ₃ ~R ₅ represents a group represented by the above general formula (R-4), R ₁₀₁ ~R ₁₀₃ independently represent a hydrogen atom or a substituent, R ₁₀₁ ~R Two of ₁₀₃ may be bonded to each other to form a ring. The actinic radiation-sensitive or radiation-sensitive resin composition as described in claim 2, wherein the compound represented by the above general formula (2) is represented by the following general formula (3),

In general formula (3), R ₁ and R ₂ each independently represent a group represented by any one of the above-mentioned general formula (R-1) ~ general formula (R-3), R ₃ and R ₅ are each independently Represents a hydrogen atom or a substituent, R ₁₀₁ ~ R ₁₀₃ independently represent a hydrogen atom or a substituent, two of R ₁₀₁ ~ R ₁₀₃ may be bonded to each other to form a ring, A represents an aromatic with a valence of (n+1) Y represents a group containing a polar group, a group containing a group whose polarity is increased by decomposition by the action of an acid, or a group containing a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer In the group of the group, n represents an integer of 1 or more, and when n represents an integer of 2 or more, a plurality of Ys may be the same or different. The actinic radiation-sensitive or radiation-sensitive resin composition as described in item 3 of the scope of the patent application, wherein in the general formula (R-1) in the general formula (3), at least one of R ₆ to R ₈ and at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ are bonded to form a ring, and in the general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to R ₁₇ and R At least one of ₁₈ is bonded to form a ring, and in the general formula (R-3), at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ bonds to form a ring. The actinic radiation-sensitive or radiation-sensitive resin composition as described in item 4 of the scope of the patent application, wherein in the general formula (R-1) in the general formula (3), at least one of R ₆ to R ₈ A ring formed by bonding with at least one of R ₉ and R ₁₀ or at least one of R ₁₁ to R ₁₃ , in the general formula (R-2), at least one of R ₁₄ to R ₁₆ and R ₁₇ and In the ring formed by bonding at least one of R ₁₈ , and in the general formula (R-3), at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or R ₂₅ to R ₂₇ In the ring formed by at least one bond, the number of carbon atoms constituting the ring members is 5-10. The actinic radiation-sensitive or radiation-sensitive resin composition described in any one of the claims 1 to 5, wherein the compound (A) is represented by the following general formula (4),

In the general formula (4), R ₃₁ ~ R ₄₀ each independently represent a hydrogen atom or a substituent, at least two of R ₃₁ ~ R ₄₀ may be bonded to each other to form a ring, and R ₄₁ ~ R ₅₀ each independently represent hydrogen Atoms or substituents, at least two of R ₄₁ ~ R ₅₀ may be bonded to each other to form a ring, R ₃ and R ₅ independently represent a hydrogen atom or a substituent, R ₁₀₁ ~ R ₁₀₃ independently represent a hydrogen atom or As a substituent, two of R ₁₀₁ to R ₁₀₃ may be bonded to each other to form a ring, A represents an aromatic group with a valence of (n+1), n represents an integer of 1 or more, Y represents a group including a polar group, including A group whose polarity is increased by decomposition by the action of an acid or a group containing a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer, when n represents 2 or more When the integers are integers, the plural Ys may be the same or different. The actinic radiation-sensitive or radiation-sensitive resin composition as described in claim 6, wherein the compound represented by the general formula (4) is represented by the following general formula (5),

In the general formula (5), R ₃ and R ₅ independently represent a hydrogen atom or a substituent, R ₁₀₁ ~ R ₁₀₃ independently represent a hydrogen atom or a substituent, and two of R ₁₀₁ ~ R ₁₀₃ may be bonded to each other To form a ring, A represents an aromatic group with a valence of (n+1), Y represents a group containing a polar group, a group containing a group whose polarity is increased by decomposition by the action of an acid, or a group containing a group developed by alkali The action of liquid decomposes and increases the solubility of the group in the alkali developing solution, n represents an integer of 1 or more, and when n represents an integer of 2 or more, the plural Ys may be the same or different. The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of the claims 1 to 5, wherein the compound (A) is represented by the following general formula (6),

In the general formula (6), R ₃ and R ₅ independently represent a hydrogen atom or a substituent, R ₁₀₁ ~ R ₁₀₃ independently represent a hydrogen atom or a substituent, and two of R ₁₀₁ ~ R ₁₀₃ may be bonded to each other To form a ring, R ₅₁ ~ R ₅₅ independently represent a hydrogen atom or a substituent, at least one of R ₅₁ ~ R ₅₅ represents a group represented by the following general formula (R-5), *-B-(Y )n (R-5) In the general formula (R-5), B represents a single bond or a (n+1) valence linking group, Y represents a group containing a polar group, including a polar group that is decomposed by the action of an acid A group having an enlarged group or a group including a group whose solubility in an alkali developing solution is increased by decomposition by the action of an alkali developing solution, n represents an integer of 1 or more, when n represents an integer of 2 or more , the plurality of Ys may be the same or different, and * represents a bond with the benzene ring in the general formula (6). Actinic radiation-sensitive or radiation-sensitive resin as described in item 8 of the patent application A composition, wherein in the general formula (6), B is a single bond or a methylene group. The actinic radiation-sensitive or radiation-sensitive resin composition described in any one of the claims 1 to 5, wherein Y in each of the general formulas represents a hydroxyl group, a carboxyl group, a group having a carbonyl bond, Acyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, aryloxycarbonyl, alkoxycarbonyl, carbamoyl or imido. The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of the claims 1 to 5, wherein Y in each formula represents a hydroxyl group, a carboxyl group or an alkoxycarbonyl group. The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of the first to fifth claims of the patent application, wherein the acid of the compound (A) is generated by irradiation with actinic rays or radiation pKa is -10 or more and 5 or less. The actinic radiation-sensitive or radiation-sensitive resin composition described in any one of items 1 to 5 of the scope of the patent application, which is used for manufacturing photomasks. An actinic radiation-sensitive or radiation-sensitive film, which is formed by using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of the claims 1 to 13. A pattern forming method, comprising: a resist film forming step of forming a resist film using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of claims 1 to 13 ; an exposing step of exposing the resist film; and a developing step of developing the exposed resist film using a developing solution. A photomask manufactured using the pattern forming method described in item 15 of the scope of the patent application. A method of manufacturing an electronic device, which includes the pattern forming method described in item 15 of the scope of the patent application. A compound represented by the following general formula (A),

In the general formula (A), R ₁ and R ₂ independently represent a group represented by any one of the following general formula (R-1) ~ general formula (R-3), R ₃ and R ₅ are independently ground represents a hydrogen atom or a substituent, A represents an aromatic group with a valence of (n+1), Y represents a group containing a polar group, a group containing a group whose polarity is increased by decomposition by the action of an acid, or a group containing A group whose solubility in an alkali developing solution is increased by decomposition by the action of an alkali developing solution, n represents an integer of 1 or more, and when n represents an integer of 2 or more, the plurality of Ys may be the same or may be Different, M ^m+ represents a cation, m represents an integer greater than 1,

In general formula (R-1) ~ general formula (R-3), R ₆ ~ R ₂₇ independently represent a hydrogen atom or a substituent, in general formula (R-1), at least 2 of R ₆ ~ R ₁₃ may be bonded to each other to form a ring, in general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to each other to form a ring, in general formula (R-3), R ₁₉ to R ₂₇ At least two of them can be bonded to each other to form a ring, * represents the bond with the benzene ring in the general formula (1), in the general formula (R-1) in the general formula (3), R ₆ At least one of ~R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ ~R ₁₃ to form a ring, in the general formula (R-2), in R ₁₄ ~R ₁₆ At least one bonded with at least one of R ₁₇ and R ₁₈ to form a ring, in the general formula (R-3), at least one of R ₁₉ ~ R ₂₁ and at least one of R ₂₂ ~ R ₂₄ or R ₂₅ At least one of ~R ₂₇ is bonded to form a ring, in the general formula (R-1) in the general formula (3), at least one of R ₆ ~R ₈ and at least one of R ₉ and R ₁₀ Or a ring formed by bonding at least one of R ₁₁ to R ₁₃ , in the general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form and in the general formula (R-3), at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ are bonded to form a ring , the number of carbon atoms constituting the ring members is 5~10 respectively. The compound as described in claim 18, wherein the compound is represented by the following general formula (3),

In general formula (3), R ₁ and R ₂ each independently represent a group represented by any one of the following general formula (R-1) ~ general formula (R-3), R ₃ and R ₅ are independently ground represents a hydrogen atom or a substituent, R ₁₀₁ ~ R ₁₀₃ independently represent a hydrogen atom or a substituent, two of R ₁₀₁ ~ R ₁₀₃ can be bonded to each other to form a ring, A represents (n+1) valent aromatic group, Y represents a group containing a polar group, a group containing a group whose polarity is increased by decomposition by the action of an acid, or a group containing a group whose solubility in an alkali developer is increased by decomposition by the action of an alkali developer. In the group of a large group, n represents an integer of 1 or more, and when n represents an integer of 2 or more, the plural Ys may be the same or different,

In general formula (R-1) ~ general formula (R-3), R ₆ ~ R ₂₇ independently represent a hydrogen atom or a substituent, in general formula (R-1), at least 2 of R ₆ ~ R ₁₃ may be bonded to each other to form a ring, in general formula (R-2), at least two of R ₁₄ to R ₁₈ may be bonded to each other to form a ring, in general formula (R-3), R ₁₉ to R ₂₇ At least two of them can be bonded to each other to form a ring, * represents the bond with the benzene ring in the general formula (1), in the general formula (R-1) in the general formula (3), R ₆ At least one of ~R ₈ is bonded to at least one of R ₉ and R ₁₀ or at least one of R ₁₁ ~R ₁₃ to form a ring, in the general formula (R-2), in R ₁₄ ~R ₁₆ At least one bonded with at least one of R ₁₇ and R ₁₈ to form a ring, in the general formula (R-3), at least one of R ₁₉ ~ R ₂₁ and at least one of R ₂₂ ~ R ₂₄ or R ₂₅ At least one of ~R ₂₇ is bonded to form a ring, in the general formula (R-1) in the general formula (3), at least one of R ₆ ~R ₈ and at least one of R ₉ and R ₁₀ Or a ring formed by bonding at least one of R ₁₁ to R ₁₃ , in the general formula (R-2), at least one of R ₁₄ to R ₁₆ is bonded to at least one of R ₁₇ and R ₁₈ to form and in the general formula (R-3), at least one of R ₁₉ to R ₂₁ and at least one of R ₂₂ to R ₂₄ or at least one of R ₂₅ to R ₂₇ are bonded to form a ring , the number of carbon atoms constituting the ring members is 5~10 respectively. The compound as described in claim 18 or claim 19, wherein the compound is represented by the following general formula (9),

In the general formula (9), R ₃ and R ₅ each independently represent a hydrogen atom or a substituent, R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom or a substituent, and two of R ₁₀₁ to R ₁₀₃ may be bonded to each other To form a ring, A represents an aromatic group with a valence of (n+1), n represents an integer greater than 1, and Y represents a group containing a polar group or a group containing a group whose polarity is increased by decomposition by the action of an acid A group or a group containing a group whose solubility in an alkali developer is decomposed by the action of an alkali developer, when n represents an integer of 2 or more, a plurality of Y may be the same or different. The compound as described in item 18 or item 19 of the patent claims, wherein the compound is represented by the following general formula (10),

In the general formula (10), R ₃ and R ₅ independently represent a hydrogen atom or a substituent, R ₁₀₁ ~ R ₁₀₃ independently represent a hydrogen atom or a substituent, and two of R ₁₀₁ ~ R ₁₀₃ may be bonded to each other To form a ring, R ₅₁ ~ R ₅₅ independently represent a hydrogen atom or a substituent, and at least one of R ₅₁ ~ R ₅₅ represents a group represented by the following general formula (R-5), *-B-(Y )n (R-5) In the general formula (R-5), B represents a single bond or a (n+1) valent linking group, n represents an integer greater than 1, and Y represents a group including a polar group, including a group by A group whose polarity is increased by decomposition by the action of an acid or a group containing a group whose solubility in an alkali developer is decomposed by the action of an alkali developer, when n represents an integer of 2 or more , the plurality of Ys may be the same or different, and * represents a bond with the benzene ring in the general formula (10). The compound described in item 18 or item 19 of the scope of the patent application, wherein Y in each of the general formulas represents hydroxyl, carboxyl, a group with a carbonyl bond, acyloxy, alkoxycarbonyloxy, aryloxy Carbonyloxy, aryloxycarbonyl, alkoxycarbonyl, carbamoyl or imido. The compound as described in item 18 or item 19 of the scope of the patent application, wherein Y in each general formula represents a hydroxyl group, a carboxyl group or an alkoxycarbonyl group.