TW201638674A - Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, method for producing electronic device using these, and electronic device - Google Patents

Abstract

Provided is a pattern forming method comprising a step in which a film is formed using an actinic ray-sensitive or radiation-sensitive resin composition, a step in which the film is exposed, and a step in which the film is developed using a developer after exposure, and a positive pattern is formed. The actinic ray-sensitive or radiation-sensitive resin composition contains a resin (P1) comprising at least a repeating unit (a) represented by general formula (1) as a repeating unit having a group that produces a polar group as a result of being decomposed by the action of an acid.

Description

Pattern forming method, sensitizing ray or radiation sensitive resin composition, sensitizing ray or radiation sensitive film, method of manufacturing electronic component using the same, and electronic component

The present invention relates to a microlithography process or other photofabrication process which can be preferably used in the manufacture of ultra-large scale integrated circuits (LSIs) and high-capacity microchips. A pattern forming method using a developing solution, a sensitizing ray-sensitive or radiation-sensitive resin composition, a sensitizing ray-sensitive or radiation-sensitive film, a method of manufacturing an electronic device using the same, and an electronic component. More specifically, the present invention relates to an alkaline development which is preferably used for microfabrication of a semiconductor element using electron z-ray or extreme ultraviolet (EUV) light (wavelength: around 13 nm). A pattern forming method of a liquid, a sensitizing ray-sensitive or radiation-sensitive resin composition, a resist film, a method of producing an electronic component using the same, and an electronic component.

Conventionally, in a manufacturing process of a semiconductor element such as an integrated circuit (IC) or an LSI, microfabrication has been performed by using a lithography of a photoresist composition. In recent years, with the high integration of integrated circuits, it has been demanded to form ultra-fine patterns of sub-micron regions or quarter-micron regions. Along with this, the exposure wavelength also tends to be shorter than the wavelength of the g-ray to the i-ray and further to the KrF excimer laser light. Further, in addition to excimer laser light, lithography using electron beams or X-rays or EUV light is currently being developed.

These electron beams, X-rays, or EUV light lithography are positioned as next-generation or next-generation pattern forming technologies, and high-sensitivity and high-resolution resist compositions are expected.

In particular, in order to shorten the wafer processing time, high sensitivity is a very important problem. However, if high sensitivity is desired, the pattern shape is deteriorated, or the resolution of the limit analysis line width is lowered, and development is strongly expected to be satisfied. These characteristics of the resist composition.

Further, as the pattern is refined, the pattern collapses more easily, and from the viewpoint of preventing such a pattern from collapsing, the resist film is required to be thinned. However, in pursuit of miniaturization, there is a dilemma that as the thin film of the resist film is formed, the etching resistance of the resist film is more lost, and the function as a resist film is not exhibited.

As described above, the refinement of the resist pattern and the etching resistance are a trade-off relationship, and it is important to satisfy the characteristics at the same time.

Further, as a result of pursuing the miniaturization of the pattern, there is a problem in that the difference (optical contrast) between the exposure amount of the exposed region and the unexposed region is lowered, the difference in the dissolution rate of the developer is small, and the dissolution contrast is deteriorated.

For a photosensitive ray-sensitive or radiation-sensitive resin composition, there are usually "positive" and "negative", which are resins which are poorly soluble or insoluble in an alkaline developing solution. The exposure of the radiation causes the exposed portion to be solubilized to the alkaline developing solution, thereby forming a pattern; the "negative type" is a resin which is soluble in the alkaline developing solution, and the exposed portion is made alkaline by exposure to radiation. The liquid is hardly melted or insolubilized, thereby forming a pattern. In the process of developing various lithography techniques, for example, various positive resist compositions using a resin having an acetal type protecting group have been developed, and according to the positive resist compositions, resolution, sensitivity, and the like are analyzed. Improvement is possible (for example, refer to Patent Document 1 to Patent Document 6).

However, with regard to the conventional chemically amplified positive resist composition, it is actually difficult to obtain a pattern which satisfies the following characteristics: when a pattern having a line width or a gap width of ultrafine (for example, tens of nm) is formed. Required resolution, dissolution contrast, and dry etch resistance. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2013-129823 [Patent Document 6] Japanese Patent Laid-Open No. Hei 2-25850

[Problems to be Solved by the Invention] An object of the present invention is to solve the problem of performance improvement techniques in microfabrication of semiconductor elements using electron beams or extreme ultraviolet rays (EUV light), and in particular to provide an ultrafine (for example, tens of In the formation of a pattern having a line width or a gap width of nm level), a pattern forming method, a sensitizing ray-sensitive or a radiation-sensitive resin composition satisfying high sensitivity, high resolution, high dissolution contrast, and high dry etching resistance A sensitizing ray-sensitive or radiation-sensitive film, a method for producing an electronic device using the same, and an electronic device. [Means for solving the problem]

The present invention is as follows in one aspect. [1] A pattern forming method comprising: a step of forming a film using a photosensitive ray-sensitive or radiation-sensitive resin composition containing a resin (P1) containing at least the following formula (1); a repeating unit (a) represented as a repeating unit having a group decomposed by an action of an acid and generating a polar group; a step of exposing the film; and developing the exposed film using a developing solution, The step of forming a positive pattern.

[Chemical 1]

In the formula (1), Y ₁ and Y ₂ each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form an aromatic ring. Y ₃ represents a single bond or a divalent aromatic ring group. Y ₃ may also be bonded to Y ₁ to form a ring, and in this case, Y ₃ represents a trivalent aromatic ring group. L ₁ represents a single bond or a divalent linking group. L ₁ may also bond with Y ₁ to form a ring, and in this case, L ₁ represents a trivalent linking group. R ₁ and R ₂ each independently represent a hydrogen atom or a substituent. M ₁ represents an organic group. One of R ₁ and R ₂ and M ₁ may be bonded to each other to form a ring together with an oxygen atom in the formula.

Here, at least one of Y ₁ , Y ₂ and Y ₃ contains an aromatic ring, or Y ₁ and Y ₂ are bonded to each other to form an aromatic ring. When Y ₃ is an aromatic ring group and L ₁ is a single bond, at least one of R ₁ and R ₂ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, an aromatic ring group, a heterocyclic group or a halogen atom. . When Y ₃ is an aromatic ring group and L ₁ is a divalent linking group, L ₁ does not contain an aliphatic ring group, and one of R ₁ and R ₂ and M ₁ are not bonded to each other to form a ring.

[2] The pattern forming method according to [1], wherein the repeating unit (a) represented by the formula (1) is a repeating unit represented by the following formula (2).

[Chemical 2]

In the general formula (2), Y ₄ and Y ₅ each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form an aromatic ring. L ₁₁ represents a single bond or a divalent linking group. L ₁₁ may also be bonded to Y ₄ to form a ring, and in this case, L ₁₁ represents a trivalent linking group. R ₃ and R ₄ each independently represent a hydrogen atom or a substituent.

M ₂ represents an organic group. One of R ₃ and R ₄ and M ₂ may be bonded to each other to form a ring together with an oxygen atom in the formula. Here, at least one of Y ₄ and Y ₅ contains an aromatic ring, or Y ₄ and Y ₅ are bonded to each other to form an aromatic ring.

[3] The pattern forming method according to [2], wherein R ₃ in the formula (2) represents a hydrogen atom, and R ₄ represents a hydrogen atom, an alkyl group, an aliphatic cyclic group or an aromatic ring group.

[4] The pattern forming method according to [2] or [3], wherein M ₂ in the formula (2) is an alkyl group.

[5] The pattern forming method according to [1], wherein the repeating unit (a) represented by the formula (1) is a repeating unit represented by the following formula (3).

[Chemical 3]

In the formula (3), Y ₆ and Y ₇ each independently represent a hydrogen atom or a monovalent organic group. L ₂ represents a divalent linking group having an atomic number of 1 between the aromatic ring and the carboxyl group sandwiched in the formula. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aliphatic cyclic group, a halogen atom, an aromatic ring group, or a heterocyclic group. M ₃ represents an organic group. One of R ₅ and R ₆ and M ₃ are not bonded to each other to form a ring. n represents an integer of 0 or more.

[6] The pattern forming method according to [5], wherein at least one of R ₅ and R ₆ in the formula (3) is an alkyl group having 7 or more carbon atoms, an aliphatic cyclic group, a halogen atom, and carbon. An aromatic ring group of 13 or more or a heterocyclic group.

[7] The pattern forming method according to [5] or [6], wherein M ₃ in the formula (3) represents an alkyl group having 7 or more carbon atoms, an aliphatic cyclic group, a halogen atom, and a carbon number of 13 or more. An aromatic ring group or a heterocyclic group.

[8] The pattern forming method according to [1], wherein the repeating unit (a) represented by the formula (1) is a repeating unit represented by the following formula (4).

[Chemical 4]

In the formula (4), Y ₈ and Y ₉ each independently represent a hydrogen atom or a monovalent organic group. R ₇ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, an aromatic ring group, a heterocyclic group or a halogen atom. R ₈ represents a hydrogen atom or a substituent. M ₄ represents an organic group. One of R ₇ and R ₈ and M ₄ may be bonded to each other to form a ring together with an oxygen atom in the formula. n represents an integer of 0 or more.

[9] The pattern forming method according to [8], wherein R ₇ in the formula (4) represents an aliphatic cyclic group.

[10] The pattern forming method according to any one of [1] to [9] wherein the resin (P1) further contains a repeating unit represented by the formula (A).

[Chemical 5]

In the formula (A), Z ₁ , Z ₂ and Z ₃ each independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein Z ₃ may also be bonded to Ar ₂ or X ₁ to form a ring, and in this case, Z ₃ represents a single bond or an alkylene group. X ₁ represents a single bond, an alkylene group, -COO-, or -CONR ₉ -. Here, R ₉ represents a hydrogen atom or an alkyl group. L ₃ represents a single bond, -COO-, or an alkylene group. Ar ₂ represents an (m+1)-valent aromatic ring group, and when it is bonded to Z ₃ to form a ring, it represents an (m+2)-valent aromatic ring group. m represents an integer of 1 to 4.

[11] A photosensitive ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method, comprising: a step of forming a film using a sensitizing ray-sensitive or radiation-sensitive resin composition; a step of exposing the film; and a step of developing the exposed film using a developing solution to form a positive pattern, and the photosensitive ray-sensitive or radiation-sensitive resin composition contains a resin (P1) The resin (P1) contains at least a repeating unit (a) represented by the following formula (1) as a repeating unit having a group which decomposes by an action of an acid and generates a polar group.

[Chemical 6]

In the formula (1), Y ₁ and Y ₂ each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form an aromatic ring. Y ₃ represents a single bond or a divalent aromatic ring group. Y ₃ may also be bonded to Y ₁ to form a ring, and in this case, Y ₃ represents a trivalent aromatic ring group. L ₁ represents a single bond or a divalent linking group. L ₁ may also bond with Y ₁ to form a ring, and in this case, L ₁ represents a trivalent linking group. R ₁ and R ₂ each independently represent a hydrogen atom or a substituent. M ₁ represents an organic group. One of R ₁ and R ₂ and M ₁ may be bonded to each other to form a ring together with an oxygen atom in the formula.

Here, at least one of Y ₁ , Y ₂ and Y ₃ contains an aromatic ring, or Y ₁ and Y ₂ are bonded to each other to form an aromatic ring. When Y ₃ is an aromatic ring group and L ₁ is a single bond, at least one of R ₁ and R ₂ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, an aromatic ring group, a heterocyclic group or a halogen atom. . When Y ₃ is an aromatic ring group and L ₁ is a divalent linking group, L ₁ does not contain an aliphatic ring group, and one of R ₁ and R ₂ and M ₁ are not bonded to each other to form a ring.

[12] The photosensitive ray-sensitive or radiation-sensitive resin composition according to [11], wherein the repeating unit (a) represented by the above formula (1) is a repeat represented by the following formula (2) unit.

[Chemistry 7]

In the general formula (2), Y ₄ and Y ₅ each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form an aromatic ring. L ₁₁ represents a single bond or a divalent linking group. L ₁₁ may also be bonded to Y ₄ to form a ring, and in this case, L ₁₁ represents a trivalent linking group. R ₃ and R ₄ each independently represent a hydrogen atom or a substituent. M ₂ represents an organic group. One of R ₃ and R ₄ and M ₂ may be bonded to each other to form a ring together with an oxygen atom in the formula. Here, at least one of Y ₄ and Y ₅ contains an aromatic ring, or Y ₄ and Y ₅ are bonded to each other to form an aromatic ring.

[13] The photosensitive ray-sensitive or radiation-sensitive resin composition according to [11], wherein the repeating unit (a) represented by the formula (1) is a repeat represented by the following formula (3) unit.

[化8]

In the formula (3), Y ₆ and Y ₇ each independently represent a hydrogen atom or a monovalent organic group. L ₂ represents a divalent linking group having an atomic number of 1 between the aromatic ring and the carboxyl group sandwiched in the formula. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aliphatic cyclic group, a halogen atom, an aromatic ring group, or a heterocyclic group. M ₃ represents an organic group. One of R ₅ and R ₆ and M ₃ are not bonded to each other to form a ring. n represents an integer of 0 or more.

[14] The photosensitive ray-sensitive or radiation-sensitive resin composition according to [11], wherein the repeating unit (a) represented by the above formula (1) is a repeat represented by the following formula (4) unit.

[Chemistry 9]

In the formula (4), Y ₈ and Y ₉ each independently represent a hydrogen atom or a monovalent organic group. R ₇ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, an aromatic ring group, a heterocyclic group or a halogen atom. R ₈ represents a hydrogen atom or a substituent. M ₄ represents an organic group. One of R ₇ and R ₈ and M ₄ may be bonded to each other to form a ring together with an oxygen atom in the formula. n represents an integer of 0 or more.

[15] A photosensitive ray-sensitive or radiation-sensitive linear film formed by using the sensitized ray-sensitive or radiation-sensitive composition according to any one of [11] to [14]. [16] A method of producing an electronic component, comprising the pattern forming method according to any one of [1] to [10]. [17] An electronic component produced by the method of producing an electronic component according to [16]. [Effects of the Invention]

According to the present invention, it is possible to provide a pattern forming method and a sensitization which simultaneously satisfy high resolution, high dissolution contrast, and high dry etching resistance in an ultrafine region (for example, a region having a line width or a gap width of several tens of nm). A radiation-sensitive or radiation-sensitive resin composition, a sensitizing ray-sensitive or radiation-sensitive film, a method for producing an electronic device using the same, and an electronic device.

Hereinafter, embodiments of the present invention will be described in detail. Further, in the expression of the group (atomic group) in the present specification, it is not explicitly stated that the substituted or unsubstituted expression includes both a substituent having no substituent and a substituent having a substituent. For example, it is not expressly stated that the substituted or unsubstituted "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The term "actinic ray" or "radiation" as used in the present specification means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet (EUV) line, an X-ray or an electron beam (Electron Beam, EB). Further, in the present invention, "light" means actinic rays or radiation.

In addition, the term "exposure" in the present invention includes not only exposure by far ultraviolet rays, X-rays, and EUV light represented by a mercury lamp or an excimer laser, but also an electron beam and an ion beam, unless otherwise specified. (ion beam) and other particle beam painting.

The pattern forming method of the present invention comprises: a step of forming a film using a photosensitive ray-sensitive or radiation-sensitive resin composition; a step of exposing the film; and developing the exposed film using a developing solution, and The step of forming a positive pattern.

In the following, first, a photosensitive ray-sensitive or radiation-sensitive resin composition (hereinafter referred to as "the composition of the present invention") used in the pattern forming method of the present invention will be described, and then each of the pattern forming methods of the present invention will be described. The steps are explained.

<Photosensitive ray-sensitive or radiation-sensitive resin composition> The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention can be used for positive development (development in which the exposed portion is removed and the unexposed portion remains as a pattern). In other words, the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention can be used as a sensitizing ray-sensitive or radiation-sensitive resin composition for alkaline development used for development using an alkaline developer. Here, the term "alkaline development" means a use of at least a step of performing development using an alkaline developer.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, and particularly a positive resist composition (i.e., a resist composition for alkaline development) can be obtained high. The effect is better. Further, the composition of the present invention is typically a chemically amplified resist composition.

[1] Resin (P1) The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (P1) containing an acid-decomposable repeating unit. Thereby, the resin (P1) becomes a resin which increases the solubility of an alkaline developing solution by the action of an acid. Here, the acid-decomposable repeating unit is, for example, a group which is decomposed by the action of an acid in the main chain or the side chain of the resin or both the main chain and the side chain (hereinafter also referred to as "acid decomposition". Repeating unit of "sex base"). In the case where the group generated by the decomposition is a polar group, it is preferred because it has a high affinity with a developing solution containing an alkaline solution and is easily melted (normalized).

The resin (P1) contains at least a repeating unit represented by the following formula (1) (hereinafter also referred to as "repeating unit (a)") as a repeating unit having a group which decomposes by an action of an acid and generates a polar group. .

[化10]

In the formula (1), Y ₁ and Y ₂ each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form an aromatic ring.

Y ₃ represents a single bond or a divalent aromatic ring group. Y ₃ may also be bonded to Y ₁ to form a ring, and in this case, Y ₃ represents a trivalent aromatic ring group.

L ₁ represents a single bond or a divalent linking group. L ₁ may also bond with Y ₁ to form a ring, and in this case, L ₁ represents a trivalent linking group.

R ₁ and R ₂ each independently represent a hydrogen atom or a substituent.

M ₁ represents an organic group.

One of R ₁ and R ₂ and M ₁ may be bonded to each other to form a ring together with an oxygen atom in the formula.

Wherein at least one of Y ₁ , Y ₂ and Y ₃ contains an aromatic ring, or at least Y ₁ and Y ₂ are bonded to each other to form an aromatic ring.

When Y ₃ is an aromatic ring group and L ₁ is a single bond, at least one of R ₁ and R ₂ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, an aromatic ring group, a heterocyclic group or a halogen atom. .

When Y ₃ is an aromatic ring group and L ₁ is a divalent linking group, L ₁ does not contain an aliphatic ring group, and one of R ₁ and R ₂ and M ₁ are not bonded to each other to form a ring.

In the above formula (1), the organic group represented by Y ₁ may, for example, be an alkyl group, an aliphatic cyclic group, an aromatic ring group or a heterocyclic group. The alkyl group of Y ₁ is preferably an alkyl group having 1 to 5 carbon atoms.

The aliphatic cyclic group of Y ₁ may be a monocyclic type or a polycyclic type, and is preferably an aliphatic cyclic group having 3 to 15 carbon atoms. Specific examples of the aliphatic cyclic group of Y ₁ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group, a cyclodecyl group, and a 1-golden ring. Alkyl, 2-adamantyl, 1-norbornyl, and 2-norbornyl.

The aromatic ring group of Y ₁ may, for example, be a group having a carbon number of 6 to 18 (more preferably 6 to 10 carbon atoms) such as a benzene ring or a naphthalene ring, or a thiophene ring or a furan ring. a heterocyclic aromatic ring group such as a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring or a thiazole ring, More preferably, it is a benzene ring or a naphthalene ring, and particularly preferably a benzene ring group.

The heterocyclic group of Y ₁ is preferably a heterocyclic group having 6 to 20 carbon atoms. Specific examples of the heterocyclic group of Y ₁ include pyridyl, pyrazinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl, piperidinyl, piperazinyl, furyl, pyranyl, and benzene. And dihydropyranyl (chromanyl) and the like.

The alkyl group, the aliphatic cyclic group, the aromatic ring group, the aralkyl group and the heterocyclic group of Y ₁ may further have a substituent.

Examples of the substituent which the alkyl group of Y ₁ may have include an aliphatic ring group, an aryl group, an amine group, a decylamino group, a guanidino group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, and the like. Alkoxy, aralkyloxy, thioether, decyl, decyloxy, alkoxycarbonyl, cyano and nitro groups. The substituents may be bonded to each other to form a ring, and the ring when the substituents are bonded to each other to form a ring may be an aliphatic cyclic group or a phenyl group.

The substituent which may be further contained as the aliphatic cyclic group of Y ₁ may be an alkyl group and each group described above as a specific example of a substituent which the alkyl group may further have.

Examples of the substituent which the aromatic ring group, the aralkyl group and the heterocyclic group of Y ₁ may further include, for example, a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkyl group or an alkoxy group. An aliphatic cyclic group, an aryl group, an alkoxycarbonyl group, a decyl group, an alkoxycarbonyloxy group or the like.

In the above formula (1), the monovalent organic group represented by Y ₂ may, for example, be an alkyl group, an aliphatic cyclic group, an aromatic ring group or a heterocyclic group.

The alkyl group of Y ₂ is preferably an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group of Y ₂ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, and a third butyl group.

Specific examples and preferred examples of the aliphatic cyclic group, the aromatic ring group or the heterocyclic group of Y ₂ are, for example, those described as the aliphatic cyclic group, the aromatic ring group or the heterocyclic group as Y ₁ . The specific examples and the preferred examples are the same.

Y as alkyl, cyclic aliphatic group, aromatic group and heterocyclic group may further have a substituent in the ₂ groups, the same as Y ₂ may further have a substituent group the alkyl group Y ₁ may have a substituent group.

In the general formula (1), specific examples of the aromatic ring group of Y ₃ include the same specific examples as those described for the aromatic ring group of Y ₁ and Y ₂ , and preferred specific examples are also preferred. the same.

Formula (1), Y _1, Y ₂ and Y ₃ is at least one group containing an aromatic ring, or Y ₁ and Y ₂ bonded to each other to form an aromatic ring. The at least one aromatic ring of the repeating unit (a) represented by the formula (1) is more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

In the general formula (1), the divalent linking group represented by L ₁ may, for example, be an alkyl group, an aromatic ring group, a cycloalkyl group, -COO-L ₁ '-, -OL ₁ '-, -CONH-, A group or the like formed by combining two or more of these. Here, L ₁ ' represents an alkyl group, a cycloalkyl group, an aromatic ring group, a group in which an alkyl group and an aromatic ring group are combined.

The alkylene group as the divalent linking group represented by L ₁ is preferably a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group or a octyl group. base.

The cycloalkyl group of the divalent linking group represented by L ₁ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentylene group, and a stretching group. Cyclohexyl, cycloheptyl, cyclooctyl, borneol or an adamantyl.

Examples of the aromatic ring group of the divalent linking group represented by L ₁ include the following groups: an aromatic ring group having 6 to 18 carbon atoms such as a benzene ring group or a naphthalene ring group, or a thiophene ring or a furan ring. a heterocyclic aromatic ring group such as a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring or a thiazole ring.

The definition and preferred range of the alkylene group, the extended cycloalkyl group and the aromatic ring group represented by L ₁ ' are the same as those of the alkylene group, the extended cycloalkyl group and the aromatic ring group which are the divalent linking groups represented by L.

The definition and preferred range of the alkylene group and the aromatic ring group in the group in which the alkyl group and the aromatic ring group are combined, represented by L ₁ ', and the alkylene group as the divalent linking group represented by Y ₃ And the aromatic ring group is the same.

When Y ₃ is bonded to Y ₁ to form a ring, Y ₃ represents a trivalent aromatic ring group, and preferably, three arbitrary hydrogens are removed from the specific example of the aromatic ring group represented by Y ₁ . A group of atoms.

When the L ₁ and Y _{1 are} bonded to each other to form a ring, the trivalent linking group represented by L ₁ may preferably be _{one in} which a hydrogen atom is removed from the specific example of the divalent linking group represented by L ₁ . a group.

In the formula (1), the substituent represented by R ₁ and R ₂ is preferably a hydrogen atom, an alkyl group, an aliphatic cyclic group, an aryl group, an arylalkyl group or a heterocyclic group.

In the embodiment of the present invention, the alkyl group of R ₁ and R ₂ is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 6 carbon atoms. . Specific examples of the alkyl group of R ₁ and R ₂ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a third butyl group, a neopentyl group, a hexyl group, and a 2- The alkyl group of R ₁ and R ₂ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group or a tert-butyl group, such as ethylhexyl, octyl or dodecyl.

The aliphatic cyclic group of R ₁ and R ₂ may be a monocyclic type or a polycyclic type. In one embodiment of the present invention, the aliphatic cyclic group of R ₁ and R ₂ is preferably an aliphatic cyclic group having 3 to 15 carbon atoms, more preferably an aliphatic cyclic group having 3 to 10 carbon atoms, and further It is preferably an aliphatic cyclic group having 3 to 6 carbon atoms. Specific examples of the aliphatic cyclic group of R ₁ and R ₂ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group, and a cyclodecyl group. 1-adamantyl, 2-adamantyl, 1-norbornyl and 2-norbornyl. The aliphatic cyclic group of R ₁ and R ₂ is preferably a cyclopropyl group, a cyclopentyl group or a cyclohexyl group.

The aryl group of R ₁ and R ₂ is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and a structure in which a plurality of aromatic rings are bonded to each other via a single bond (for example, a biphenyl group) , terphenyl). Specific examples of the aryl group of R ₁ and R ₂ include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, and a terphenyl group. The aryl group of R111 to R113 is preferably a phenyl group, a naphthyl group or a biphenyl group.

The aralkyl group of R ₁ and R ₂ is preferably an aralkyl group having 6 to 20 carbon atoms, more preferably an aralkyl group having 7 to 12 carbon atoms. Specific examples of the aralkyl group of R ₁ and R ₂ include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

The heterocyclic group of R ₁ and R ₂ is preferably a heterocyclic group having 6 to 20 carbon atoms, more preferably a heterocyclic group having 6 to 12 carbon atoms. Specific examples of the heterocyclic group of R ₁ and R ₂ include a pyridyl group, a pyrazinyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a tetrahydrothiophenyl group, a piperidinyl group, a piperazinyl group, a furyl group, and a pyran group. Base, benzohydropyranyl and the like.

The alkyl group, the aliphatic cyclic group, the aryl group, the arylalkyl group and the heterocyclic group of R ₁ and R ₂ may further have a substituent.

Examples of the substituent which the alkyl group of R ₁ and R ₂ may have include an aliphatic ring group, an aryl group, an amine group, a decylamino group, a guanidino group, a urethane group, a hydroxyl group, a carboxyl group, and the like. A halogen atom, an alkoxy group, an aralkyloxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group or the like. The substituents may be bonded to each other to form a ring, and the ring when the substituents are bonded to each other to form a ring may, for example, be an aliphatic cyclic group having 3 to 10 carbon atoms or a phenyl group.

The substituent which may further have an aliphatic cyclic group of R ₁ and R ₂ may, for example, be an alkyl group and each group described above as a specific example of a substituent which the alkyl group may further have.

Further, the carbon number of the alkyl group and the carbon number of the substituent which the aliphatic ring group may have are preferably from 1 to 8, respectively.

Examples of the substituent which the aryl group, the aralkyl group and the heterocyclic group of R ₁ and R ₂ may further include, for example, a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group or an alkyl group. Preferably, the carbon number is 1 to 15), the alkoxy group (preferably having 1 to 15 carbon atoms), the aliphatic cyclic group (preferably having 3 to 15 carbon atoms), and the aryl group (preferably having 6 to 14 carbon atoms). And an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), a mercapto group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms).

In one aspect of the invention, when Y ₃ in the formula (1) is an aromatic ring group and L ₁ is a single bond, at least one of R ₁ and R ₂ represents an alkyl group having 6 or more carbon atoms and a fat. A cyclic group, an aromatic ring group, a heterocyclic group or a halogen atom.

The groups other than the halogen atom may have more substituents, and the more substituents may be, for example, an alkyl group, an aliphatic cyclic group, an aryl group, an amine group, a decylamino group, a guanyl urea group, an amine group. The formate group, the hydroxyl group, the carboxyl group, the halogen atom, the alkoxy group, the aralkyloxy group, the thioether group, the decyl group, the decyloxy group, the alkoxycarbonyl group, the cyano group and the nitro group are appropriately selected.

When at least one of R ₁ and R ₂ is an alkyl group having 6 or more carbon atoms, an alkyl group having 6 to 15 carbon atoms is preferred, and an alkyl group having 6 to 10 carbon atoms is more preferred.

Moreover, in one aspect of the invention, any of R ₁ and R ₂ is preferably an aliphatic cyclic group, for example.

In the formula (1), the organic group represented by M ₁ is preferably a group represented by *-MQ. * represents a bond bond to an oxygen atom of the formula (1). M represents a single bond or a divalent linking group. Q represents an alkyl group, an aliphatic cyclic group, an aryl group or a heterocyclic group.

The divalent linking group as M is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethyl group, a propyl group, a butyl group, a hexyl group or a decyl group). a cycloalkyl group (preferably a cycloalkyl group having a carbon number of 3 to 15, such as a cyclopentyl group or a cyclohexyl group), -S-, -O-, -CO-, -CS-, -SO ₂ -, -N(R ₀ )- or a combination of two or more of these, preferably a group having a total carbon number of 20 or less. Here, R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, a hexyl group, an octyl group, etc.) .

M is preferably a single bond, an alkylene group or a divalent linking group comprising a combination of an alkyl group and at least one of -O-, -CO-, -CS- and -N(R ₀ )-, more preferably a single A bond, an alkyl group or a divalent linking group comprising a combination of an alkyl group and -O-. Here, R ₀ has the same meaning as the R ₀ .

M may further have a substituent, and examples of the substituent which M may have include an aliphatic ring group, an aryl group, an amine group, a guanylamino group, a guanidino group, a urethane group, a hydroxyl group, a carboxyl group, and the like. A halogen atom, an alkoxy group, an aralkyloxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group or the like. The substituents may be bonded to each other to form a ring, and the ring when the substituents are bonded to each other to form a ring may, for example, be an aliphatic cyclic group having 3 to 10 carbon atoms or a phenyl group.

Specific examples and preferred examples of the alkyl group of Q are, for example, an alkyl group having 1 to 15 carbon atoms. Specific examples of the alkyl group of Q include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a third butyl group, a neopentyl group, a hexyl group, and a 2-ethylhexyl group. Octyl and dodecyl groups.

The aliphatic cyclic group as Q may be a monocyclic type or a polycyclic type. Examples of the aliphatic cyclic group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-adamantyl, 2-adamantyl, 1-norbornyl. , 2-norbornyl, borneol, isobornyl, 4-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodecyl, 8-tricyclo[5.2.1.0 ^2,6 ]decyl , 2-bicyclo[2.2.1] heptyl. Among them, a cyclopentyl group, a cyclohexyl group, a 2-adamantyl group, an 8-tricyclo[5.2.1.0 ^2,6 ]fluorenyl group, and a 2-bicyclo[2.2.1]heptyl group are exemplified.

Specific examples and preferred examples of the aryl group of Q are, for example, preferably an aryl group having 6 to 15 carbon atoms, and a structure in which a plurality of aromatic rings are linked to each other via a single bond (for example, a biphenyl group or a terphenyl group). Specific examples of the aryl group of Q include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, and a terphenyl group. The aryl group of Q is preferably a phenyl group, a naphthyl group or a biphenyl group.

Specific examples and preferred examples of the heterocyclic group of Q are, for example, a heterocyclic group having 6 to 20 carbon atoms. Specific examples of the heterocyclic group of Q include pyridyl, pyrazinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl, piperidinyl, piperazinyl, furyl, pyranyl, and benzo. Dihydropyranyl and the like.

The alkyl group, the aliphatic cyclic group, the aryl group and the heterocyclic group of Q may have a substituent, and examples thereof include an alkyl group, an aliphatic cyclic group, a cyano group, a halogen atom, a hydroxyl group, an alkoxy group, and a carboxyl group. Alkoxycarbonyl.

In one aspect of the invention, M _{1 is} preferably an alkyl group, an alkyl group substituted with an aliphatic cyclic group, an aliphatic cyclic group, an aralkyl group, an aryloxyalkyl group or a heterocyclic group, more preferably An alkyl or aliphatic cyclic group. As the alkyl group R ₂ as R "aliphatic cyclic group" and ₂ of "aliphatic cyclic group via a substituted alkyl group" in the aliphatic cyclic group, and "a group represented by M ₁ Specific examples and preferred examples of the aryl group in the aralkyl group (arylalkyl group) and the "aryloxyalkyl group" are the same as those described for the alkyl group, the aliphatic ring group, and the aryl group as Q, respectively. .

Specific examples and preferred examples of the alkyl moiety in the "aliphatic cyclic group-substituted alkyl group", "aralkyl group (arylalkyl group)" and "aryloxyalkyl group" of M ₁ and The same is true for the alkylene group of M.

Specific examples and preferred examples of the heterocyclic group of M ₁ are the same as those described for the heterocyclic group of Q.

Specific examples of the organic group represented by M ₁ include a methyl group, an ethyl group, an isopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylethyl group, a 2-adamantyl group, and an 8-tricyclo ring [5.2. 1.0 ^2,6 ] mercapto, 2-bicyclo[2.2.1]heptyl, benzyl, 2-phenylethyl, 2-phenoxyethyl and the like.

When Y ₃ in the formula (1) is an aromatic ring group and L ₁ is a single bond, the organic group represented by M ₁ may be a group having no ring structure based on one form.

One of R ₁ and R ₂ and M ₁ may be bonded to each other to form a ring together with an oxygen atom in the formula. The oxygen-containing heterocyclic ring structure formed in this case may be a monocyclic, polycyclic or spiro ring, preferably a monocyclic oxygen-containing heterocyclic ring structure having a carbon number of preferably 3 to 10, more preferably 4 or 5 .

Further, as described above, when M is a divalent linking group, Q may be a single bond or may be bonded to M via another linking group to form a ring. The other linking group may, for example, be an alkyl group (preferably an alkylene group having 1 to 3 carbon atoms), and the ring formed is preferably a 5-membered ring or a 6-membered ring.

Further, in another aspect of the present invention, when Y ₃ in the formula (1) is an aromatic ring group and L ₁ is a divalent linking group, L ₁ does not contain an aliphatic ring group, and R ₁ and One of R ₂ and M ₁ are not bonded to each other to form a ring.

In this case, at least one of R ₁ and R ₂ in the formula (1) is preferably an alkyl group having 7 or more carbon atoms, an aliphatic cyclic group, a halogen atom, an aromatic ring group having 13 or more carbon atoms, or Heterocyclic group.

The repeating unit (a) represented by the formula (1) is preferably a repeating unit represented by any one of the formulae (2) to (4). First, a repeating unit represented by the general formula (2) (hereinafter also referred to as "repeating unit (b)") will be described.

[11]

In the general formula (2), Y ₄ and Y ₅ each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form an aromatic ring.

L ₁₁ represents a single bond or a divalent linking group. L ₁₁ may also be bonded to Y ₄ to form a ring, and in this case, L ₁₁ represents a trivalent linking group.

R ₃ and R ₄ each independently represent a hydrogen atom or a substituent.

M ₂ represents an organic group.

One of R ₃ and R ₄ and M ₂ may be bonded to each other to form a ring together with an oxygen atom in the formula.

Here, at least one of Y ₄ and Y ₅ contains an aromatic ring, or Y ₄ and Y ₅ are bonded to each other to form an aromatic ring.

In the general formula (2), the definition and preferred range of the organic group represented by Y ₄ and Y ₅ are the same as those of the organic group represented by Y ₁ and Y ₂ in the general formula (1).

In the general formula (2), the definition and preferred range of the divalent linking group represented by L ₁₁ are the same as those of the divalent linking group represented by Y ₃ in the general formula (1).

In the formula (2), the definition and preferred range of the substituent represented by R ₃ are the same as those of the divalent linking group represented by R ₁ in the formula (1). In one embodiment of the invention, R _{3 is} preferably a hydrogen atom.

In the formula (2), the definition and preferred range of the substituent represented by R ₄ are the same as those of the divalent linking group represented by R ₂ in the formula (1). In one embodiment of the invention, R _{4 is} preferably a hydrogen atom, an alkyl group, an aliphatic cyclic group or an aromatic ring group.

In the general formula (2), the definition and preferred range of the organic group represented by M ₂ are the same as those of the organic group represented by M ₁ in the general formula (1). In one embodiment of the invention, M _{2 is} preferably an alkyl group.

In the formula (2), at least one of Y ₄ and Y ₅ contains an aromatic ring, or Y ₄ and Y ₅ are bonded to each other to form an aromatic ring.

That is, the repeating unit (b) represented by the general formula (2) is a position defining at least one aromatic ring contained as a necessary member with respect to the repeating unit (a) represented by the general formula (1). By.

The at least one aromatic ring group which the formula (2) has is exemplified by the following groups: an aromatic ring having 6 to 18 carbon atoms (more preferably 6 to 10 carbon atoms) such as a benzene ring group or a naphthalene ring group. Or containing, for example, a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, The aromatic ring group of the heterocyclic ring such as a thiazole ring is more preferably a naphthalene ring, and particularly preferably a benzene ring group.

Further, at least one aromatic ring group which the formula (2) has may further have a substituent, and examples of the substituent include an alkyl group, an aliphatic cyclic group, an aryl group, an amine group, a decylamino group, and a guanidine urea. a group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, an aralkyloxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group or the like.

In one embodiment of the invention, in the formula (2), the substituent represented by Y ₄ is preferably an aromatic ring group, more preferably a benzene ring group. In the case where Y ₄ is an aromatic ring group, Y _{5 is} preferably a hydrogen atom.

Next, the repeating unit represented by the general formula (3) (hereinafter also referred to as "repeating unit (c)") will be described.

[化12]

In the formula (3), Y ₆ and Y ₇ each independently represent a hydrogen atom or a monovalent organic group.

L ₂ represents a divalent linking group having an atomic number of 1 between the aromatic ring and the carboxyl group sandwiched in the formula.

R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aliphatic cyclic group, a halogen atom, an aromatic ring group, or a heterocyclic group.

M ₃ represents an organic group.

One of R ₅ and R ₆ and M ₃ are not bonded to each other to form a ring.

n represents an integer of 0 or more.

The repeating unit (c) represented by the formula (3) contains at least one aromatic ring contained in the repeating unit (a) as a necessary member as the following aromatic ring group in the formula, and the aromatic ring group is preferably benzene. A ring or a naphthalene ring is more preferably a benzene ring. That is, n in the formula (3) is preferably 0 or 1, more preferably 0.

[Chemistry 13]

In the general formula (3), the monovalent organic group represented by Y ₆ may, for example, be an alkyl group, an aliphatic cyclic group, an aryl group or a heterocyclic group.

The alkyl group of Y ₆ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.

The aliphatic cyclic group of Y ₆ may be a monocyclic type or a polycyclic type, preferably an aliphatic cyclic group having 3 to 15 carbon atoms, more preferably an aliphatic cyclic group having 3 to 10 carbon atoms. Further, it is preferably an aliphatic cyclic group having 3 to 6 carbon atoms. Specific examples of the aliphatic cyclic group of Y ₆ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group, a cyclodecyl group, and a 1-golden ring. Alkyl, 2-adamantyl, 1-norbornyl, and 2-norbornyl.

The aryl group of Y ₆ is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and a structure in which a plurality of aromatic rings are linked to each other via a single bond (for example, biphenyl group, terphenyl group) base). Specific examples of the aryl group of Y ₆ include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, and a terphenyl group. When Y ₆ is an aryl group, the (n+1)-valent aromatic ring group is represented by an (n+2)-valent aromatic ring group when bonded to Y ₇ to form a ring.

The heterocyclic group of Y ₆ is preferably a heterocyclic group having 6 to 20 carbon atoms, more preferably a heterocyclic group having 6 to 12 carbon atoms. Specific examples of the heterocyclic group of Y ₆ include a pyridyl group, a pyrazinyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a tetrahydrothiophenyl group, a piperidinyl group, a piperazinyl group, a furyl group, a pyranyl group, and a benzene group. And dihydropyranyl group and the like.

The alkyl group, the aliphatic cyclic group, the aryl group, the arylalkyl group and the heterocyclic group of Y ₆ may further have a substituent.

Examples of the substituent which the alkyl group of Y ₆ may have include an aliphatic ring group, an aryl group, an amine group, a decylamino group, a guanidino group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, and the like. Alkoxy, aralkyloxy, thioether, decyl, decyloxy, alkoxycarbonyl, cyano and nitro groups. The substituents may be bonded to each other to form a ring, and the ring when the substituents are bonded to each other to form a ring may, for example, be an aliphatic cyclic group having 3 to 10 carbon atoms or a phenyl group. In one aspect of the invention, when the alkyl group as Y ₆ has a substituent, the substituent is preferably a fluorine atom.

The substituent which may further have an aliphatic cyclic group of Y ₆ may, for example, be an alkyl group and each group described above as a specific example of a substituent which the alkyl group may have.

Further, the carbon number of the alkyl group and the number of carbon atoms of the substituent which the aliphatic cyclic group may have are preferably from 1 to 8, respectively.

Examples of the substituent which the aryl group, the aralkyl group and the heterocyclic group of Y ₆ may further include, for example, a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group or an alkyl group (preferably carbon). a number of 1 to 15), an alkoxy group (preferably having a carbon number of 1 to 15), an aliphatic cyclic group (preferably having a carbon number of 3 to 15), an aryl group (preferably having a carbon number of 6 to 14), and an alkane An oxycarbonyl group (preferably having 2 to 7 carbon atoms), a fluorenyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), and the like.

Y _{6 is} preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, further preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably hydrogen. atom.

The monovalent organic group represented by Y ₇ in the formula (3) may, for example, be an alkyl group, an aliphatic cyclic group, an aryl group or a heterocyclic group.

The alkyl group of Y ₇ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms. Alkyl (ie, methyl or ethyl). Specific examples of the alkyl group of Y ₇ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, and a third butyl group.

Specific examples and preferred examples of the aliphatic cyclic group, aryl group or heterocyclic group of Y ₇ include, for example, specific examples described as the aliphatic cyclic group, aryl group or heterocyclic group as Y ₆ . The preferred examples are the same.

The alkyl group, the aliphatic cyclic group, the aryl group or the heterocyclic group which is Y ₇ may further have a substituent, and the group may have a further substituent with the alkyl group as the Y ₆ or an aliphatic ring type. The group, aryl or heterocyclic group may have the same substituent.

Y _{7 is} preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, further preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably hydrogen. atom.

In the general formula (3), as the divalent linking group of L ₂ , for example, a methylene group, -S-, -O-, -CO-, -CS-, -SO ₂ -, -N(R ₀ ) is preferable. - more preferably methylene and -O-, especially preferably methylene. Here, R ₀ has the same meaning as the R ₀ . Further, in the case where n in the general formula (3) is 0, the divalent linking group as L ₂ may be bonded to any of the ortho, meta, and para positions, and is preferably a para position.

In the formula (3), R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aliphatic cyclic group, a halogen atom, an aromatic ring group or a heterocyclic group.

The alkyl group of R ₅ and R ₆ is preferably an alkyl group having 1 to 20 carbon atoms. Further, the alkyl group preferably has 7 or more carbon atoms. Thereby improving the dry etching performance.

The aliphatic cyclic group of R ₅ and R ₆ may be a monocyclic type or a polycyclic type, preferably an aliphatic cyclic group having 3 to 15 carbon atoms, more preferably an aliphatic group having 3 to 10 carbon atoms. The cyclic group is preferably an aliphatic cyclic group having 5 to 10 carbon atoms. Specific examples of the aliphatic cyclic group of R ₅ and R ₆ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group, and a cyclodecyl group. 1-adamantyl, 2-adamantyl, 1-norbornyl, and 2-norbornyl, etc., preferably cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1- Norse base, and 2-norborn base.

The halogen atom of R ₅ and R ₆ may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom.

The aromatic ring group of R ₅ and R ₆ is preferably an aryl group having 6 to 18 carbon atoms, and also a structure in which a plurality of aromatic rings are bonded to each other via a single bond (for example, a biphenyl group or a terphenyl group). Specific examples of the aryl group of R ₅ and R ₆ include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, and a terphenyl group. Further, the carbon number of the aromatic ring group is preferably 13 or more. Thereby improving the dry etching performance.

The heterocyclic group of R ₅ and R ₆ is preferably a heterocyclic group having 6 to 20 carbon atoms, more preferably a heterocyclic group having 6 to 12 carbon atoms. Specific examples of the heterocyclic group of R ₅ and R ₆ include a pyridyl group, a pyrazinyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a tetrahydrothiophenyl group, a piperidinyl group, a piperazinyl group, a furyl group, and a pyran group. Base, benzohydropyranyl and the like.

R ₅ and R as an alkyl group, an aliphatic cyclic group, a halogen atom, an aromatic group, a heterocyclic group having ₆ or more may also have a substituent, R ₅ may further have a substituent group the alkyl group of Y ₁ The substituents which may be present are the same.

In one aspect of the invention, at least one of R ₅ and R ₆ is preferably an alkyl group having 7 or more carbon atoms, an aliphatic cyclic group, a halogen atom, an aromatic ring group having 13 or more carbon atoms, or a heterocyclic group. .

The groups other than the halogen atom may have more substituents, and may have more substituents such as an alkyl group, an aliphatic cyclic group, an aryl group, an amine group, a decylamino group, a guanyl urea group, an amine group. The acid ester group, the hydroxyl group, the carboxyl group, the halogen atom, the alkoxy group, the aralkyloxy group, the thioether group, the decyl group, the decyloxy group, the alkoxycarbonyl group, the cyano group and the nitro group are appropriately selected.

When at least one of R ₅ and R ₆ is an alkyl group having 7 or more carbon atoms, it is more preferably an alkyl group having 7 to 15 carbon atoms, and still more preferably an alkyl group having 7 to 10 carbon atoms.

In the case where at least one of R ₅ and R ₆ is an aromatic ring group having 13 or more carbon atoms, it is more preferably an aromatic ring group having 13 or more carbon atoms, and further preferably an aromatic ring group having 13 to 18 carbon atoms.

Furthermore, in one aspect of the invention, at least one of R ₅ and R ₆ is preferably a hydrogen atom, an alkyl group, an aliphatic cyclic group or an aromatic ring group.

In the general formula (3), the definition and preferred range of the organic group represented by M ₃ are the same as those of the organic group represented by M ₁ in the general formula (1). Wherein M ₃ is not bonded to one of R ₅ and R ₆ to form a ring.

In one embodiment of the present invention, M _{3 is} preferably an alkyl group having 7 or more carbon atoms, an aliphatic cyclic group, a halogen atom or an aromatic ring group having 13 or more carbon atoms or a heterocyclic group.

When M ₃ is an alkyl group having 7 or more carbon atoms, it is more preferably an alkyl group having 7 to 15 carbon atoms, and still more preferably an alkyl group having 7 to 10 carbon atoms.

Further, when M ₃ is an aromatic ring group having 13 or more carbon atoms, it is more preferably an aromatic ring group having 13 to 18 carbon atoms.

In one embodiment of the present invention, the repeating unit (c) represented by the formula (3) is preferably a repeating unit represented by the formula (3c).

[Chemistry 14]

In the general formula (3a), Y ₆ , Y ₇ , L ₂ , R ₅ , R ₆ and n have the same meanings as the respective groups in the above formula (3).

In the general formula (3a), M and Q have the same meanings as M and Q in *-MQ which is a form of M ₁ in the above formula (1).

Next, the repeating unit represented by the general formula (4) (hereinafter also referred to as "repeating unit (d)") will be described.

[化15]

In the formula (4), Y ₈ and Y ₉ each independently represent a hydrogen atom or a monovalent organic group.

R ₇ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, an aromatic ring group, a heterocyclic group or a halogen atom.

R ₈ represents a hydrogen atom or a substituent.

M ₄ represents an organic group.

One of R ₇ and R ₈ and M ₄ may be bonded to each other to form a ring together with an oxygen atom in the formula.

n represents an integer of 0 or more.

The repeating unit (d) represented by the formula (4) contains at least one aromatic ring contained in the repeating unit (a) as a necessary member as the following aromatic ring group in the formula, and the aromatic ring group is preferably benzene. A ring or a naphthalene ring is more preferably a benzene ring. That is, n in the formula (4) is preferably 0 or 1, more preferably 0.

[Chemistry 16]

In the general formula (4), Y ₈ and Y ₉ have the same meanings as Y ₆ and Y ₇ in the above formula (3), and the preferred ranges are also the same.

In the formula (4), R ₇ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, a halogen atom, an aromatic ring group or a heterocyclic group.

The groups other than the halogen atom may have more substituents, and may have more substituents such as an alkyl group, an aliphatic cyclic group, an aryl group, an amine group, a decylamino group, a guanyl urea group, an amine group. The acid ester group, the hydroxyl group, the carboxyl group, the halogen atom, the alkoxy group, the aralkyloxy group, the thioether group, the decyl group, the decyloxy group, the alkoxycarbonyl group, the cyano group and the nitro group are appropriately selected.

The alkyl group of R ₇ preferably has a carbon number of 6 or more from the viewpoint of dry etching performance.

R _{7 is} preferably an alkyl group having 6 to 15 carbon atoms, more preferably an alkyl group having 6 to 10 carbon atoms.

In the above formula (4), the definition and preferred range of the aliphatic cyclic group, the halogen atom, the aromatic ring group, and the heterocyclic group represented by R ₇ and the aliphatic cyclic group as R ₅ , The halogen atom, the aromatic ring group, and the heterocyclic group are the same. Further, the groups may have a substituent which is the same as the substituent which the alkyl group of Y ₁ may have.

In one aspect of the invention, R _{7 is} preferably an aliphatic cyclic group.

The alkyl group, the aliphatic cyclic group, the aromatic ring group or the heterocyclic group as R ₇ may further have a substituent, and the groups may have a further substituent with the alkyl group as the Y ₁ , an aliphatic group. The cyclic group, the aromatic ring group, or the heterocyclic group may have the same substituents.

In the general formula (4), the organic group represented by R ₈ has the same meaning as the organic group represented by R ₁ in the general formula (1). In one embodiment of the invention, R _{8 is} preferably a hydrogen atom, an alkyl group, an aliphatic cyclic group or an aromatic ring group.

In the general formula (4), the definition and preferred range of the organic group represented by M ₄ are the same as those of the organic group represented by M ₁ in the general formula (1). Further, the organic group represented by M ₄ may be a group having no ring structure based on one form.

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

[化17]

[化18]

[Chemistry 19]

With respect to all the repeating units in the resin (P1), the content of the repeating unit (a) represented by the above formula (1) in the resin (P1) is preferably a total amount of the repeating unit (a) 10 mol% to 90 mol%, more preferably 30 mol% to 80 mol%, and further preferably 50 mol% to 70 mol%.

In one aspect of the invention, the resin (P1) preferably has a repeating unit represented by the following formula (A).

[Chemistry 20]

In the formula (A), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group (wherein R ₄₂ may also bond with Ar ₄ or X _{4 ;} The ring is formed, in which case R ₄₂ represents a single bond or an alkyl group.

X ₄ represents a single bond, an alkylene group, -COO-, or -CONR ₆₄ - (wherein R ₆₄ represents a hydrogen atom or an alkyl group).

L ₄ represents a single bond, -COO-, or an alkylene group.

Ar ₄ represents an (n+1)-valent aromatic ring group, and when it is bonded to R ₄₂ to form a ring, it represents an (n+2)-valent aromatic ring group.

n represents an integer of 1 to 4.

The alkyl group of R ₄₁ , R ₄₂ and R ₄₃ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a hexyl group or a 2-ethylhexyl group which may have a substituent. The alkyl group having a carbon number of 20 or less, such as an octyl group or a dodecyl group, more preferably an alkyl group having 8 or less carbon atoms, and particularly preferably an alkyl group having 3 or less carbon atoms.

R _41, R _42, specific examples of the alkyl group R _{43 is} an alkoxycarbonyl group included in the preferred embodiment and the R _41, R _42, R ₄₃ are the same alkyl group.

The halogen atom of R ₄₁ , R ₄₂ and R ₄₃ may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom.

Ar ₄ represents an (n+1)-valent aromatic ring group. When the n is 1, the divalent aromatic ring group may have a substituent. For example, the following groups are preferred: a carbon number of 6 to 6 such as a phenyl group, a methylphenyl group, a naphthyl group, or a fluorenyl group. An aryl group of 18, or an aromatic ring containing a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole base.

A specific example of the (n+1)-valent aromatic ring group in the case where n is an integer of 2 or more is preferably exemplified by (n-1) arbitrary from the specific example of the divalent aromatic ring group. a group of hydrogen atoms.

The (n+1)-valent aromatic ring group may also have a more substituent.

The alkylene group of L ₄ is preferably a methylene group which may have a substituent, a methyl group, an exoethyl group, a propyl group, a butyl group, a hexyl group, a octyl group, and the like. base.

The alkylene group represented by X ₄ is the same as the alkylene group as the divalent linking group represented by L in the general formula (Ab), and the preferred range is also the same.

When R ₄₂ is bonded to Ar ₄ or X ₄ to form a ring, the alkyl group of R ₄₂ may be linear or branched, and preferably has 1 to 5 carbon atoms.

When R ₄₂ and X _{4 are} bonded to each other to form a ring, the alkyl group of X ₄ may be linear or branched, and preferably has 1 to 5 carbon atoms.

The alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ may be the same as the alkyl group of R ₄₁ to R ₄₃ .

X _{4 is} preferably a single bond, an alkyl group, -COO-, -CONH-, more preferably a single bond, -COO-.

Ar _{4 is more} preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a benzene ring group, a naphthalene ring group or a biphenyl ring group.

The repeating unit (b) preferably has a hydroxystyrene structure. That is, Ar _{4 is} preferably a benzene ring group.

Preferred examples of the substituent in the respective groups include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a guanidino group, a urethane group, a hydroxyl group, a carboxyl group, and a halogen atom. An alkoxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group or the like, and the carbon number of the substituent is preferably 8 or less.

The repeating unit represented by the formula (A) is preferably a repeating unit represented by the following formula (A1) or formula (A2). R'' represents a hydrogen atom or a methyl group.

[Chem. 21]

Specific examples of the repeating unit (b) represented by the formula (A) include the repeating units shown below, and those described in paragraphs 0226 to 0227 of JP-A-2014-41328, and the like. This content is incorporated into this specification.

[化22]

The resin (P1) may contain two or more types of repeating units represented by the formula (A).

The above formula (A1) in the resin (P1) with respect to all repeating units in the resin (P1) from the viewpoint of improving the dissolution contrast of the sensitizing ray-sensitive or radiation-sensitive film to the developer containing the organic solvent The content of the repeating unit represented by the above (in the case of a plurality of cases) is preferably 10 mol% to 70 mol%, more preferably 15 mol% to 55 mol%, most preferably 20 mol% to 40 Mol%.

The resin (P1) may further contain a repeating unit represented by the following formula (A5).

[化23]

In the formula (A5), X represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a decyl group, a decyloxy group, a cycloalkyl group, an aryl group, a carboxyl group, an alkoxycarbonyl group, An alkylcarbonyloxy group, or an aralkyl group.

A ₄ represents a hydrocarbon group which is not desorbed by the action of an acid.

The hydrocarbon group which is not desorbed by the action of the acid in the A ₄ of the formula (A5) may be a hydrocarbon group other than the acid-decomposable group, and examples thereof include an alkyl group which is not desorbed by the action of an acid (preferably carbon). Numerals 1 to 15), a cycloalkyl group which is not desorbed by the action of an acid (preferably having a carbon number of 3 to 15), an aryl group which is not desorbed by the action of an acid (preferably having a carbon number of 6 to 15), or the like.

The hydrocarbon group of A _{4 which} is not removed by the action of an acid may be further substituted with a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group or the like.

Specific examples of the repeating unit represented by the formula (A5) are listed below, but are not limited to the specific examples.

[Chem. 24]

Further, as a repeating unit having an acid-decomposable group different from the repeating unit exemplified above, the resin (P1) may have a repeating unit which generates an alcoholic hydroxyl group. In this case, the repeating unit which produces an alcoholic hydroxyl group is preferably represented by at least one selected from the group consisting of the following general formula (I-1) to the general formula (I-10). The repeating unit which produces an alcoholic hydroxyl group is more preferably represented by at least one selected from the group consisting of the following general formula (I-1) to the general formula (I-3), and further preferably by the following formula ( I-1) indicates.

[化25]

In the formula, Ra each independently represents a hydrogen atom, an alkyl group or a group represented by -CH ₂ -O-Ra ₂ . Here, Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group.

R ₁ represents an organic group of (n+1) valence.

In the case of m ≧ 2, R ₂ independently represents a single bond or an (n+1)-valent organic group.

OP independently represents the group which decomposes by the action of an acid and produces an alcoholic hydroxyl group. In the case of n≧2 and/or m≧2, two or more OPs may be bonded to each other to form a ring.

W represents a methylene group, an oxygen atom or a sulfur atom.

n and m represent an integer of 1 or more. Further, in the case of the general formula (I-2), the general formula (I-3) or the general formula (I-8), when R ₂ represents a single bond, n is 1.

l represents an integer greater than 0.

L ₁ represents a linking group represented by -COO-, -OCO-, -CONH-, -O-, -Ar-, -SO ₃ - or -SO ₂ NH-. Here, Ar represents a divalent aromatic ring group.

R independently represents a hydrogen atom or an alkyl group.

R ₀ represents a hydrogen atom or an organic group.

L ₃ represents a (m + 2) valent linking group.

When R ^{L is} in the case of m ≧ 2, the (n+1)-valent linking group is independently represented.

R ^S independently represents a substituent in the case of p ≧ 2 . In the case of p≧2, a plurality of R ^S may be bonded to each other to form a ring.

p represents an integer of 0 to 3.

Ra represents a hydrogen atom, an alkyl group or a group represented by -CH ₂ -O-Ra ₂ . Ra is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group.

W represents a methylene group, an oxygen atom or a sulfur atom. W is preferably a methylene group or an oxygen atom.

R ₁ represents an organic group of (n+1) valence. R _{1 is} preferably a non-aromatic hydrocarbon group. In this case, R ₁ may be a chain hydrocarbon group or an aliphatic cyclic hydrocarbon group. R _{1 is more} preferably an aliphatic cyclic hydrocarbon group.

R ₂ represents a single bond or an (n+1)-valent organic group. R _{2 is} preferably a single bond or a non-aromatic hydrocarbon group. In this case, R ₂ may be a chain hydrocarbon group or an aliphatic cyclic hydrocarbon group.

In the case where R ₁ and/or R ₂ is a chain hydrocarbon group, the chain hydrocarbon group may be linear or branched. Further, the chain hydrocarbon group preferably has 1 to 8 carbon atoms. For example, when R ₁ and/or R ₂ is an alkylene group, R ₁ and/or R _{2 are} preferably methylene, ethyl, propyl, isopropyl, butyl, and extens. Isobutyl or a second butyl group.

In the case where R ₁ and/or R ₂ is an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be a monocyclic ring or a polycyclic ring. The aliphatic cyclic hydrocarbon group has, for example, a monocyclic, bicyclic, tricyclic or tetracyclic structure. The aliphatic cyclic hydrocarbon group has a carbon number of usually 5 or more, preferably 6 to 30, and more preferably 7 to 25.

Examples of the aliphatic cyclic hydrocarbon group include those having the following partial structures. Each of the partial structures may also have a substituent. Further, in each of the partial structures, the methylene group (-CH ₂ -) may also pass through an oxygen atom (-O-), a sulfur atom (-S-), a carbonyl group [-C(=O)-], a sulfonate. Substituted by fluorenyl [-S(=O) ₂ -], sulfinyl [-S(=O)-], or imino [-N(R)-] (R is a hydrogen atom or an alkyl group) .

[Chem. 26]

For example, in the case where R ₁ and/or R ₂ is a cycloalkyl group, R ₁ and/or R _{2 are} preferably an adamantyl group, an extended adamantyl group, a decahydronaphthyl group, or a tricyclic ring. Alkyl, tetracyclododecyl, heptane, pentylene, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, or dodecyl, more Preferably, it is an adamantyl group, an extended borneol group, a cyclohexylene group, a cyclopentyl group, a tetracyclododecyl group or a tricyclodecyl group.

The non-aromatic hydrocarbon group of R ₁ and/or R ₂ may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, and an alkoxycarbonyl group having 2 to 6 carbon atoms. The alkyl group, alkoxy group and alkoxycarbonyl group may also have a more substituent. Examples of the substituent include a hydroxyl group, a halogen atom, and an alkoxy group.

L ₁ represents a linking group represented by -COO-, -OCO-, -CONH-, -O-, -Ar-, -SO ₃ - or -SO ₂ NH-. Here, Ar represents a divalent aromatic ring group. L _{1 is} preferably a linking group represented by -COO-, -CONH- or -Ar-, more preferably a linking group represented by -COO- or -CONH-.

R represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. R is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

R ₀ represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an alkynyl group, and an alkenyl group. R _{0 is} preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.

L ₃ represents a (m + 2) valent linking group. That is, L ₃ represents a trivalent or higher linking group. Examples of such a linking group include the corresponding groups in the specific examples described below.

R ^L represents a (n+1)-valent linking group. That is, R ^L represents a divalent or higher linking group. Examples of such a linking group include an alkylene group, a cycloalkylene group, and a corresponding group in a specific example described below. R ^L may also be bonded to each other or to the following R ^S to form a ring structure.

R ^S represents a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, a decyloxy group, an alkoxycarbonyl group, and a halogen atom.

n is an integer of 1 or more. n is preferably an integer of from 1 to 3, more preferably 1 or 2. Further, when n is 2 or more, the dissolution contrast of the developer containing the organic solvent can be further improved. Therefore, as described above, the ultimate resolution and roughness characteristics can be further improved.

m is an integer of 1 or more. m is preferably an integer of from 1 to 3, more preferably 1 or 2.

l is an integer greater than 0. l is preferably 0 or 1.

p is an integer from 0 to 3.

The repeating unit which produces an alcoholic hydroxyl group is preferably a repeating unit having a group which decomposes by an action of an acid and produces an alcoholic hydroxyl group.

Specific examples of the repeating unit having a group which decomposes by an action of an acid to produce an alcoholic hydroxyl group are shown below. Further, in a specific example, Ra and OP have the same meanings as Ra and OP in the general formula (I-1) to the general formula (I-3). Further, when a plurality of OPs are bonded to each other to form a loop, the corresponding loop structure is expressed as "O-P-O" for the sake of convenience.

[化27]

The group which decomposes by the action of an acid and produces an alcoholic hydroxyl group is preferably represented by at least one selected from the group consisting of the following general formulae (II-1) to (II-4).

[化28]

In the formula, R ₃ each independently represents a hydrogen atom or a monovalent organic group. R ₃ may also be bonded to each other to form a ring.

R ₄ each independently represents a monovalent organic group. R ₄ may also be bonded to each other to form a ring. R ₃ and R ₄ may also be bonded to each other to form a ring.

R ₅ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. At least two R ₅ may also be bonded to each other to form a ring. Wherein, in the case where one or both of the three R ₅ are a hydrogen atom, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group.

The group which decomposes by the action of an acid and produces an alcoholic hydroxyl group is also preferably represented by at least one selected from the group consisting of the following general formulae (II-5) to (II-9).

[化29]

In the formula, R ₄ has the same meaning as R ₄ in the formula (II-1) to the formula (II-3).

R ₆ each independently represents a hydrogen atom or a monovalent organic group. R ₆ may also be bonded to each other to form a ring.

The group which is decomposed by the action of an acid and which produces an alcoholic hydroxyl group is more preferably represented by at least one selected from the group consisting of the formula (II-1) to the formula (II-3), and further preferably from the formula (II) The formula (1) or the formula (II-3) is particularly preferably represented by the formula (II-1).

As described above, R ₃ represents a hydrogen atom or a monovalent organic group. R _{3 is} preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group.

The alkyl group of R ₃ may be linear or branched. The alkyl group of R ₃ preferably has 1 to 10 carbon atoms, more preferably 1 to ₃ carbon atoms. Examples of the alkyl group of R ₃ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group.

The cycloalkyl group of R ₃ may be a monocyclic ring or a polycyclic ring. The number of carbon atoms of the cycloalkyl group of R ₃ is preferably from 3 to 10, more preferably from 4 to 8. Examples of the cycloalkyl group of R ₃ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

Further, in the formula (II-1), at least one of R ₃ is preferably a monovalent organic group. With such a configuration, a particularly high sensitivity can be achieved.

R ₄ represents a monovalent organic group. R _{4 is} preferably an alkyl group or a cycloalkyl group, more preferably an alkyl group. The alkyl group and the cycloalkyl group may also have a substituent.

The alkyl group of R ₄ preferably has no substituent or has one or more aryl groups and/or one or more decyl groups as a substituent. The unsubstituted alkyl group preferably has 1 to 20 carbon atoms. The alkyl group in the alkyl group substituted with one or more aryl groups preferably has 1 to 25 carbon atoms. The alkyl group in the alkyl group substituted by one or more decyl groups preferably has 1 to 30 carbon atoms. Further, when the cycloalkyl group of R ₄ does not have a substituent, the carbon number thereof is preferably from 3 to 20.

R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. Wherein, in the case where one or both of the three R ₅ are a hydrogen atom, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group. R _{5 is} preferably a hydrogen atom or an alkyl group. The alkyl group may have a substituent or may have no substituent. When the alkyl group does not have a substituent, the carbon number is preferably from 1 to 6, preferably from 1 to 3.

As described above, R ₆ represents a hydrogen atom or a monovalent organic group. R _{6 is} preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or an alkyl group having no substituent. R _{6 is} preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and no substituent.

Further, examples of the alkyl group and the cycloalkyl group of R ₄ , R ₅ and R ₆ include the same alkyl group and cycloalkyl group as those described above for R ₃ .

Specific examples of the group which decomposes by the action of an acid and produces an alcoholic hydroxyl group are shown below.

[化30]

[化31]

[化32]

Specific examples of the repeating unit having a group which decomposes by an action of an acid to produce an alcoholic hydroxyl group are shown below. In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

[化33]

The repeating unit having an acid-decomposable group may be one type or two or more types may be used in combination.

The content of the repeating unit having an acid-decomposable group in the resin (P1) (inclusive of a plurality of cases) is preferably 10 mol% to 90 mol%, based on all the repeating units in the resin (P1). More preferably, it is 30 mol% to 80 mol%, and most preferably 50 mol% to 70 mol%.

The resin (P1) may further contain a repeating unit represented by the following formula (4).

[化34]

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ^{4 2} represents a divalent linking group. S represents a structural portion which is decomposed by irradiation of actinic rays or radiation to generate an acid in a side chain.

Specific examples of the repeating unit represented by the formula (4) include, for example, paragraphs 0195 to 0209 of JP-A-2014-41328, paragraphs 0016 to 0145 of JP-A-2013-54196, and the like. The inventors, the contents of which are incorporated in the present specification.

The content of the repeating unit represented by the formula (4) in the resin (P1) is preferably in the range of 1 mol% to 40 mol%, more preferably 2 mol% to 30, based on all the repeating units of the resin (P1). The range of mol% is particularly preferably in the range of 5 mol% to 25 mol%.

The resin (P1) preferably contains a repeating unit (b') having a polar group different from the repeating unit represented by the formula (A). By containing the repeating unit (b'), for example, the sensitivity of the resin-containing composition can be improved. The repeating unit (b') is preferably a non-acid-decomposable repeating unit (that is, having no acid-decomposable group).

Examples of the "polar group" which the repeating unit (b') can contain include the following (1) to (4). In addition, the following "electronegativity" refers to a value based on Pauling.

(1) A functional group having a structure in which an oxygen atom and an anion having a difference in an anion degree from an oxygen atom of 1.1 or more are bonded by a single bond, and examples of the polar group include a hydroxyl group and the like, which are represented by OH. The group of the structure.

(2) A functional group having a structure in which a nitrogen atom and a negative electrode with a nitrogen atom having a difference in an anion degree of 0.6 or more are bonded by a single bond, and examples of the polar group include, for example, an amine group and the like. The structure of the group.

(3) A functional group having a structure in which two different atoms having an anion degree of 0.5 or more are bonded by a double bond or a triple bond, and examples of such a polar group include C≡N, C=O, and A group of a structure represented by N=O, S=O or C=N.

(4) Functional group having an ionic moiety Such a polar group is, for example, a group having a moiety represented by N ⁺ or S ⁺ .

Specific examples of the partial structure which the "polar group" can contain are listed below.

[化35]

The polar group which the repeating unit (b') may contain is preferably selected from the group consisting of a hydroxyl group, a cyano group, a lactone group, a sultone group, a carboxylic acid group, a sulfonic acid group, a decylamino group, a sulfonylamino group, an ammonium group, a group in which a mercapto group, a carbonate group (-O-CO-O-) (for example, a cyclic carbonate structure), and a combination of two or more of these are preferably an alcoholic hydroxyl group, a cyano group, or an internal group. An ester group, a sultone group, or a group containing a cyanolactone structure.

When the resin further contains a repeating unit having an alcoholic hydroxyl group, the exposure latitude (EL) of the resin-containing composition can be further improved.

When the resin further contains a repeating unit having a cyano group, the sensitivity of the resin-containing composition can be further improved.

When the resin further contains a repeating unit having a lactone group, the dissolution contrast of the developer containing the organic solvent can be further improved. Further, as described above, the dry etching resistance, the coating property, and the adhesion to the substrate of the resin-containing composition can be further improved.

When the resin further contains a repeating unit having a group containing a lactone having a cyano group, the solubility of the developer containing the organic solvent can be further improved. Further, as described above, it is possible to further improve the sensitivity, the dry etching resistance, the coatability, and the adhesion to the substrate of the resin-containing composition. In addition to this, the function of each of the cyano group and the lactone group can be carried by a single repeating unit, and the degree of design freedom of the resin can be further increased.

In the case where the polar group of the repeating unit (b') is an alcoholic hydroxyl group, it is preferably selected from the group consisting of the following general formula (I-1H) to the general formula (I-10H). At least one representation. In particular, it is more preferably represented by at least one selected from the group consisting of the following general formula (I-1H) to the general formula (I-3H), and further preferably represented by the following general formula (I-1H) .

[化36]

Wherein, Ra, R ₁ , R ₂ , W, n, m, 1, L ₁ , R, R ₀ , L ₃ , R ^L , R ^S and p and the formula (I-1) to formula (I) In the case of -10), Ra, R ₁ , R ₂ , W, n, m, 1, L ₁ , R, R ₀ , L ₃ , R ^L , R ^S and p have the same meanings.

a combination of a repeating unit having a group decomposed by an action of an acid and producing an alcoholic hydroxyl group, and a group selected from the group consisting of the formula (I-1H) to the formula (I-10H) At least one of the repeating units represented, for example, suppresses acid diffusion by an alcoholic hydroxyl group, and increases the sensitivity by decomposing by an action of an acid to generate an alcoholic hydroxyl group, thereby improving without deteriorating other properties. Exposure latitude (EL).

In the case of having an alcoholic hydroxyl group, the content of the repeating unit is preferably from 1 mol% to 60 mol%, more preferably from 3 mol% to 50 mol%, based on all the repeating units in the resin (P1). Further preferably, it is 5 mol% to 40 mol%.

Specific examples of the repeating unit represented by any one of the formula (I-1H) to the formula (I-10H) are shown below. Further, in a specific example, Ra has the same meaning as Ra in the general formula (I-1H) to the general formula (I-10H).

[化37]

In the case where the polar group of the repeating unit (b') is an alcoholic hydroxyl group or a cyano group, one aspect of a preferred repeating unit may be a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. . In this case, it is preferred that the acid-decomposable group is not provided. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by a hydroxy group or a cyano group is preferably an adamantyl group, a diamantyl group or a norbornyl group. The alicyclic hydrocarbon structure preferably substituted by a hydroxyl group or a cyano group is preferably a partial structure represented by the following formula (VIIa) to formula (VIIc). Thereby, the substrate adhesion and the developer affinity are improved.

[化38]

In the general formulae (VIIa) to (VIIc), R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. Here, at least one of R ₂ c to R ₄ c represents a hydroxyl group. Preferably, one or both of R ₂ c to R ₄ c are hydroxyl groups, and the remainder is a hydrogen atom. In the formula (VIIa), it is further preferred that two of R ₂ c to R ₄ c are a hydroxyl group, and the remainder is a hydrogen atom.

The repeating unit having a partial structure represented by the general formulae (VIIa) to (VIIc) may be a repeating unit represented by the following general formula (AIIa) to (AIIc).

[39]

In the general formula (AIIa) to the general formula (AIIc), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c ~ R ₄ c in the general formula (VIIa) ~ formula (VIIc) in R ₂ c ~ R ₄ c have the same meaning.

The resin (P1) may contain a repeating unit having a hydroxyl group or a cyano group, or may not contain a repeating unit having a hydroxyl group or a cyano group, and in the case of containing a repeating unit having a hydroxyl group or a cyano group, relative to all in the resin (P1) The content of the repeating unit having a hydroxyl group or a cyano group is preferably from 1 mol% to 60 mol%, more preferably from 3 mol% to 50 mol%, even more preferably from 5 mol% to 40 mol%.

Specific examples of the repeating unit having a hydroxyl group or a cyano group are listed below, but the present invention is not limited to these specific examples.

[化40]

The repeating unit (b') may also be a repeating unit having a lactone structure as a polar group.

The repeating unit having a lactone structure is more preferably a repeating unit represented by the following formula (AII).

[化41]

In the formula (AII), Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent (preferably, carbon number 1-4).

Preferred examples of the substituent of the alkyl group of Rb ₀ include a hydroxyl group and a halogen atom. 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, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly 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 cycloalkyl structure, an ether bond, an ester bond, a carbon group, or a combination of these. Ab is preferably a single bond, a divalent linking group represented by -Ab ₁ -CO ₂ -.

Ab ₁ is a linear or branched alkyl, monocyclic or polycyclic cycloalkyl group, preferably a methylene group, an ethyl group, a cyclohexylene group, an adamantyl group, or a borneol group.

V represents a group having a lactone structure.

The group having a lactone structure may be optionally used as long as it has a lactone structure, preferably a 5-membered ring to a 7-membered ring lactone structure, and is preferably formed on a 5-membered ring to a 7-membered ring lactone structure. The double ring structure and the form of the spiro ring structure have other ring structures. More preferably, it is a repeating unit which has a lactone structure represented by any of the following General formula (LC1-1) - Formula (LC1-17). In addition, the lactone structure can also be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), (LC1-14).

[化42]

The lactone moiety may have a substituent (Rb ₂ ) or a substituent (Rb ₂ ). Preferred examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkylene having 2 to 8 carbon atoms. An oxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, or the like. More preferably, it is an alkyl group of 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

The repeating unit having a lactone group usually has an optical isomer, and any optical isomer can be used. Further, one optical isomer may be used alone, or a plurality of optical isomers may be used in combination. In the case where an optical isomer is mainly used, the optical purity (enantiomeric excess (ee)) is preferably 90% or more, more preferably 95% or more.

The resin (P1) may contain a repeating unit having a lactone structure, or may not contain a repeating unit having a lactone structure, and in the case of containing a repeating unit having a lactone structure, in the resin (P1) with respect to all the repeating units The content of the repeating unit having a lactone structure is preferably in the range of 1 mol% to 70 mol%, more preferably in the range of 3 mol% to 65 mol%, and still more preferably in the range of 5 mol% to 60 mol%.

Specific examples of the repeating unit having a lactone structure in the resin (P1) are shown below, but the present invention is not limited thereto. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[化43]

[化44]

Further, the sultone group of the resin (P1) is preferably the following formula (SL-1) or formula (SL-2). Rb ₂ and n ₂ in the formula have the same meanings as in the above formula (LC1-1) to formula (LC1-17).

[化45]

The repeating unit containing a sultone group which the resin (P1) has is preferably obtained by substituting a lactone group in the repeating unit having a lactone group into a sultone group.

Further, the repeating unit (b') may have a polar group which is an acidic group and is also one of a particularly preferable aspect. Preferred examples of the acidic group include a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, a fluorinated alcohol group (for example, hexafluoroisopropanol group), a sulfonylamino group, a sulfonyl fluorenylene group, and an alkyl group. (sulfonyl) (alkylcarbonyl) methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl) fluorenylene , bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)indolylene, tris(alkylcarbonyl)methylene, tris(alkylsulfonyl)methylene. Among them, the repeating unit (b) is more preferably a repeating unit having a carboxyl group. The clarification in the use of the contact hole is increased by containing a repeating unit having an acidic group. The repeating unit having an acidic group is preferably any of the following repeating units: a repeating unit in which a main chain of the resin is directly bonded to an acidic group, such as a repeating unit of acrylic acid or methacrylic acid, or via a linking group; The main chain of the resin is bonded to a repeating unit of an acidic group, and further, a terminal which is introduced into the polymer chain by using a polymerization initiator or a chain transfer agent having an acidic group during polymerization. It is especially preferred to use a repeating unit of acrylic acid or methacrylic acid.

The acidic group which the repeating unit (b') may have may have an aromatic ring or an aromatic ring. When the repeating unit (b') has an acidic group, the content of the repeating unit having an acidic group is preferably 30 mol% or less, more preferably 20 mol% or less, based on all the repeating units in the resin (P1). When the resin (P1) contains a repeating unit having an acidic group, the content of the repeating unit having an acidic group in the resin (P1) is usually 1 mol% or more.

Specific examples of the repeating unit having an acidic group are shown below, but the present invention is not limited thereto.

In a specific example, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

[Chem. 46]

The resin (P1) may further contain a repeating unit (c) having a plurality of aromatic rings represented by the following formula (c1).

[化47]

In the formula (c1), R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or a nitro group; Y represents a single bond or a divalent linking group; Z represents a single bond or a divalent linking group; and Ar represents an aromatic ring group. ; p represents an integer of 1 or more.

Regarding the repeating unit represented by the formula (c1), the contents described in paragraphs 0265 to 0279 of JP-A-2014-41328 can be referred to, and the contents are incorporated in the present specification.

The resin (P1) may contain the repeating unit (c) or the repeating unit (c), and in the case of containing the repeating unit (c), repeat the unit (c) with respect to all repeating units in the resin (P1) The ratio is preferably in the range of 1 mol% to 30 mol%, more preferably in the range of 1 mol% to 20 mol%, and still more preferably in the range of 1 mol% to 15 mol%. The repeating unit (c) contained in the resin (P1) may be contained in combination of two or more kinds.

The resin (P1) in the present invention may suitably have a repeating unit other than the repeating unit (a) to the repeating unit (c). An example of such a repeating unit having an alicyclic hydrocarbon structure not containing a polar group (for example, the acid group, a hydroxyl group, or a cyano group) and having no acid decomposition property may be further provided as a repeating unit. Thereby, the solubility of the resin can be appropriately adjusted at the time of development using a developing solution containing an organic solvent. Such a repeating unit can be exemplified by the repeating unit represented by the formula (IV).

[48]

In the formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.

Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

R ₅ has a cyclic structure containing a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group, and a cycloalkenyl group having 3 to 12 carbon atoms such as a cyclohexenyl group. A preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group contains a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group, and examples of the cyclic hydrocarbon group include a dicyclohexyl group, a perhydronaphthyl group and the like. Examples of the crosslinked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo [ 3.2.1] Octane ring) and other bicyclic hydrocarbon rings, and tricyclo [5.2.1.0 ^3,8 ]nonane (homobrendane), adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, tricyclic [4.3.1.1 ^2,5 ] tricyclic hydrocarbon ring such as undecane ring, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane, perhydro-1,4-methyl bridge-5, A tetracyclic hydrocarbon ring such as an 8-a-bridge naphthalene ring. In addition, the crosslinked cyclic hydrocarbon ring also contains a condensed cyclic hydrocarbon ring, such as perhydronaphthalene (decalin), perhydroquinone, perhydrophenanthrene, perhydroindene, perhydroindene, perhydroanthracene, A condensed ring obtained by condensing a plurality of 5-membered cycloalkane rings to 8-membered cycloalkane rings such as a perhydroindole ring.

Preferred examples of the crosslinked cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctyl group, a tricyclo[5.2.1.0 ^2,6 ]decyl group, and the like. More preferably, the crosslinked cyclic hydrocarbon ring may be a norbornyl group or an adamantyl group.

The alicyclic hydrocarbon group may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, an amine group substituted with a hydrogen atom, and the like. Preferable examples of the halogen atom include bromine, chlorine and fluorine. Preferred alkyl groups include a methyl group, an ethyl group, a butyl group and a tert-butyl group. The alkyl group may have a more substituent, and may further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amine group substituted with a hydrogen atom.

Examples of the substituent of the hydrogen atom include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, and preferred substituted methyl groups include methoxymethyl group, methoxythiomethyl group, benzyloxymethyl group and third group. Preferred examples of the ethoxymethyl group and the 2-methoxyethoxymethyl group include a 1-ethoxyethyl group and a 1-methyl-1-methoxyethyl group. Examples of the fluorenyl group include an aliphatic fluorenyl group having 1 to 6 carbon atoms such as a mercapto group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl group, an isobutyl group, a pentamidine group, and a pivaloyl group, and an alkoxycarbonyl group. The alkoxycarbonyl group having 1 to 4 carbon atoms may, for example, be mentioned.

The resin (P1) may contain the following repeating unit or may not contain a repeating unit having an alicyclic hydrocarbon structure not containing a polar group and exhibiting no acid decomposition property, and in the case of containing the repeating unit, The content of the repeating unit in all the repeating units in the resin (P1) is preferably from 1 mol% to 20 mol%, more preferably from 5 mol% to 15 mol%.

Specific examples of the repeating unit having an alicyclic hydrocarbon structure which does not contain a polar group and which does not exhibit acid decomposition property are listed below, but the present invention is not limited to these specific examples. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[化49]

Further, the resin (P1) may contain the following monomer components in view of an improvement in Tg or an improvement in dry etching resistance, an effect of the internal filter of the out of band light, and the like.

The resin (P1) may also contain a repeating unit represented by the following formula (V) or the following formula (VI).

[化50]

In the formula, R ₆ and R ₇ each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or a decyloxy group, a cyano group or a nitro group. An amine group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.

n ₃ represents an integer of 0-6. X ⁴ is a methylene group, an oxygen atom or a sulfur atom.

Specific examples of the repeating unit represented by the general formula (V) or the general formula (VI) are shown below, but are not limited to these specific examples.

[化51]

Further, the resin (P1) may also contain a repeating unit having a cyclic carbonate structure.

The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following formula (A-1).

[化52]

In the formula (A-1), R _A ¹ represents a hydrogen atom or an alkyl group.

When R _A ² is 2 or more, the substituents are independently represented.

A represents a single bond or a divalent linking group.

Z represents an atomic group which forms a monocyclic or polycyclic structure together with a group represented by -O-C(=O)-O- in the formula.

n represents an integer of 0 or more.

With respect to the repeating unit represented by the formula (A-1), the contents described in paragraphs 0293 to 0304 of JP-A-2014-41328 can be referred to, and the contents are incorporated in the present specification.

In the resin (P1) used in the composition of the present invention, in order to adjust the dry etching resistance or the standard developer suitability of the resist, the substrate adhesion, the resist profile, and the like as a resist, The resolving power, heat resistance, sensitivity, and the like of the necessary performance are appropriately set, and the molar ratio of each repeating structural unit is appropriately set.

Specific examples of the resin (P1) are listed below, but the present invention is not limited thereto.

[化53]

[54]

[化55]

[化56]

[化57]

The form of the resin (P1) of the present invention may be in any form of a random type, a block type, a comb type, or a star type.

The resin (P1) can be synthesized, for example, by radical, cationic, or anionic polymerization of an unsaturated monomer corresponding to each structure. Further, after the polymerization is carried out using an unsaturated monomer corresponding to the precursor of each structure, a polymer reaction may be carried out to obtain a target resin.

For example, a general synthesis method is a general polymerization method in which an unsaturated monomer and a polymerization initiator are dissolved in a solvent and heated to carry out polymerization; and the unsaturated solvent is added dropwise in 1 hour to 10 hours in a heating solvent. The dropwise addition polymerization method of the solution of the monomer and the polymerization initiator is preferably a dropping polymerization method.

The solvent to be used for the polymerization is, for example, a solvent which can be used in the preparation of a sensitizing ray-sensitive or radiation-sensitive resin composition to be described later, and more preferably a solvent which is the same as the solvent used in the composition of the present invention. Polymerization is preferred. Thereby, generation of particles at the time of storage can be suppressed.

The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate polymerization. The radical initiator is preferably an azo initiator, and is preferably an azo initiator having an ester group, a cyano group or a carboxyl group. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), and the like. The polymerization may also be carried out in the presence of a chain transfer agent (for example, an alkyl mercaptan or the like) as needed.

The concentration of the reaction is from 5% by mass to 70% by mass, preferably from 10% by mass to 50% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, and more preferably from 40 ° C to 100 ° C. The reaction time is usually from 1 hour to 48 hours, preferably from 1 hour to 24 hours, and more preferably from 1 hour to 12 hours.

After completion of the reaction, the mixture was allowed to cool to room temperature and purified. For the purification, a usual method such as the following method: a liquid-liquid extraction method in which residual monomers or oligomer components are removed by a combination of water washing or a suitable solvent, and a solution state such as ultrafiltration which is extracted by removing only a specific molecular weight or less is used. a purification method; or a resin which is solidified in a poor solvent by dropping a resin solution into a poor solvent, thereby removing a residual monomer or the like by a reprecipitation method or using a poor solvent to wash the filtered resin slurry. A purification method or the like in a solid state. For example, a solvent (poor solvent) in which the resin is poorly soluble or insoluble is brought into contact with the resin in a volume of 10 times or less, preferably 10 times to 5 times the volume of the reaction solution, whereby the resin is solid. Form of precipitation.

The solvent (precipitating or reprecipitating solvent) used in the precipitation or reprecipitation operation of the polymer solution may be a poor solvent of the polymer, and may be derived from a hydrocarbon, a halogenated hydrocarbon, a nitro compound, or an ether depending on the kind of the polymer. A ketone, an ester, a carbonate, an alcohol, a carboxylic acid, water, a mixed solvent containing the solvent, and the like are appropriately selected and used. Among these solvents, the precipitation or reprecipitation solvent is preferably a solvent containing at least an alcohol (particularly methanol or the like) or water.

The amount of the solvent to be used for precipitation or reprecipitation is appropriately selected in consideration of efficiency, productivity, etc., and is usually 100 parts by mass to 10,000 parts by mass, preferably 200 parts by mass to 2,000 parts by mass, based on 100 parts by mass of the polymer solution, and further Preferably, it is 300 parts by mass to 1000 parts by mass.

The temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency or workability, and is usually about 0 ° C to 50 ° C, preferably about room temperature (for example, about 20 ° C to 35 ° C). The precipitation or reprecipitation operation is carried out by a known method such as a batch type or a continuous type using a conventional mixing container such as a stirring tank.

The precipitated or reprecipitated polymer is usually subjected to conventional solid-liquid separation such as filtration, centrifugation, and the like, and dried for use. Filtration is preferably carried out under pressure using a solvent resistant filter material. The drying is carried out at a temperature of from about 30 ° C to 100 ° C, preferably from about 30 ° C to 50 ° C under normal pressure or reduced pressure (preferably under reduced pressure).

Further, the resin may be precipitated and separated, and then dissolved again in the solvent to be in contact with the solvent in which the resin is poorly soluble or insoluble. That is, it may be a method comprising the steps of: after the completion of the radical polymerization reaction, contacting the polymer with a polymer which is poorly soluble or insoluble, and precipitating the resin (step a); Separating (step b); re-dissolving in a solvent to prepare a resin solution A (step c); thereafter, making the resin insoluble or insoluble solvent less than 10 times the volume of the resin solution A (preferably 5 times) The following volume amount) is brought into contact with the resin solution A, thereby precipitating the resin solid (step d); and separating the precipitated resin (step e).

The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate polymerization. The radical initiator is preferably an azo initiator, and is preferably an azo initiator having an ester group, a cyano group or a carboxyl group. Preferred examples of the initiator include azobisisobutyronitrile, azobis-dimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), and the like. The initiator is added as needed or separately, and after completion of the reaction, it is introduced into a solvent and the desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is from 5% by mass to 50% by mass, preferably from 10% by mass to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, and more preferably from 60 ° C to 100 ° C.

The molecular weight of the resin (P1) of the present invention is not particularly limited, and the weight average molecular weight is preferably in the range of from 1,000 to 100,000, more preferably in the range of from 1,500 to 60,000, still more preferably in the range of from 2,000 to 30,000. When the weight average molecular weight is in the range of 1,000 to 100,000, deterioration of heat resistance or dry etching resistance can be prevented, and deterioration of developability or viscosity can be prevented, and film formability can be deteriorated. Here, the weight average molecular weight of the resin is determined by gel permeation chromatography (GPC) (carrier: Tetrahydrofuran (THF) or N-methyl-2-pyrrolidone (N-methyl-). 2-pyrrolidone, NMP)) The polystyrene-converted molecular weight measured.

Further, the degree of dispersion (Mw/Mn) is preferably from 1.00 to 5.00, more preferably from 1.03 to 3.50, still more preferably from 1.05 to 2.50. The smaller the molecular weight distribution, the more excellent the resolution and the resist shape, and the smoothness of the side walls of the resist pattern and the excellent roughness.

The resin (P1) of the present invention may be used alone or in combination of two or more. The content of the resin (P1) is preferably 20% by mass to 99% by mass, more preferably 30% by mass to 89% by mass based on the total solid content of the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention. %, particularly preferably 40% by mass to 79% by mass. [2] Resin (B) which is different from the resin (P1) and which is decomposed by the action of an acid to change the solubility of the developer. The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention may also contain A resin (hereinafter also referred to as a resin (B)) which is different in the resin (P1) and decomposed by the action of an acid to change the solubility of the developer.

The resin (B) is a resin having a structure in which a polar group is decomposed and decomposed by an action of an acid (hereinafter also referred to as an "acid-decomposable group").

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

Examples of the polar group include a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a sulfonic acid group, and a thiol group.

Examples of the group which is detached by the action of an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(=O). -OC(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )-C(=O)-OC(R ₃₆ ) (R ₃₇ ) (R ₃₈ ) and the like.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may also be bonded to each other to form a ring. R ₀₁ to R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The resin (B) can be synthesized in accordance with a usual method (for example, radical polymerization).

The weight average molecular weight of the resin (B) is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000, still more preferably from 3,000 to 15,000, still more preferably from 3,000 to 10,000, in terms of polystyrene equivalent value by the GPC method. By setting the weight average molecular weight to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance or dry etching resistance, and it is possible to prevent deterioration of developability or increase in viscosity and deterioration of film formability.

The degree of dispersion (molecular weight distribution) is usually from 1 to 3, preferably from 1 to 2.6, more preferably from 1 to 2, and particularly preferably from 1.4 to 1.7. The smaller the molecular weight distribution, the more excellent the resolution and the resist shape, and the smoothness of the side walls of the resist pattern and the excellent roughness.

The resin (B) may be used in combination of two or more kinds.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may contain the resin (B) or the resin (B), and in the case of containing the resin (B), it may be composed of a photosensitive ray-sensitive or radiation-sensitive resin. The total solid content of the product and the amount of the resin (B) to be added are usually from 1% by mass to 50% by mass, preferably from 1% by mass to 30% by mass, particularly preferably from 1% by mass to 15% by mass.

The resin (B) is exemplified in paragraphs [0059] to [0594] of the paragraphs [0059] to [0169] of JP-A-2010-217884, and the paragraph [0214] to [0594] of Japanese Patent Application No. 2011-217048. Recorder. [3] (B) Compound which generates an acid by irradiation with actinic rays or radiation. The composition of the present invention preferably contains a compound which generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as "acid". Producer" or "photoacid generator").

The acid generator is not particularly limited as long as it is known, and it is preferred to generate an organic acid such as sulfonic acid, bis(alkylsulfonyl) ruthenium or tri(alkane) by irradiation with actinic rays or radiation. A compound of at least any of the sulfonyl) methide.

The compound (B) which generates an acid by irradiation with actinic rays or radiation may be in the form of a low molecular compound or may be in a form incorporated into a part of the polymer. Further, the form of the low molecular compound and the form of a part of the polymer may be used in combination.

When the compound (B) which generates an acid by irradiation with actinic rays or radiation is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.

When the compound (B) which generates an acid by irradiation with actinic rays or radiation is in a form of being incorporated into a part of the polymer, a part of the acid-decomposable resin may be incorporated, or may be incorporated into The acid-decomposable resin is different in the resin.

More preferably, it is a compound represented by the following general formula (ZI), general formula (ZII), and general formula (ZIII).

[化58]

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a carbon number of usually 1 to 30, preferably 1 to 20.

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring. The group formed by bonding two of R ₂₀₁ to R ₂₀₃ may, for example, be an alkyl group (for example, a butyl group or a pentyl group).

Z ^- represents a non-nucleophilic anion (an anion having a significantly lower ability to cause a nucleophilic reaction).

Examples of the non-nucleophilic anion include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkyl group). a carboxylate anion or the like), a sulfonyl quinone imine anion, a bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl) methide anion, and the like.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number of 3 to 30. Cycloalkyl.

The aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group or a naphthyl group.

The recited alkyl, cycloalkyl and aryl groups may have a substituent. Specific examples thereof include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3 to 3). 15) an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), a mercapto group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyloxy group. (preferably having a carbon number of 2 to 7), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), or an alkylimidosulfonyl group ( Preferably, the carbon number is 2 to 15), the aryloxysulfonyl group (preferably having a carbon number of 6 to 20), the alkylaryloxysulfonyl group (preferably having a carbon number of 7 to 20), or a cycloalkyl group. An oxysulfonyl group (preferably having a carbon number of 10 to 20), an alkyloxyalkyloxy group (preferably having a carbon number of 5 to 20), a cycloalkylalkyloxyalkyloxy group (preferably Carbon number 8 to 20). Further, as the aryl group and the ring structure of each group, an alkyl group (preferably having 1 to 15 carbon atoms) may be mentioned as a substituent.

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group or a naphthylbutyl group.

Examples of the sulfonyl quinone imine anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl)phosphonium anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. The substituent of the alkyl group may, for example, be a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group or a cycloalkylaryloxysulfonate. The group or the like is preferably a fluorine atom or an alkyl group substituted by a fluorine atom.

Further, the alkyl groups in the bis(alkylsulfonyl) quinone imine anion may be bonded to each other to form a ring structure. Thereby, the acid strength increases.

Examples of the other non-nucleophilic anion include phosphorus fluoride (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), and cesium fluoride (for example, SbF ₆ ^- ).

The non-nucleophilic anion is preferably an aliphatic sulfonate anion having at least the α position of the sulfonic acid substituted by a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a fluorine atom-containing group, and an alkyl group substituted by a fluorine atom. A bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl) methide anion having an alkyl group substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (and more preferably a carbon number of 4 to 8), a fluorine atom-containing benzenesulfonate anion, and more preferably a nonafluorobutanesulfonate anion or a perfluorooctanesulfonate. Acid anion, pentafluorobenzenesulfonate anion, 3,5-bis(trifluoromethyl)benzenesulfonate anion.

From the viewpoint of acid strength, in order to improve the sensitivity, it is preferred that the pKa of the generated acid is -1 or less.

Further, the non-nucleophilic anion may be an anion represented by the following general formula (AN1) as a preferred embodiment.

[化59]

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of cases, R ¹ and R ² may be the same or different.

L represents a divalent linking group, and when there are a plurality of L, the L may be the same or different.

A represents a cyclic organic group.

x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.

The alkyl group in the alkyl group substituted by a fluorine atom of Xf preferably has a carbon number of from 1 to 10, more preferably a carbon number of from 1 to 4. Further, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C. ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , of which a fluorine atom or CF _{3 is} preferred. It is especially preferred that the two Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and is preferably a group having 1 to 4 carbon atoms. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent of R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _{15 .} , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , wherein CF _{3 is} preferred.

R ¹ and R ^{2 are} preferably a fluorine atom or CF ₃ .

x is preferably from 1 to 10, more preferably from 1 to 5.

y is preferably 0 to 4, more preferably 0.

z is preferably from 0 to 5, more preferably from 0 to 3.

The divalent linking group of L is not particularly limited, and examples thereof include: -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, cycloalkane The base group, the alkenyl group, or the above-mentioned plurality of linking groups are preferably a linking group having a total carbon number of 12 or less. Among them, preferred are -COO-, -OCO-, -CO-, -O-, and more preferably -COO-, -OCO-.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (including not only aromatics but also aromatic ones).

The alicyclic group may be a monocyclic ring or a polycyclic ring, preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, a norbornyl group, a tricyclodecylalkyl group or a tetracyclodecylalkyl group. A polycyclic cycloalkyl group such as tetracyclododecyl or adamantyl. Among them, from the viewpoint of suppressing the diffusibility in the film in the post-exposure heating step and improving the Mask Error Enhancement-Factor (MEEF), it is preferably a norbornene group, a tricyclodecyl group, or a tetrazide. An alicyclic group having a large volume structure having a carbon number of 7 or more, such as a cycloalkyl group, a tetracyclododecyl group or an adamantyl group.

Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.

Examples of the heterocyclic group include a group derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, a group derived from a furan ring, a thiophene ring or a pyridine ring is preferred.

In addition, the cyclic organic group may be a lactone structure, and a lactone structure represented by the general formula (LC1-1) to the general formula (LC1-17) which the resin (P1) may have is mentioned.

The cyclic organic group may have a substituent, and the substituent may be an alkyl group (which may be any of a linear chain, a branched group, or a cyclic group, preferably a carbon number of 1 to 12) or a cycloalkyl group (may be Any one of a monocyclic ring, a polycyclic ring and a spiro ring, preferably having a carbon number of 3 to 20), an aryl group (preferably having a carbon number of 6 to 14), a hydroxyl group, an alkoxy group, an ester group, a decylamino group or an amine group. Formate group, guanidino group, thioether group, sulfonamide group, sulfonate group, and the like. Further, the carbon constituting the cyclic organic group (carbon which contributes to the formation of a ring) may also be a carbonyl carbon.

The organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may, for example, be an aryl group, an alkyl group or a cycloalkyl group.

Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , preferably at least one is an aryl group, and more preferably all three are aryl groups. The aryl group may be a heteroaryl group such as an anthracene residue or a pyrrole residue, in addition to a phenyl group or a naphthyl group. The alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. More preferably, the alkyl group may be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. More preferably, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group. These groups may have more substituents. Examples of the substituent include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3 to 3). 15) an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), a mercapto group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyloxy group. (preferably, carbon number is 2 to 7), etc., but it is not limited to these groups.

Further, when two of R ₂₀₁ to R ₂₀₃ are bonded to each other to form a ring structure, the structure represented by the following formula (A1) is preferred.

[60]

In the formula (A1), R ^1a to R ^13a each independently represent a hydrogen atom or a substituent.

In the case of R ^1a to R ^13a , preferably one to three are not hydrogen atoms, and more preferably any of R ^9a to R ^13a is not a hydrogen atom.

Za represents a single bond or a divalent linking group.

X ^- is the same as Z ^- in the formula (ZI).

Specific examples of the case where R ^1a to R ^{13a are} not a hydrogen atom include the following groups: a halogen atom, a linear or branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and a cyanogen. Base, nitro, carboxyl, alkoxy, aryloxy, decyloxy, heterocyclic oxy, decyloxy, amine methoxycarbonyl, alkoxycarbonyloxy, aryloxycarbonyloxy, amine Base (including anilino), ammonium, mercaptoamine, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkylsulfonylamino and Arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfo, alkylsulfinyl and arylsulfinyl, alkylsulfonyl And arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminemethanyl, arylazo and heterocyclic azo, fluorenylene, phosphino, phosphinyl, oxygen Phosphonooxy, phosphinylamino, phosphono, decyl, decyl, ureido, boric acid (-B(OH) ₂ ), phosphate (-OPO(OH) ₂ ), sulfate groups (-OSO ₃ H), other Known substituents.

When R ^1a to R ^{13a are} not a hydrogen atom, a linear, branched or cyclic alkyl group substituted with a hydroxyl group is preferred.

The divalent linking group of Za may, for example, be an alkyl group, an aryl group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamino group, an ether bond, a thioether bond, an amine group, or a disulfide group. Ether group, -(CH ₂ ) _n -CO-, -(CH ₂ ) _n -SO ₂ -, -CH=CH-, aminocarbonylamino group, aminosulfonylamino group, etc. (n is 1 to 3) Integer).

Further, a preferred structure of the case where at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group is exemplified by paragraph 0047 of the Japanese Patent Laid-Open Publication No. 2004-233661, paragraph 0048, and Japanese Patent Laid-Open No. 2003-35948 The compound exemplified as the formula (I-1) to the formula (I-70) in the specification of the U.S. Patent Application Publication No. 2003/0224288 A1, the disclosure of which is incorporated herein by reference. A cationic structure such as a compound exemplified by the formula (IA-1) to the formula (IA-54) and the formula (IB-1) to the formula (IB-24).

In the general formula (ZII) and the general formula (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ are the same as those described for the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI).

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. The substituent may also be a group which the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI) may have.

Z ^- represents a non-nucleophilic anion, and is the same as the non-nucleophilic anion of Z ^- in the general formula (ZI).

Further, the acid generator may be a compound represented by the following formula (ZIV), formula (ZV) or formula (ZVI).

[化61]

In the general formulae (ZIV) to (ZVI), Ar ₃ and Ar ₄ each independently represent an aryl group.

R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ include the same groups as the specific examples of the aryl group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the above formula (ZI). group.

Specific examples of the alkyl group and the cycloalkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ include specific examples of the alkyl group and the cycloalkyl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the above formula (ZI). The same group.

The alkylene group of A may, for example, be an alkylene group having 1 to 12 carbon atoms (e.g., methylene, ethyl, propyl, isopropyl, butyl, isobutyl, etc.), The base may be an alkenyl group having 2 to 12 carbon atoms (e.g., a vinyl group, a propenyl group, a butyl group, etc.), and the aryl group of A may, for example, be a phenyl group having 6 to 10 carbon atoms (e.g., a phenyl group). , methyl phenyl, naphthyl, etc.).

Specific examples of the acid generator include, for example, paragraphs 0368 to 0377 of JP-A-2014-41328, paragraphs 0240 to 0262 of JP-A-2013-228681, and US patents. The application is described in paragraph 0339 of the specification of the publication No. 2015/004533.

[化62]

[化63]

The acid generators may be used alone or in combination of two or more.

The content of the acid generator is preferably from 0.1% by mass to 50% by mass, more preferably from 0.5% by mass to 45% by mass, even more preferably from 1% by mass to 40% by mass based on the total solid content of the composition.

[4] A compound which decomposes and generates an acid by the action of an acid. The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention may further contain one or two or more kinds of acids which are decomposed by an action of an acid to generate an acid. Compound. The acid produced by the compound which decomposes by the action of an acid and generates an acid is preferably a sulfonic acid, a methionic acid or a quinone.

A compound which can be used in the present invention to decompose and generate an acid by the action of an acid can be referred to, for example, in the description of paragraphs 0379 to 0382 of JP-A-2014-41328, the contents of which are incorporated herein by reference. .

The compound which decomposes by the action of an acid and generates an acid may be used alone or in combination of two or more.

Further, the content of the compound which decomposes by the action of an acid and generates an acid is preferably from 0.1% by mass to 40% by mass based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition, and more preferably 0.5% by mass to 30% by mass, and more preferably 1.0% by mass to 20% by mass. [5] Resin solvent (coating solvent) The solvent which can be used for the preparation of the composition is not particularly limited as long as the components are dissolved, and examples thereof include an alkylene glycol monoalkyl ether carboxylate (propylene glycol monomethyl ether). Propylene Glycol Monomethyl Ether Acetate (PGMEA; alias 1-methoxy-2-ethoxypropane propane), etc., alkanediol monoalkyl ether (Propylene Glycol Monomethyl Ether (PGME; An alias of 1-methoxy-2-propanol), an alkyl lactate (ethyl lactate, methyl lactate, etc.), a cyclic lactone (γ-butyrolactone, etc., preferably a carbon number of 4 to 10) a chain or cyclic ketone (2-heptanone, cyclohexanone, etc., preferably having a carbon number of 4 to 10), an alkyl carbonate (ethyl carbonate, propyl carbonate, etc.), a carboxylic acid The alkyl ester (preferably an alkyl acetate such as butyl acetate), an alkyl alkoxyacetate (ethyl ethoxypropionate), or the like may be used singly or in combination.

Other solvents which can be used include, for example, the solvent described in [0244] of the specification of U.S. Patent Application Publication No. 2008/0248425 A1.

Among them, an alkanediol monoalkyl ether carboxylate and an alkylene glycol monoalkyl ether are preferred.

These solvents may be used alone or in combination of two or more. In the case of mixing two or more kinds, it is preferred to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40.

The solvent having a hydroxyl group is preferably an alkanediol monoalkyl ether, and the solvent having no hydroxyl group is preferably an alkanediol monoalkyl ether carboxylate. [6] Basic compound The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a basic compound. The basic compound is preferably a compound which is more basic than phenol. Further, the basic compound is preferably an organic basic compound, more preferably a nitrogen-containing basic compound.

The nitrogen-containing basic compound which can be used is not particularly limited, and for example, the compounds classified into the following (1) to (7) can be used.

(1) a compound represented by the general formula (BS-1)

[化64]

In the general formula (BS-1), R independently represents a hydrogen atom or an organic group. Among them, at least one of the three R is an organic group. The organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group or an aralkyl group.

The carbon number of the alkyl group as R is not particularly limited, but is usually 1 to 20, preferably 1 to 12.

The carbon number of the cycloalkyl group as R is not particularly limited, and is usually from 3 to 20, preferably from 5 to 15.

The carbon number of the aryl group as R is not particularly limited, but is usually 6 to 20, preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

The carbon number of the aralkyl group as R is not particularly limited, but is usually 7 to 20, preferably 7 to 11. Specific examples thereof include a benzyl group and the like.

In the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group of R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkoxycarbonyl group.

Further, among the compounds represented by the formula (BS-1), at least two of R are preferably an organic group.

Specific examples of the compound represented by the formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, and ten. Tetraalkylamine, pentadecylamine, hexadecylamine, octadecylamine, diamine, methyloctadecylamine, dimethylundecylamine, N,N-dimethyl Dodecylamine, methyl di-octadecylamine, N,N-dibutylaniline, N,N-dihexylaniline, 2,6-diisopropylaniline and 2,4,6- Tris(t-butyl)aniline.

Further, preferred examples of the basic compound represented by the formula (BS-1) include at least one compound wherein R is a hydroxyl group-substituted alkyl group. Specific examples thereof include triethanolamine and N,N-dihydroxyethylaniline.

Further, the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxygen-extended alkyl chain can also be formed. The oxygen alkyl chain is preferably -CH ₂ CH ₂ O-. Specific examples thereof include tris(methoxyethoxyethyl)amine and the compounds exemplified in the third row and the 60th column of the specification of US Pat. No. 6,401,012.

In the basic compound represented by the formula (BS-1), examples of the basic compound having a hydroxyl group or an oxygen atom include the following compounds.

[化65]

[化66]

(2) Compound having a nitrogen-containing heterocyclic structure The nitrogen-containing heterocyclic ring may have aromaticity or may not be aromatic. In addition, it may have a plurality of nitrogen atoms. Further, it may contain a hetero atom other than nitrogen. Specific examples thereof include a compound having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), a compound having a piperidine structure [N-hydroxyethylpiperidine, and Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) phthalate, a compound having a pyridine structure (4-dimethylaminopyridine, etc.), and having an anthracene An antipyrine structure compound (antipyrine and hydroxyantipyrine, etc.).

Examples of preferred compounds having a nitrogen-containing heterocyclic structure include guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, oxazole, imidazole, pyrazole, pyrazine, pyrimidine, and the like. Anthracene, imidazoline, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholine. These compounds may have more substituents.

Preferred examples of the substituent include an amine group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, a decyl group, a decyloxy group, an aryl group, and an aromatic group. Oxyl, nitro, hydroxy and cyano groups.

Preferred examples of the basic compound include imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4,5. -triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine 2-(Aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6 -methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N-(2-aminoethyl)piperazine, N-(2-amine Benzyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1-(2-aminoethyl Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2-(aminomethyl)- 5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine and N-(2- Aminoethyl)morpholine.

Further, a compound having two or more ring structures can also be preferably used. Specific examples thereof include 1,5-diazobicyclo[4.3.0]non-5-ene and 1,8-diazobicyclo[5.4.0]-undec-7-ene.

(3) Amine compound having a phenoxy group The amine compound having a phenoxy group means a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group may have, for example, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, a decyloxy group, an aryloxy group, or the like. Substituent.

More preferably, the compound has at least one oxygen alkyl chain between the phenoxy group and the nitrogen atom. The number of oxygen-extended alkyl chains in one molecule is preferably from 3 to 9, more preferably from 4 to 6. In the oxygen alkyl chain, it is particularly preferably -CH ₂ CH ₂ O-.

Specific examples thereof include 2-[2-{2-(2,2-dimethoxy-phenoxyethoxy)ethyl}-bis-(2-methoxyethyl)]-amine, and Compound (C1-1) to compound (C3-3) exemplified in paragraph [0066] of the specification of US 2007/0224539 A1.

The amine compound having a phenoxy group can be obtained, for example, by heating a primary or secondary amine having a phenoxy group and a halogenated alkyl ether, and adding sodium hydroxide, potassium hydroxide, tetraalkylammonium, or the like. After the aqueous solution of the strong base is extracted, it is extracted with an organic solvent such as ethyl acetate or chloroform. Further, an amine compound having a phenoxy group can also be obtained by heating a primary or secondary amine with a halogenated alkyl ether having a phenoxy group at the terminal, and adding sodium hydroxide, potassium hydroxide and tetra After an aqueous solution of a strong base such as an alkylammonium is extracted with an organic solvent such as ethyl acetate or chloroform.

(4) Ammonium salt An ammonium salt can also be suitably used as the basic compound.

The cation of the ammonium salt is preferably a tetraalkylammonium cation substituted with an alkyl group having 1 to 18 carbon atoms, more preferably a tetramethylammonium cation, a tetraethylammonium cation, a tetrakis(n-butyl)ammonium cation, or four. (n-heptyl)ammonium cation, tetra(n-octyl)ammonium cation, dimethylhexadecyl ammonium cation, benzyltrimethyl cation, etc., preferably tetra(n-butyl)ammonium cation.

Examples of the anion of the ammonium salt include a halide, a sulfonate, a borate, a phosphate, a hydroxide, and a carboxylate. Among these, a hydroxide or a carboxylate is particularly preferred.

Halides are particularly preferred as chlorides, bromides and iodides. The sulfonate is particularly preferably an organic sulfonate having 1 to 20 carbon atoms. Examples of the organic sulfonate include an alkylsulfonate having 1 to 20 carbon atoms and an arylsulfonate.

The alkyl group contained in the alkyl sulfonate may also have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, a fluorenyl group, and an aryl group. Specific examples of the alkyl sulfonate include mesylate, ethanesulfonate, butanesulfonate, hexanosulfonate, octanesulfonate, benzylsulfonate, trifluoromethanesulfonate, and pentafluoroethane. Sulfonate and nonafluorobutanesulfonate.

Examples of the aryl group contained in the arylsulfonate include a phenyl group, a naphthyl group, and an anthracenyl group. The aryl groups may also have a substituent. The substituent is, for example, preferably a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms. Specifically, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a n-hexyl group, and a cyclohexyl group are preferable. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an anthracenyl group and a decyloxy group.

The carboxylate may be an aliphatic carboxylate or an aromatic carboxylate, and examples thereof include an acetate, a lactate, a pyruvate, a trifluoroacetate, an adamantane carboxylate, and a hydroxyadamantane carboxylate. Benzoate, naphthoate, salicylate, phthalate, phenolate, etc., especially preferably benzoate, naphthoate, phenolate, etc., most preferably benzene Formate.

In this case, the ammonium salt is preferably tetra(n-butyl)ammonium benzoate or tetrakis(n-butyl)ammonium phenolate.

In the case where the ammonium salt is a hydroxide, the ammonium salt is particularly preferably a tetraalkylammonium hydroxide having a carbon number of 1 to 8 (tetramethylammonium hydroxide and tetraethylammonium hydroxide, tetra-( N-butyl) ammonium or the like tetraalkylammonium hydroxide).

(5) A compound (PA) having a proton-receptive functional group and decomposing by irradiation with actinic rays or radiation to cause a decrease in proton acceptability, disappearance, or a change from a proton acceptor to an acidic compound (PA). The composition may further contain a compound as a basic compound having a proton-receptive functional group and decomposing by irradiation with actinic rays or radiation to cause a decrease in proton acceptability, disappearance, or a change in proton acceptability. A compound which is an acidic compound [hereinafter also referred to as a compound (PA)].

The term "proton acceptor functional group" refers to a group which can electrostatically interact with a proton or a functional group having an electron, such as a functional group having a macrocyclic structure such as a cyclic polyether, or a A functional group of a nitrogen atom of a non-shared electron pair of a yoke. The nitrogen atom having an unshared electron pair which does not contribute to π conjugate is, for example, a nitrogen atom having a partial structure represented by the following general formula.

[67] Non-shared electronic pair

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

The compound (PA) is decomposed by irradiation with actinic rays or radiation to produce a compound having reduced proton acceptability, disappearance, or acidity change from proton acceptor. Here, the decrease or disappearance of proton acceptor property or the change from proton acceptor property to acidity refers to a change in proton acceptor property caused by the addition of a proton to a proton acceptor functional group. Specifically, When a proton-addition product is formed from a compound (PA) having a proton-receptive functional group and a proton, the equilibrium constant in the chemical equilibrium is reduced.

Specific examples of the compound (PA) include the following compounds. Further, specific examples of the compound (PA) include those described in paragraphs 0421 to 0428 of JP-A-2014-41328, and paragraphs 0108 to 0116 of JP-A-2014-134686. These are incorporated into this specification. [化68-1]

Further, in the present invention, a compound (PA) other than the compound which produces the compound represented by the formula (PA-1) can be appropriately selected. For example, a compound which is an ionic compound and has a proton acceptor moiety in the cation moiety can also be used. More specifically, a compound represented by the following formula (7) or the like can be given.

[化68-2]

In the formula, A represents a sulfur atom or an iodine atom.

m represents 1 or 2, and n represents 1 or 2. Wherein, when A is a sulfur atom, m+n=3, and when A is an iodine atom, m+n=2.

R represents an aryl group.

R _N represents an aryl group substituted with a proton acceptor functional group.

X ^- represents a counter anion.

Specific examples of X ^- may be the same as Z- in the above formula (ZI).

Specific examples of R and R _N aryl group may preferably be mentioned a phenyl group.

Specific examples of the proton acceptor functional group possessed by R _N are the same as the proton acceptor functional group described in the above formula (PA-1).

In the composition of the present invention, the compounding ratio of the compound (PA) in the total composition of the total solid content is preferably from 0.1% by mass to 10% by mass, more preferably from 1% by mass to 8% by mass.

(6) Antimony compound The composition of the present invention may further contain an anthracene compound having a structure represented by the following formula.

[化69]

Since the ruthenium compound stabilizes the positive charge dispersion of the conjugate acid by three nitrogens, it exhibits strong alkalinity.

The basicity of the ruthenium compound (A) of the present invention is preferably such that the pKa of the conjugated acid is 6.0 or more, and when it is 7.0 to 20.0, the neutralization reactivity with the acid is high and the roughness characteristics are excellent, which is preferable and preferable. It is 8.0 to 16.0.

Therefore, since the species is strongly alkaline, it can suppress the diffusibility of the acid and contribute to the formation of an excellent pattern shape.

In addition, the "pKa" here means that the pKa in an aqueous solution is described, for example, in "Chemical Fact (II)" (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). A low value indicates a greater acid strength. The pKa in the aqueous solution can be specifically determined by measuring the acid dissociation constant at 25 ° C using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can be used to calculate the Hammett based on the calculation. The substituent constant of Hammett) and the value of the database of well-known literature values. The values of pKa described in the present specification all indicate values obtained by calculation using the kit software.

Software Package 1: Advanced Chemistry Development (ACD/Labs) Software Version 8.14 (V8.14) for Solaris Systems (for Solaris) (1994-2007 ACD/Labs).

In the present invention, the term "logP" means a logarithmic value of the n-octanol/water partition coefficient (P), and is an effective parameter for imparting hydrophilicity/hydrophobicity to a wide range of compounds. The distribution coefficient is usually obtained by calculation rather than experiment. In the present invention, it is represented by CS Chem Draw Ultra version 8.0 (Ver. 8.0) software package (Crippen's method) Fragmentation method)) The calculated value.

Further, the log P of the hydrazine compound (A) is preferably 10 or less. By being less than the above value, it can be uniformly contained in the resist film.

The log P of the hydrazine compound (A) of the present invention is preferably in the range of 2 to 10, more preferably in the range of 3 to 8, and still more preferably in the range of 4 to 8.

Further, the ruthenium compound (A) of the present invention preferably has no nitrogen atom other than the ruthenium structure.

Specific examples of the ruthenium compound are shown below, but are not limited to these specific examples.

[化70]

(7) Low Molecular Compound Having a Nitrogen Atom and Has a Group Detached by the Action of an Acid The composition of the present invention may contain a low molecular compound having a nitrogen atom and having a group which is liberated by the action of an acid. (hereinafter also referred to as "low molecular compound (D)" or "compound (D)"). The low molecular compound (D) is preferably basic after being detached from the group which is detached by the action of an acid.

The group to be detached by the action of an acid is not particularly limited, and is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a semiamine acetal. A hemiaminal ether group is more preferably a urethane group or a hemiamine acetal group.

The molecular weight of the low molecular compound (D) having a group which is liberated by the action of an acid is preferably from 100 to 1,000, more preferably from 100 to 700, still more preferably from 100 to 500.

The compound (D) is preferably an amine derivative having a group which is liberated by an action of an acid on a nitrogen atom.

The compound (D) may also contain a urethane group having a protective group on a nitrogen atom. The protecting group constituting the urethane group can be represented by the following formula (d-1).

[71]

In the formula (d-1), R' each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkoxyalkyl group. R' may also be bonded to each other to form a ring.

R' is preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group. More preferably, it is a linear or branched alkyl group or a cycloalkyl group.

The specific structure of such a group is shown below.

[化72]

The compound (D) can also be constituted by arbitrarily combining the basic compound with the structure represented by the formula (d-1). The compound (D) is particularly preferably a structure represented by the following formula (A). Further, the compound (D) may be a low molecular compound having a group which is detached by the action of an acid, and may be equivalent to the basic compound.

[化73]

In the formula (A), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Further, when n = 2, the two Ra may be the same or different, and the two Ra may be bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having a carbon number of 20 or less) or a derivative thereof.

Rb each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. Wherein, in -C(Rb)(Rb)(Rb), when at least one Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.

At least two Rbs may also be bonded to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof. n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

In the formula (A), the alkyl group, the cycloalkyl group, the aryl group or the aralkyl group represented by Ra and Rb may be via a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, a side oxygen group. Substituted by a functional group such as a group, an alkoxy group or a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

An alkyl group, a cycloalkyl group, an aryl group and an aralkyl group of Ra and/or Rb (the alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted by the functional group, alkoxy group or halogen atom) ), for example, linear, branched, etc. derived from methane, ethane, propane, butane, pentane, hexane, heptane, octane, decane, decane, undecane, dodecane a group derived from an alkane, a group derived from one or more of the cycloalkyl groups such as cyclobutyl, cyclopentyl or cyclohexyl; derived from cyclobutane, cyclopentane a group of a cycloalkane such as cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane or adamantane, or a group derived from the cycloalkane such as methyl, ethyl or n-propyl One or more substituted groups of a linear or branched alkyl group such as isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl or t-butyl; a group derived from an aromatic compound such as benzene, naphthalene or anthracene, a group derived from the aromatic compound such as methyl, ethyl, n-propyl, isopropyl or n-butyl One or more substituted groups of a linear or branched alkyl group such as 2-methylpropyl, 1-methylpropyl or tert-butyl; derived from pyrrolidine, piperidine, morpholine a group of a heterocyclic compound such as tetrahydrofuran, tetrahydropyran, anthracene, porphyrin, quinoline, perhydroquinoline, oxazole or benzimidazole, the group derived from the heterocyclic compound is linear a group or a branched alkyl group or a group derived from one or more of the groups derived from an aromatic compound, a group derived from a linear or branched alkane or a group derived from a cycloalkane a phenyl group, a naphthyl group, a fluorenyl group or the like, one or more or more substituted groups derived from an aromatic compound group, or the substituent is a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, A group substituted with a functional group such as a morpholinyl group or a pendant oxy group.

Further, the divalent heterocyclic hydrocarbon group (preferably having a carbon number of 1 to 20) or a derivative thereof in which Ra is bonded to each other may, for example, be derived from pyrrolidine, piperidine, morpholine, 1, 4, 5, 6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5- Azabenzotriazole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, carbazole, benzimidazole, imidazolium [1,2-a]pyridine, (1S,4S)-(+)-2,5-diazabicyclo[2.2.1]heptane, 1,5,7-triazabicyclo[4.4.0] Heterocyclic compounds such as 癸-5-ene, anthracene, porphyrin, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane a group derived from a group derived from the heterocyclic compound by a group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, and derived from a hetero group One or more or one or more substituted groups of a functional group such as a ring compound, a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group or a pendant oxy group.

The compound represented by the formula (A) can be synthesized in accordance with JP-A-2007-298569, JP-A-2009-199021, and the like.

In the present invention, the low molecular compound (D) may be used alone or in combination of two or more.

Specific examples of the compound (D) which is particularly preferred in the present invention can be referred to, for example, in the paragraphs 0468 to 0470 of JP-A-2014-41328, the contents of which are incorporated herein by reference.

(8) Ionic compound represented by the formula (I) The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may further contain an ionic compound represented by the following formula (I).

[化74]

In the formula (I), A ^- represents an organic acid anion, L represents a single bond or a divalent linking group, X ⁺ represents a nitrogen cation or a sulfur cation, and Rx each independently represents an alkyl group or an aryl group. A plurality of Rx may be bonded to each other to form a ring, and the ring formed may have a nitrogen atom, an oxygen atom or a sulfur atom as a ring member.

N2 represents 3 when X ⁺ is a nitrogen cation, and 2 when X ⁺ is a sulfur cation.

With regard to the ionic compound represented by the general formula (I), for example, the contents described in paragraphs 0167 to 0177 of JP-A-2014-199273 can be cited, and the contents are incorporated in the present specification.

The composition of the present invention may contain the low molecular compound (D) or the low molecular compound (D), and in the case of the low molecular compound (D), the total solid content of the composition in combination with the basic compound The content of the compound (D) is usually 0.001% by mass to 20% by mass, preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass.

Further, when the composition of the present invention contains an acid generator, the ratio of the acid generator to the compound (D) used in the composition is preferably an acid generator / [compound (D) + the following basic compound] (Morby) = 2.5 to 300. In other words, in terms of the sensitivity and the resolution, the molar ratio is preferably 2.5 or more, and the degree of resolution due to the coarseness of the resist pattern over time after the post-exposure heat treatment is suppressed. Good for 300 or less. The acid generator / [compound (D) + the basic compound] (mole ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

In addition, the composition of the present invention can be exemplified by a compound synthesized in the examples of JP-A-2002-363146, and a compound described in paragraph 0108 of JP-A-2007-298569. Wait.

A photosensitive basic compound can also be used as the basic compound. As the photosensitive basic compound, for example, Japanese Patent Laid-Open Publication No. 2003-524799 and "J. Photopolym. Sci & Tech." (Vol. 8, P. 543-553 (1995)) and the like can be used. The compound described.

The molecular weight of the basic compound is usually from 100 to 1,500, preferably from 150 to 1300, more preferably from 200 to 1,000.

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

When the composition of the present invention contains a basic compound, the content of the basic compound is preferably from 0.01% by mass to 8.0% by mass, more preferably from 0.1% by mass to 5.0% by mass based on the total solid content of the composition. More preferably, it is 0.2 mass% - 4.0 mass%.

The molar ratio of the basic compound to the photoacid generator is preferably from 0.01 to 10, more preferably from 0.05 to 5, still more preferably from 0.1 to 3. If the molar ratio is excessively increased, the sensitivity and/or resolution may be lowered. If the molar ratio is excessively reduced, a reduction in pattern may occur between exposure and heating (post-baking). More preferably, it is 0.05 to 5, and further preferably 0.1 to 3. In addition, the photo-acid generator of the molar ratio is based on the total amount of the repeating unit (B) of the resin and the photoacid generator which may be further contained in the resin. [7] Hydrophobic Resin (HR) The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention may have a hydrophobic resin (HR) in addition to the resin (P1).

The hydrophobic resin (HR) preferably contains a group having a fluorine atom, a group having a ruthenium atom, or a hydrocarbon group having 5 or more carbon atoms in order to be present on the surface of the film. These groups may be present in the main chain of the resin or may be substituted on the side chain. Specific examples of the hydrophobic resin (HR) are shown below.

[化75]

[化76]

[化77]

In addition, as described above, the hydrophobic resin can be preferably used as described in JP-A-2011-248019, JP-A-2010-175859, and JP-A-2012-032544. [8] Surfactant The composition of the present invention may further contain a surfactant. By using a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used, a pattern having less adhesion and less development defects can be formed with good sensitivity and resolution.

It is especially preferable to use a fluorine-based and/or a lanthanoid surfactant as the surfactant.

Examples of the fluorine-based and/or lanthanoid surfactants include the surfactants described in [0276] of the specification of U.S. Patent Application Publication No. 2008/0248425. Also available: Eftop EF301 or EF303 (made by New Akita Chemicals Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M); Megafac F171 , F173, F176, F189, F113, F110, F177, F120 or R08 (made by Di shengsheng (DIC)); Surflon S-382, SC101, 102, 103, 104, 105 or 106 ( Asahi Glass Co., Ltd.; Troysol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by East Asian Synthetic Chemicals Co., Ltd.); Surflon (Surflon) ) S-393 (made by Seimi Chemical); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (Jemco (JEMCO) ) (manufacturing); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (Nios ( NEOS) (manufacturing)). Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a lanthanoid surfactant.

Further, in addition to the well-known surfactants as described above, the surfactant may also be used by a telomerization method (also referred to as a telomer method) or an oligomerization (oligomerization). A fluoroaliphatic compound produced by a method (also known as an oligomer method) is synthesized. Specifically, a polymer having a fluoroaliphatic group introduced from the aliphatic compound can also be used as a surfactant. The fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

The polymer having a fluoroaliphatic group is preferably a monomer having a fluoroaliphatic group and (poly(oxyalkylene)) acrylate or methacrylate and/or (poly(oxyalkylene))methyl group. The acrylate copolymer may be distributed irregularly or may be subjected to block copolymerization.

Examples of the poly(oxyalkylene) group include a poly(oxyethylidene) group, a poly(oxypropyl) group, and a poly(oxybutylene) group. Further, it may be in the same chain as poly(oxygen extension ethyl, block extension of oxygen-extended propyl group and oxygen-extended ethyl group) and poly(block-connecting body of oxygen-extended ethyl group and oxygen-extended propyl group). A unit having an alkyl group having a different chain length.

Further, the copolymer of a fluoroaliphatic group and a (poly(oxyalkylene)) acrylate or methacrylate may be different or different from two or more monomers having a fluoroaliphatic group. A ternary or higher copolymer obtained by simultaneously copolymerizing two or more kinds of (poly(oxyalkylene)) acrylate or methacrylate.

For example, commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by Diane Health (DIC) Co., Ltd.). Further, a copolymer of acrylate or methacrylate having a C ₆ F ₁₃ group and (poly(oxyalkylene)) acrylate or methacrylate, an acrylate having a C ₆ F ₁₃ group or a group can be exemplified. Copolymer of acrylate and (poly(oxyethylidene)) acrylate or methacrylate with (poly(oxypropyl)) acrylate or methacrylate, acrylate having C ₈ F ₁₇ group Or a copolymer of methacrylate with (poly(oxyalkylene)) acrylate or methacrylate, and an acrylate or methacrylate having a C ₈ F ₁₇ group with (poly(oxyethyl) a copolymer of acrylate or methacrylate with (poly(oxypropyl)) acrylate or methacrylate, and the like.

Further, a surfactant other than the fluorine-based and/or lanthanide-based surfactants described in [0280] of the specification of the 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, the content of the surfactant is preferably from 0% by mass to 2% by mass based on the total solid content of the composition, and more preferably from 0.0001% by mass to 2%. The mass% is further preferably 0.0005 mass% to 1 mass%. [9] Other Additives The composition of the present invention may contain, in addition to the components described above, a carboxylic acid, a carboxylic acid strontium salt, and a Proceeding of The International Society for Optical. Engineering, Proceeding of SPEI) (2724, 355 (1996)), etc., a dissolution inhibiting compound having a molecular weight of 3,000 or less, a dye, a plasticizer, a photosensitizer, a light absorbing agent, an antioxidant, and the like.

Particularly, in order to improve the performance, a carboxylic acid can be preferably used. The carboxylic acid is preferably an aromatic carboxylic acid such as benzoic acid or naphthoic acid.

The content of the carboxylic acid in the total solid content concentration of the composition is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, even more preferably 0.01% by mass to 3% by mass.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used in a film thickness of 10 nm to 250 nm, and more preferably in a film thickness of 20 nm to 200 nm, from the viewpoint of improving the resolution. Further, it is preferably used in a film thickness of 30 nm to 100 nm. The film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range and having an appropriate viscosity to improve coatability and film formability.

The solid content concentration of the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is usually 1.0% by mass to 10% by mass, preferably 2.0% by mass to 5.7% by mass, and more preferably 2.0% by mass to 5.3% by mass. By setting the solid content concentration to the above range, the resist solution can be uniformly applied onto the substrate, and a resist pattern having excellent line width roughness can be formed. Though the reason for this is not clear, it is considered that the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, thereby suppressing aggregation of a material, particularly a photoacid generator, in the resist solution. As a result, a uniform resist film can be formed.

The solid content concentration refers to the weight percentage of the weight of the resist component other than the solvent to the total weight of the sensitizing ray-sensitive or radiation-sensitive resin composition.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is obtained by dissolving the component in a predetermined organic solvent, preferably in the mixed solvent, filtering the filter, and applying it to a predetermined support (substrate). ) use it. The filter used for the filtration of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon having a pore diameter of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. When the filter is filtered, for example, it can be circulated and filtered as in the case of JP-A-2002-62667, and a plurality of filters can be filtered in series or in parallel. Alternatively, the composition can be filtered multiple times. Further, the composition may be subjected to a degassing treatment or the like before and after the filter is filtered. [Pattern Forming Method] Next, the pattern forming method of the present invention will be described. As described above, the pattern forming method of the present invention sequentially includes: a step of forming a film using a photosensitive ray-sensitive or radiation-sensitive resin composition; a step of exposing the film; and using the developing solution for the exposed portion The film is developed to form a positive pattern.

According to the pattern forming method of the present invention, it is possible to provide an ultrafine region (for example, a region having a line width or a gap width of several tens of nm) while satisfying high resolution, high dissolution contrast, and high dry etching resistance. A method for forming a pattern, a sensitizing ray-sensitive or radiation-sensitive resin composition, a sensitizing ray-sensitive or radiation-sensitive film, a method for producing an electronic device using the same, and an electronic device. The reason is not clear, but it is estimated as follows.

It is considered that the photosensitive ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention contains the resin (P1) having a repeating unit represented by the general formula (1), and thus the sensitizing ray is used. The adhesion between the sensitizing ray-sensitive or radiation-sensitive film formed by the radiation-sensitive resin composition and the substrate is improved.

It is considered that the collapse of the pattern is suppressed when the line and gap patterns are formed, and as a result, the resolution is improved.

Further, it is considered that the repeating unit represented by the above formula (1) has an aromatic ring group, and thus is formed by a sensitizing ray-sensitive or radiation-sensitive resin composition containing the resin (P1) having the repeating unit. The intensity of the ray- or radiation-sensitive linear film is improved, and the dry etching resistance is improved.

Further, it is considered that the resin (P1) contains a repeating unit represented by the formula (1), and the reactivity of the resin (P1) with respect to an acid is improved, and the polarity of the resin (P1) is decomposed by acid decomposition. .

It is considered that the dissolution contrast of the exposed portion and the unexposed portion with respect to the developer is improved, and the resolution at the time of forming the line and the gap pattern is improved.

It is considered that the effect is particularly remarkable in the case where a fine pattern is formed by electron beam or extreme ultraviolet light exposure. (1) Film formation The sensitized ray-sensitive or radiation-sensitive film of the present invention is a film formed of the sensitized ray-sensitive or radiation-sensitive resin composition.

More specifically, the formation of the sensitizing ray-sensitive or radiation-sensitive film can be carried out by dissolving the respective components of the sensitized ray-sensitive or radiation-sensitive resin composition in a solvent, and performing filter filtration as needed. Thereafter, it is applied onto a support (substrate). The filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon having a pore diameter of 0.5 μm or less, more preferably 0.2 μm or less, and still more preferably 0.1 μm or less.

The composition is applied to a substrate (for example, ruthenium or ruthenium dioxide coating) used in the production of an integrated circuit element by an appropriate coating method such as a spin coater. Thereafter, it is dried to form a photosensitive film. It is preferred to carry out the heating (prebaking) in the drying stage.

The film thickness is not particularly limited, and is preferably adjusted to a range of 10 nm to 500 nm, more preferably 10 nm to 200 nm, and preferably adjusted to a range of 10 nm to 100 nm. In the case where the sensitizing ray-sensitive or radiation-sensitive resin composition is applied by a spinner, the rotation speed thereof is usually from 500 rpm to 3000 rpm, preferably from 800 rpm to 2000 rpm, more preferably from 1,000 rpm to 1500 rpm.

The temperature for heating (prebaking) is preferably from 60 ° C to 200 ° C, more preferably from 80 ° C to 150 ° C, and still more preferably from 90 ° C to 140 ° C.

The heating (prebaking) time is not particularly limited, but is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and still more preferably 30 seconds to 90 seconds.

The heating can be carried out by means of a usual exposure/developer, or by using a heating plate or the like.

A commercially available inorganic or organic antireflection film can be used as needed. Further, the antireflection film may be applied to the lower layer of the sensitizing ray-sensitive or radiation-sensitive resin composition. As the antireflection film, any of an inorganic film type such as titanium, titanium oxide, titanium nitride, chromium oxide, carbon, or amorphous germanium, or an organic film type containing a light absorbing agent and a polymer material can be used. In addition, the organic anti-reflection film can also be used: DUV30 series sensitized ray- or radiation-sensitive film made by Brewer Science, DUV-40 series, AR-2 manufactured by Shipley , commercially available organic antireflection films such as AR-3 and AR-5. (2) Exposure exposure is performed by actinic rays or radiation. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, extreme ultraviolet light (EUV light), and an electron beam. The actinic rays or radiation are, for example, more preferably having a wavelength of 250 nm or less, especially 220 nm or less. Examples of such actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, and extreme ultraviolet light (EUV light). ) and electron beam. Preferred actinic rays or radiations include, for example, KrF excimer lasers, electron beams, X-rays, and EUV light. More preferably, electron beam, X-ray and EUV light, and thus electron beam and EUV light. (3) Baking is preferably performed by baking (heating) after exposure and before development.

The heating temperature is preferably from 60 ° C to 150 ° C, more preferably from 80 ° C to 150 ° C, and still more preferably from 90 ° C to 140 ° C.

The heating time is not particularly limited, but is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and still more preferably 30 seconds to 90 seconds.

The heating can be carried out by means of a usual exposure/developer, or by using a heating plate or the like.

The reaction of the exposed portion is promoted by baking to improve the sensitivity or pattern outline. Further, it is also preferred to include a heating step (Post Bake) after the rinsing step. The heating temperature and heating time are as described above. The developer and the eluent remaining between the patterns and the inside of the pattern are removed by baking. (4) Development and developing solution The developing solution used in the step of developing the photosensitive ray-sensitive or radiation-sensitive film formed by using the composition of the present invention is not particularly limited, and for example, an alkaline developing solution can be used.

As the alkaline developing solution, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine and di-n-butyl can be used. Secondary amines such as amines, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and hydroxide Tetrapropylammonium, tetrabutylammonium hydroxide, tetraamylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, Tetraalkylammonium hydroxide such as methyltributylammonium hydroxide or dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide or triethylbenzyl hydroxide A quaternary ammonium salt such as a quaternary ammonium salt or an alkaline aqueous solution such as a cyclic amine such as pyrrole or piperidine. Further, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution to be used. The alkali concentration of the alkaline developer is usually from 0.1% by mass to 20% by mass. The pH of the alkaline developer is usually from 10.0 to 15.0. The alkali concentration and pH value of the alkaline developer can be appropriately adjusted and used. The alkaline developer may also be added by adding a surfactant or an organic solvent. Surfactant The developer may contain an appropriate amount of a surfactant as needed.

The surfactant may be the same as the surfactant used in the sensitizing ray-sensitive or radiation-sensitive resin composition.

The amount of the surfactant to be used is usually 0.001% by mass to 5% by mass, preferably 0.005% by mass to 2% by mass, and more preferably 0.01% by mass to 0.5% by mass based on the total amount of the developer. • Basic compound The developer may also contain a basic compound. Specific examples and preferred examples of the basic compound which may be contained in the developer used in the present invention are the same as those of the basic compound which may be contained in the sensitizing ray-sensitive or radiation-sensitive resin composition. Developing method Developing method For example, a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dipping method), and developing the liquid by applying surface tension to the surface of the substrate and standing still for a certain period of time can be applied. Method (liquid-coating method); method of spraying a developing solution on a substrate surface (spray method); method of continuously ejecting a developing solution while scanning a developing solution nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method) . Further, after the step of performing development, a step of stopping the development while replacing the other solvent may be performed.

The development time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, and is usually from 100 seconds to 300 seconds. It is preferably from 20 seconds to 120 seconds.

The temperature of the developer is preferably from 0 ° C to 50 ° C, more preferably from 15 ° C to 35 ° C. (5) Leaching The pattern forming method of the present invention preferably includes a rinsing step after the developing step.

The eluent in the rinsing treatment performed after the alkaline development is made of pure water, and an appropriate amount of a surfactant may be added and used.

The surfactant may be the same as the surfactant used in the sensitizing ray-sensitive or radiation-sensitive resin composition, and the amount thereof is usually 0.001% by mass to 5% by mass based on the total amount of the eluent. It is preferably 0.005 mass% to 2 mass%, more preferably 0.01 mass% to 0.5 mass%. Eluent Method In the elution step, the developed wafer is subjected to a cleaning process using the eluent.

The method of the cleaning treatment is not particularly limited. For example, the following method can be applied: a method of continuously ejecting the eluent on a substrate rotating at a constant speed (rotary ejection method), and immersing the substrate in a tank filled with the eluent for a certain period of time. The method (dipping method), the method of spraying the eluent on the surface of the substrate (spray method), wherein the cleaning process is preferably performed by a rotary discharge method, and the substrate is rotated at 2000 rpm to 4000 rpm after the cleaning. The eluent is removed from the substrate.

The rinsing time is not particularly limited and is usually from 10 seconds to 300 seconds. It is preferably from 10 seconds to 180 seconds, and most preferably from 20 seconds to 120 seconds.

The temperature of the eluent is preferably from 0 ° C to 50 ° C, and more preferably from 15 ° C to 35 ° C.

Further, after the development treatment or the rinsing treatment, a treatment for removing the developer or eluent adhering to the pattern by the supercritical fluid may be performed.

Further, after the development treatment or the rinsing treatment or the treatment using the supercritical fluid, a heat treatment for removing the solvent remaining in the pattern can be performed. The heating temperature is not particularly limited as long as a good resist pattern is obtained, and is usually 40 to 160 °C. The heating temperature is preferably 50 ° C or more and 150 ° C or less, and more preferably 50 ° C or more and 110 ° C or less. The heating time is not particularly limited as long as a good resist pattern can be obtained, and is usually 15 seconds to 300 seconds, preferably 15 seconds to 180 seconds.

On the other hand, in the case of EB exposure or EUV exposure, for the purpose of suppressing outgassing, suppressing stain defects, preventing deterioration of collapse due to improvement of the shape of the reverse taper, and line width roughness due to surface roughness (Line) For the purpose of Width Roughness, LWR, or the like, a top coat layer may be formed on the upper layer of the sensitized ray-sensitive or radiation-sensitive film formed of the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention. The top coat composition used in the formation of the top coat is explained below. The solvent of the top coat composition in the present invention is preferably water or an organic solvent. More preferably, it is a water or an alcohol solvent. When the solvent is an organic solvent, it is preferably a solvent which does not dissolve the sensitizing ray-sensitive or radiation-sensitive film. The solvent which can be used is preferably an alcohol solvent, a fluorine solvent or a hydrocarbon solvent, and further preferably a non-fluorine alcohol solvent. From the viewpoint of coatability, the alcohol solvent is preferably a primary alcohol, and more preferably a primary alcohol having 4 to 8 carbon atoms. As the primary alcohol having 4 to 8 carbon atoms, a linear, branched or cyclic alcohol can be used, and a linear or branched alcohol is preferable. Specific examples thereof include 1-butanol, 1-hexanol, 1-pentanol, and 3-methyl-1-butanol.

When the solvent of the top coat composition in the present invention is water or an alcohol solvent, it is preferred to contain a water-soluble resin. It is considered that the solubility of the developer can be further improved by the inclusion of the water-soluble resin. Preferred water-soluble resins include polyacrylic acid, polymethacrylic acid, polyhydroxystyrene, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ether, polyvinyl acetal, and polypropylene quinone. , polyethylene glycol, polyethylene oxide, polyethylene, polyester polyol and polyether polyol, polysaccharides and the like. Particularly preferred are polyacrylic acid, polymethacrylic acid, polyhydroxystyrene, polyvinylpyrrolidone, polyvinyl alcohol. Further, the water-soluble resin is not limited to a homopolymer, and may be a copolymer. For example, it may be a copolymer having a monomer corresponding to the repeating unit of the above-mentioned homopolymer, and a copolymer of the other monomer unit. Specifically, an acrylic acid-methacrylic acid copolymer, an acrylic acid-hydroxystyrene copolymer, or the like can also be used in the present invention.

Further, as the resin for the top coat composition, a resin having an acidic group described in JP-A-2009-134177 and JP-A-2009-91798 can be preferably used.

The weight average molecular weight of the water-soluble resin is not particularly limited, and is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 100,000. Here, the weight average molecular weight of the resin means a polystyrene-equivalent molecular weight measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

The pH of the top coat composition is not particularly limited, but is preferably from 0 to 10, more preferably from 0 to 8, particularly preferably from 1 to 7.

In the case where the solvent of the top coat composition is an organic solvent, the top coat composition may also contain a hydrophobic such as the hydrophobic resin (HR) described in the item of the sensitizing ray-sensitive or radiation-sensitive resin composition. Sexual resin. The hydrophobic resin is also preferably used as the hydrophobic resin described in JP-A-2008-209889. The concentration of the resin in the top coat composition is preferably from 0.1% by mass to 10% by mass, further preferably from 0.2% by mass to 5% by mass, particularly preferably from 0.3% by mass to 3% by mass.

The top coat material may further contain a component other than the resin, and the proportion of the resin in the solid content of the top coat composition is preferably from 80% by mass to 100% by mass, and more preferably from 90% by mass to 100% by mass. More preferably, it is 95% by mass to 100% by mass.

The solid content concentration of the top coat composition in the present invention is preferably from 0.1% by mass to 10% by mass, more preferably from 0.2% by mass to 6% by mass, even more preferably from 0.3% by mass to 5% by mass. By setting the solid content concentration to the above range, the top coat composition can be uniformly applied to the sensitized ray-sensitive or radiation-sensitive film.

A component other than the resin which can be added to the top coat material may, for example, be a surfactant, a photoacid generator, a basic compound or the like. Specific examples of the photoacid generator and the basic compound include the same compounds as the basic compound which generates an acid by irradiation with actinic rays or radiation.

In the case of using a surfactant, the amount of the surfactant to be used is preferably 0.0001% by mass to 2% by mass, and more preferably 0.001% by mass to 1% by mass based on the total amount of the top coat composition. By adding a surfactant to the top coat composition, the coatability in the case of coating the top coat composition can be improved. Examples of the surfactant include nonionic, anionic, cationic and amphoteric surfactants.

Non-ionic surfactants can be used: Plufarac series manufactured by BASF, ELEBASE series manufactured by Aoki Oil & Fats Industries Co., Ltd., FINESURF series, Brasserie (Blaunon) series, Adeka Pluronic P-103 manufactured by Asahi Chemical Industry Co., Ltd., Emalgen series, AMIET series, AMINON manufactured by Kao Chemical Co., Ltd. ) PK-02S, EMANON CH-25, RHEODOL series, AGC Semi Chemical's Surflon S-141, the first industrial pharmaceutical company Manufactured in the Noigen series, the Newkalgen series manufactured by Takemoto Oil Co., Ltd., DYNOL 604, Enviro Gem AD01, manufactured by Nissin Chemical Industry Co., Ltd. Olfine EXP series, Surfynol series, Ftergent 300 manufactured by Lingjiang Chemical Company.

Anionic surfactants can be used: EMAL 20T, Poise 532A, produced by Toho Chemical Co., Ltd., Phosphanol ML-200, manufactured by Toho Corporation, Clariant, Japan (EMULSOGEN) series manufactured by Clariant Japan, Surflon S-111N and Surflon S-211 manufactured by AGC Semi Chemical, First Industrial Pharmaceuticals The Plysurf series manufactured by the company, the Pionin series manufactured by Takemoto Oil Co., Ltd., the Olfine PD-201 and the Olfine PD- manufactured by Nissin Chemical Industry Co., Ltd. 202. Akpo (RLY45), ECT-3 manufactured by Nihon Surfactant Kogyo Co., Ltd., and Lipon manufactured by Lion Corporation.

As the cationic surfactant, Acetamin 24, Acetamin 86, and the like manufactured by Kao Chemical Co., Ltd. can be used. Amphoteric surfactants can be used: Surflon S-131 (AGC Semi Chemical), Enagicol C-40H, Ripomin LA (above) Made for Kao Chemical Co., Ltd.).

Alternatively, these surfactants may be used in combination.

In the pattern forming method of the present invention, the sensitizing ray-sensitive or radiation-sensitive resin composition can be formed on a substrate to form a sensitizing ray-sensitive or radiation-sensitive film, which can be applied to a sensitized ray-sensitive or radiation-sensitive film. The top coat composition is used to form a top coat. The film thickness of the sensitizing ray-sensitive or radiation-sensitive film is preferably 10 nm to 100 nm, and the film thickness of the top coat layer is preferably 10 nm to 200 nm, and more preferably 20 nm to 100 nm, and particularly preferably 40 Nm ~ 80 nm.

The method of coating the photosensitive ray-sensitive or radiation-sensitive resin composition on the substrate is preferably spin coating, and the rotation speed thereof is preferably from 1,000 rpm to 3000 rpm.

For example, a photosensitive ray-sensitive or radiation-sensitive resin composition is applied to a substrate used in the production of a precision integrated circuit component by an appropriate coating method such as a spinner or a coater (for example: 矽/二The cerium oxide is coated and dried to form a sensitized ray-sensitive or radiation-sensitive film. Further, a known anti-reflection film may be applied in advance. Further, it is preferred to dry the sensitizing ray-sensitive or radiation-sensitive film before forming the top coat layer.

Then, the top coat composition can be applied onto the obtained sensitized ray-sensitive or radiation-sensitive film by the same means as the method of forming the sensitized ray-sensitive or radiation-sensitive film, and dried. A top coat is formed.

The photosensitive ray-sensitive or radiation-sensitive film having a top coat layer on the upper layer is usually irradiated with an electron beam (EB), X-ray or EUV light through a mask, preferably baked (heated), and developed. Thereby a good pattern can be obtained.

Further, the present invention relates to a sensitizing ray-sensitive or radiation-sensitive composition coated with the present invention, that is, a resist coated with a sensitizing ray-sensitive or radiation-sensitive film obtained in the above manner. Mask blanks. In order to obtain such a resist coating blank mask, when a resist pattern is formed on a photomask blanks for photomask production, examples of the transparent substrate used include quartz, calcium fluoride, and the like. Transparent substrate. In general, a light-shielding film and an anti-reflection film are laminated on a substrate, and a phase-shift film is laminated thereon, and an essential functional film such as an etching barrier film or an etching mask film is additionally laminated. Regarding the material of the functional film, a film containing a transition metal such as ruthenium or chromium, molybdenum, zirconium, hafnium, tungsten, titanium or niobium is laminated. In addition, the material used for the outermost layer may be exemplified by a ruthenium compound material mainly composed of a material containing oxygen and/or nitrogen in ruthenium or a ruthenium, and a material containing a transition metal as a main constituent material. Or a transition metal, particularly one or more selected from the group consisting of chromium, molybdenum, zirconium, hafnium, tungsten, titanium, niobium, and the like, or further comprising one or more elements selected from the group consisting of oxygen, nitrogen, and carbon. A transition metal compound material mainly composed of a material.

The light shielding film may be a single layer, and more preferably a multilayer structure in which a plurality of materials are overlapped and coated. In the case of a multilayer structure, the thickness of the film of each layer is not particularly limited, and is preferably 5 nm to 100 nm, more preferably 10 nm to 80 nm. The thickness of the entire light shielding film is not particularly limited, but is preferably 5 nm to 200 nm, more preferably 10 nm to 150 nm.

Among these materials, a shrinkage shape is formed in the vicinity of the substrate when a negative-type chemically amplified resist composition is used for patterning on a blank mask having a material containing oxygen or nitrogen in the outermost layer. It is easy to become a so-called undercut shape, and when the sensitizing ray-sensitive or radiation-sensitive composition of the present invention is used, the undercut problem can be improved as compared with the former.

Then, the resist coated blank mask is exposed by electron beam or EUV light, preferably baking (usually 80 ° C to 150 ° C, more preferably 90 ° C to 130 ° C, and usually 1 minute) After -20 minutes, preferably 1 minute to 10 minutes, development is carried out using an alkaline developer. Thereby a good pattern can be obtained. In addition, the pattern is used as a mask, and an etching process, ion implantation, or the like is appropriately performed to produce a semiconductor fine circuit, a die structure for imprint, a mask, and the like.

Further, the present invention relates to a photomask obtained by exposing and developing a resist-coated blank mask. The steps described in the above are applied to exposure and development. The photomask can be preferably used as a semiconductor manufacturing.

The photomask of the present invention may be a light transmissive type mask used for an ArF excimer laser or the like, or may be a light reflection type mask used for a reflection system lithography using EUV light as a light source. [Use] The pattern forming method of the present invention can be preferably used for the fabrication of a semiconductor fine circuit such as a super LSI or a high-capacity microchip. Further, when a semiconductor fine circuit is produced, after the formation of the photosensitive ray-sensitive or radiation-sensitive film having a pattern, the remaining sensitized ray-sensitive or radiation-sensitive film portion is finally replaced by a solvent or the like. Since it is removed, unlike the so-called permanent resist used for a printed circuit board or the like, the sensitizing ray or the sensation derived from the sensitized ray-sensitive or radiation-sensitive resin composition described in the present invention does not remain in the final product such as the microchip. Radiation linear film.

Further, the present invention relates to a method of manufacturing an electronic component including the pattern forming method of the present invention, and an electronic component manufactured by the manufacturing method.

The electronic component of the present invention can be preferably mounted on an electric and electronic device (a home appliance, an office automation (OA), a media-related device, an optical device, a communication device, or the like). [Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. <Reference Synthesis Example 1: Synthesis of Compound MI-1> (Synthesis of Chloroether Compound) 46.50 g of cyclohexanecarboxaldehyde was dissolved in 263.5 g of n-hexane, and 64.5 g of third butanol and 46.50 g of anhydrous were added. Magnesium sulfate, 4.81 g of 10-camphorsulfonic acid, was stirred at room temperature for 6 hours. 10.49 g of triethylamine was added, and after stirring for 10 minutes, filtration was carried out to remove the solid. After adding 400 g of ethyl acetate, the organic layer was washed five times with 200 g of ion-exchanged water, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain 108.33 g of a solution containing the compound (1).

To the 36.11 g of the solution containing the compound (1), 12.47 g of ethyl hydrazine chloride was added, and the mixture was stirred at 50 ° C for 2 hours. After returning to room temperature, unreacted acetamidine chloride was removed under reduced pressure, whereby 34.21 g of a solution containing the compound (2) was obtained as a chloroether compound.

(Synthesis of Compound M-I-1) 18.82 g of reverse cinnamic acid was dissolved in 136.8 g of dehydrated tetrahydrofuran, 23.67 g of triethylamine was added, and the mixture was stirred under a nitrogen atmosphere. After cooling to 0 ° C, 34.21 g of a solution containing the compound (2) was added dropwise over 30 minutes, and stirred for 2 hours. After returning to room temperature, 400 g of ethyl acetate was added, and the organic layer was washed five times with 200 g of ion-exchanged water, and then dried over anhydrous magnesium sulfate to distill off the solvent. Separation and purification were carried out by column chromatography to obtain 30.41 g of Compound (M-I-1).

[化78]

<Reference Synthesis Example 2: Synthesis of Compound MI-2> 11.92 g of 2-(4-vinylphenyl)acetic acid was dissolved in 61.32 g of dehydrated tetrahydrofuran, and 10.64 g of triethylamine was added thereto under nitrogen atmosphere. Stir. After cooling to 0 ° C, 15.33 g of a solution containing the compound (2') synthesized by the same method as the synthesis of the chloroether compound (2) was added dropwise over 30 minutes, and stirred for 2 hours. After returning to room temperature, 400 g of ethyl acetate was added, and the organic layer was washed five times with 200 g of ion-exchanged water, and then dried over anhydrous magnesium sulfate to distill off the solvent. Separation and purification by column chromatography gave 23.55 g of Compound (M-I-2).

[化79]

<Reference Synthesis Example 3: Synthesis of Compound M-I-3> 18.82 g of 4-vinylbenzoic acid was dissolved in 136.8 g of dehydrated tetrahydrofuran, and 23.67 g of triethylamine was added thereto, and the mixture was stirred under a nitrogen atmosphere. After cooling to 0 ° C, 34.21 g of a solution containing the compound (2) was added dropwise over 30 minutes, and stirred for 2 hours. After returning to room temperature, 400 g of ethyl acetate was added, and the organic layer was washed five times with 200 g of ion-exchanged water, and then dried over anhydrous magnesium sulfate to distill off the solvent. Separation and purification by column chromatography gave 26.77 g of Compound (M-I-3).

[化80]

<Synthesis Example 1: Synthesis of Resin P-6> 3.61 g of a 50.00 mass% cyclohexanone solution of the compound (3), 6.31 g of a compound (MI-1), and 0.35 g of a polymerization initiator V-601 ( Wako Pure Chemical Industries Co., Ltd. was dissolved in 28.07 g of cyclohexanone. To the reaction vessel, 16.09 g of cyclohexanone was added, and the mixture was added dropwise for 4 hours under a nitrogen atmosphere at 85 °C. After the reaction solution was heated and stirred for 2 hours, it was left to cool to room temperature.

The reaction solution was added dropwise to 400 g of heptane / ethyl acetate = 9 / 1 (mass ratio), and the polymer was precipitated and filtered. The filtration of the filtered solid was carried out using 200 g of heptane / ethyl acetate = 9 / 1 (mass ratio). Thereafter, the washed solid was dried under reduced pressure to obtain 4.20 g of a resin (P-6).

[化81]

<Synthesis Example 2: Synthesis of Resin P-15> A compound of (5), a 50.00 mass% cyclohexanone solution, 4.87 g, 5.68 g of a compound (MI-2), and 0.32 g of a polymerization initiator V-601 ( Wako Pure Chemical Industries Co., Ltd. was dissolved in 25.26 g of cyclohexanone. 14.48 g of cyclohexanone was added to the reaction vessel, and the mixture was added dropwise for 4 hours under a nitrogen atmosphere at 85 °C. After the reaction solution was heated and stirred for 2 hours, it was left to cool to room temperature.

The reaction solution was added dropwise to 350 g of heptane / ethyl acetate = 9 / 1 (mass ratio), and the polymer was precipitated and filtered. The filtration of the filtered solid was carried out using 200 g of heptane / ethyl acetate = 9 / 1 (mass ratio). Thereafter, the washed solid was dried under reduced pressure to obtain 3.82 g of a resin (P-15).

[化82]

<Synthesis Example 3: Synthesis of Resin P-26> A compound of (5), a 50.00 mass% cyclohexanone solution, 4.69 g, 8.20 g of a compound (MI-3), and 0.46 g of a polymerization initiator V-601 ( Wako Pure Chemical Industries Co., Ltd. was dissolved in 36.49 g of cyclohexanone. To the reaction vessel, 20.92 g of cyclohexanone was added, and the mixture was added dropwise for 4 hours under a nitrogen atmosphere at 85 °C. After the reaction solution was heated and stirred for 2 hours, it was left to cool to room temperature.

The reaction solution was added dropwise to 400 g of heptane / ethyl acetate = 9 / 1 (mass ratio), and the polymer was precipitated and filtered. The filtration of the filtered solid was carried out using 200 g of heptane / ethyl acetate = 9 / 1 (mass ratio). Thereafter, the washed solid was dried under reduced pressure to obtain 5.88 g of a resin (P-26).

[化83]

The resin (P-1) to the resin (P-40) were synthesized in the same manner as the resin (P-6), the resin (P-15), and the resin (P-26).

The obtained resin was measured by GPC (carrier: tetrahydrofuran (THF)) to calculate a weight average molecular weight (Mw: polystyrene equivalent), a number average molecular weight (Mn: polystyrene), and a degree of dispersion (Mw/Mn, or less). Called "Pd"). Further, the composition ratio (mole ratio) was calculated by ¹ H-nuclear magnetic resonance (NMR) measurement.

The composition of the synthesized resin and the composition ratio (mol ratio) of the repeating unit, the mass average molecular weight (Mw), and the degree of dispersion (Mw/Mn) are shown below.

[化84]

[化85]

[化86]

[化87]

Hereinafter, the resin (P'-1) to the resin (P'-6) were synthesized in the same manner. The structure, composition ratio (mole ratio), weight average molecular weight, and dispersity of each of the synthesized resins are shown below.

[化88]

Hereinafter, the hydrophobic resin, the acid generator, the basic compound, the surfactant, the solvent, the developer, and the eluent used in the examples and the comparative examples are shown. [Photoacid generator] The photoacid generator is appropriately selected from the above-exemplified acid generator z1 to acid generator z30. [alkaline compound]

[化89]

[hydrophobic resin]

[化90]

[Solvent] S-1: propylene glycol monomethyl ether acetate (PGMEA) (boiling point 146 ° C) S-2: propylene glycol monomethyl ether (PGME) (boiling point 120 ° C) S-3: methyl lactate (boiling point 145 ° C) S-4: cyclohexanone (boiling point 157 ° C) [surfactant] W-1: Megafac R08 (manufactured by Di Ai Sheng (DIC) Co., Ltd.; fluorine and lanthanide) W-2: polyoxyl Alkane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; lanthanide) W-3: Troy Sol S-366 (manufactured by Troy Chemical Co., Ltd.; fluorine system) W-4: PF6320 (manufactured by OMNOVA; fluorine system) [developer/eluent] G-1: 2.38 mass% aqueous solution of tetramethylammonium hydroxide G-2: pure water [Examples 1A to 40A] Comparative Example 1A' to Comparative Example 6A' (Electron Beam (EB) Exposure) (1) Coating liquid preparation and coating of a photosensitive ray-sensitive or sensitized radioactive resin composition using a membrane filter pair having a pore diameter of 0.1 μm The coating composition having a solid content concentration of 2.5% by mass as shown in the following Table 1 was subjected to microfiltration to obtain a sensitized ray-sensitive or sensitized radioactive resin composition. The resist composition) solution. The sensitizing ray-sensitive or sensitized radioactive resin composition solution was applied to a 6-inch hexamethyldisilazane (HMDS)-pretreated solution using a spin coater Mark8 manufactured by Tokyo Electron. The 吋Si wafer was dried on a hot plate at 100 ° C for 60 seconds to obtain a resist film having a film thickness of 50 nm.

(2) EB exposure and development Patterning of the resist film-coated wafer obtained in the above (1) using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage of 50 KeV) . At this time, drawing is performed in such a manner as to form a line and a gap of 1:1. After electron beam drawing, the substrate was heated at 100 ° C for 60 seconds on a hot plate, and then the alkaline developing solution described in the following table was applied to cover the solution for 30 seconds, except for a part of the examples and the comparative examples. The rinsing liquid described in the table was used for rinsing, and then the wafer was rotated at 4000 rpm for 30 seconds, and then heated at 95 ° C for 60 seconds, thereby obtaining a 1:1 line width of 100 nm. A resist pattern of line and gap patterns.

(3) Evaluation of Resist Pattern Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), the obtained resist pattern was evaluated for resolving power, dry etching resistance, and dissolution by the following method. Contrast. The results are shown in Table 1 below.

(3-1) Resolving power The irradiation energy when analyzing the 1:1 line having a line width of 100 nm and the gap pattern is the sensitivity (Eop). The minimum line width of the (1:1) line and gap pattern that will be separated under Eop is set as the resolution. The smaller the value, the better the performance.

(3-2) Dry etching resistance (1) In the preparation and coating of the coating liquid of the sensitized ray-sensitive or radiation-sensitive resin composition, after forming a resist film having a film thickness of 200 nm, C is used. A mixed gas of ₄ F ₆ (20 mL/min) and O ₂ (40 mL/min) was plasma-etched for 30 seconds at a temperature of 23 °C. Thereafter, the amount of residual film was determined to calculate the etching rate. Moreover, the etching resistance was evaluated based on the following criteria. (Criteria for determination) A: Case where the etching rate is less than 1 nm/sec B: Case where the etching rate is 1 nm/sec or more and less than 1.5 nm/sec C: The etching rate is 1.5 nm/sec or more (3-3) In the "(2) EB exposure and development", the exposure amount is changed in the range of 0 μC to 25.0 μC in a range of 0.5 μC, and the surface exposure is performed, and further, at 100 ° C for 90 seconds. bake. Thereafter, a dissolution rate at each exposure amount was measured using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to obtain a sensitivity curve. In the sensitivity curve, the exposure amount when the dissolution rate of the resist is saturated is used as the sensitivity, and the dissolution contrast (γ value) is calculated from the gradient of the linear portion of the sensitivity curve. The larger the γ value, the more excellent the dissolution contrast.

Table 1

Table 1 (continued)

[1B to 40B, Comparative Example 1B' to Comparative Example 6B' (Extreme Ultraviolet (EUV) Exposure)] (4) Preparation and coating of the coating liquid of the sensitized ray-sensitive or sensitized radioactive resin composition are as shown in Table 2 below. The component was dissolved in the solvent shown in Table 2 at a solid content of 1.5% by mass, and subjected to microfiltration using a membrane filter having a pore diameter of 0.05 μm to obtain a sensitized ray-sensitive or radiation-sensitive resin composition (resist composition). Solution).

The sensitizing ray-sensitive or radiation-sensitive resin composition solution was applied to a 6-inch Si wafer previously treated with hexamethyldioxane using a spin coater Mark8 manufactured by Tokyo Electron. The film was dried on a hot plate at 100 ° C for 60 seconds to obtain a resist film having a film thickness of 50 nm.

(5) EUV exposure and development The Ev exposure apparatus (Micro Exposure Tool, manufactured by Exitech Co., Ltd.) was used for the wafer coated with the resist film obtained in the above (4). The Numerical Aperture (NA) is 0.3, Quadrupole, outer sigma is 0.68, inner sigma is 0.36, and exposure is performed using an exposure mask (line/gap=1/1). . After the exposure, the substrate was heated at 100 ° C for 90 seconds on a hot plate, and then the alkaline developing solution described in the following table was applied to cover the solution for 30 seconds, and the same was used except for a part of the examples and the comparative examples. The eluent described in the table was rinsed, and then the wafer was rotated at 4000 rpm for 30 seconds and then baked at 95 ° C for 60 seconds to obtain a 1:1 line with a line width of 50 nm. A resist pattern with a gap pattern.

(6) Evaluation of Resist Pattern Using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.), the obtained resist pattern was evaluated for resolving power, dry etching resistance, and dissolution by the following method. Contrast. The results are shown in Table 2 below.

(6-1) Resolving power The irradiation energy when the 1:1 line having a line width of 100 nm and the gap pattern are analyzed is the sensitivity (Eop). The minimum line width of the (1:1) line and gap pattern that will be separated under Eop is set as the resolution. The smaller the value, the better the performance.

(6-2) Dry etching resistance (1) In the preparation and coating of the coating liquid of the sensitizing ray-sensitive or radiation-sensitive resin composition, after forming a resist film having a film thickness of 200 nm, C is used. A mixed gas of ₄ F ₆ (20 mL/min) and O ₂ (40 mL/min) was plasma-etched for 30 seconds at a temperature of 23 °C. Thereafter, the amount of residual film was determined to calculate the etching rate. Moreover, the etching resistance was evaluated based on the following criteria. (Criteria for determination) A: Case where the etching rate is less than 1 nm/sec B: Case where the etching rate is 1 nm/sec or more and less than 1.5 nm/sec C: The etching rate is 1.5 nm/sec or more (6-3) Dissolution contrast (5) EUV exposure and development, while exposing the exposure amount in the range of 0 mJ to 10.0 mJ in units of 0.5 mJ, and performing surface exposure, and baking at 100 ° C for 90 seconds. . Thereafter, a dissolution rate at each exposure amount was measured using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to obtain a sensitivity curve. In the sensitivity curve, the exposure amount when the dissolution rate of the resist is saturated is used as the sensitivity, and the dissolution contrast (γ value) is calculated from the gradient of the linear portion of the sensitivity curve. The larger the γ value, the more excellent the dissolution contrast.

Table 2

Table 2 (continued)

As is clear from the above table, Comparative Examples 1A' to 1A to 40A and Examples 1B to 40B were compared with a resin 1A to a resin having no repeating unit represented by the general formula (1). In comparison with Examples 6A' and 1B' to 6B', high resolution, high dry etching resistance, and high dissolution contrast were satisfied.

no

no

Claims (16)

A pattern forming method comprising: a step of forming a film using a photosensitive ray-sensitive or radiation-sensitive resin composition containing a resin (P1) containing at least a repeat represented by the following formula (1) a unit (a) as a repeating unit having a group decomposed by an action of an acid and generating a polar group; a step of exposing the film; and developing the exposed film using a developing solution to form a positive Type of pattern steps, In the formula (1), Y ₁ and Y ₂ each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form an aromatic ring; Y ₃ represents a single bond or a divalent aromatic ring group; Y ₃ may also be Y _{1 is} bonded to form a ring, in which case Y ₃ represents a trivalent aromatic ring group; L ₁ represents a single bond or a divalent linking group; and L ₁ may also bond with Y ₁ to form a ring, in the case of L ₁ represents a trivalent linking group; R ₁ and R ₂ each independently represent a hydrogen atom or a substituent; M ₁ represents an organic group; and one of R ₁ and R ₂ and M ₁ may be bonded to each other and The oxygen atoms together form a ring; wherein at least one of Y ₁ , Y ₂ and Y ₃ contains an aromatic ring, or Y ₁ and Y ₂ are bonded to each other to form an aromatic ring; when Y ₃ is an aromatic ring group, and L ₁ is In the case of a single bond, at least one of R ₁ and R ₂ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, an aromatic ring group, a heterocyclic group or a halogen atom; when Y ₃ is an aromatic ring group, and L ₁ In the case of a divalent linking group, L ₁ does not contain an aliphatic cyclic group, and one of R ₁ and R ₂ and M ₁ are not bonded to each other to form a ring. The pattern forming method according to the first aspect of the invention, wherein the repeating unit (a) represented by the formula (1) is a repeating unit represented by the following formula (2), In the formula (2), Y ₄ and Y ₅ each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form an aromatic ring; L ₁₁ represents a single bond or a divalent linking group; and L ₁₁ may also be combined with Y ₄ Bonding to form a ring, in which case L ₁₁ represents a trivalent linking group; R ₃ and R ₄ each independently represent a hydrogen atom or a substituent; M ₂ represents an organic group; and one of R ₃ and R ₄ and M ₂ may be bonded to each other to form a ring together with an oxygen atom in the formula; wherein at least one of Y ₄ and Y ₅ contains an aromatic ring, or Y ₄ and Y ₅ are bonded to each other to form an aromatic ring. The pattern forming method according to claim 2, wherein R ₃ in the formula (2) represents a hydrogen atom, and R ₄ represents a hydrogen atom, an alkyl group, an aliphatic cyclic group or an aromatic ring group. The pattern forming method according to claim 2, wherein M ₂ in the formula (2) is an alkyl group. The pattern forming method according to the first aspect of the invention, wherein the repeating unit (a) represented by the formula (1) is a repeating unit represented by the following formula (3), In the formula (3), Y ₆ and Y ₇ each independently represent a hydrogen atom or a monovalent organic group; and L ₂ represents a divalent linking group having an atomic number of 1 between an aromatic ring and a carboxyl group; ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aliphatic cyclic group, a halogen atom, an aromatic ring group, or a heterocyclic group; M ₃ represents an organic group; and one of R ₅ and R ₆ is bonded to M ₃ Rings are not bonded to each other; n represents an integer of 0 or more. The pattern forming method according to claim 5, wherein at least one of R ₅ and R ₆ in the formula (3) is an alkyl group having 7 or more carbon atoms, an aliphatic cyclic group, a halogen atom, and carbon. An aromatic ring group of 13 or more or a heterocyclic group. The pattern forming method according to claim 5, wherein M ₃ in the formula (3) is an alkyl group having 7 or more carbon atoms, an aliphatic cyclic group, a halogen atom, and an aromatic ring group having 13 or more carbon atoms. Or a heterocyclic group. The pattern forming method according to the first aspect of the invention, wherein the repeating unit (a) represented by the formula (1) is a repeating unit represented by the following formula (4), In the formula (4), Y ₈ and Y ₉ each independently represent a hydrogen atom or a monovalent organic group; R ₇ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, an aromatic ring group, a heterocyclic group or a halogen. Atom; R ₈ represents a hydrogen atom, or a substituent; M ₄ represents an organic group; and one of R ₇ and R ₈ and M ₄ may be bonded to each other to form a ring together with an oxygen atom in the formula; n represents 0 or 1 The above integer. The pattern forming method according to claim 8, wherein R ₇ in the formula (4) represents an aliphatic cyclic group. The pattern forming method according to any one of the items 1 to 9, wherein the resin (P1) further contains a repeating unit represented by the formula (A). In the formula (A), Z ₁ , Z ₂ and Z ₃ each independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; wherein Z ₃ may also bond with Ar ₂ or X ₁ And forming a ring, in which case Z ₃ represents a single bond or an alkyl group; X ₁ represents a single bond, an alkyl group, -COO-, or -CONR ₉ -; here, R ₉ represents a hydrogen atom or an alkyl group. L ₃ represents a single bond, -COO-, or an alkylene group; Ar ₂ represents an (m+1)-valent aromatic ring group, and represents a (m+2) valence when bonded to Z ₃ to form a ring. An aromatic ring group; m represents an integer of 1 to 4. A photosensitive ray- or radiation-sensitive resin composition for use in a pattern forming method, the pattern forming method comprising: a step of forming a film using a photosensitive ray-sensitive or radiation-sensitive resin composition; a step of exposing; and a step of developing the exposed film using a developing solution to form a positive pattern, and the photosensitive ray-sensitive or radiation-sensitive resin composition contains a resin (P1), the resin (P1) at least a repeating unit (a) represented by the following formula (1) as a repeating unit having a group which decomposes by an action of an acid and generates a polar group, In the formula (1), Y ₁ and Y ₂ each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form an aromatic ring; Y ₃ represents a single bond or a divalent aromatic ring group; Y ₃ may also be Y _{1 is} bonded to form a ring, in which case Y ₃ represents a trivalent aromatic ring group; L ₁ represents a single bond or a divalent linking group; and L ₁ may also bond with Y ₁ to form a ring, in the case of L ₁ represents a trivalent linking group; R ₁ and R ₂ each independently represent a hydrogen atom or a substituent; M ₁ represents an organic group; and one of R ₁ and R ₂ and M ₁ may be bonded to each other and The oxygen atoms together form a ring; wherein at least one of Y ₁ , Y ₂ and Y ₃ contains an aromatic ring, or Y ₁ and Y ₂ are bonded to each other to form an aromatic ring; when Y ₃ is an aromatic ring group, and L ₁ is In the case of a single bond, at least one of R ₁ and R ₂ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, an aromatic ring group, a heterocyclic group or a halogen atom; when Y ₃ is an aromatic ring group, and L ₁ In the case of a divalent linking group, L ₁ does not contain an aliphatic cyclic group, and one of R ₁ and R ₂ and M ₁ are not bonded to each other to form a ring. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 11, wherein the repeating unit (a) represented by the formula (1) is a repeat represented by the following formula (2) unit, In the formula (2), Y ₄ and Y ₅ each independently represent a hydrogen atom or an organic group, and may be bonded to each other to form an aromatic ring; L ₁₁ represents a single bond or a divalent linking group; and L ₁₁ may also be combined with Y ₄ Bonding to form a ring, in which case L ₁₁ represents a trivalent linking group; R ₃ and R ₄ each independently represent a hydrogen atom or a substituent; M ₂ represents an organic group; and one of R ₃ and R ₄ and M ₂ may be bonded to each other to form a ring together with an oxygen atom in the formula; wherein at least one of Y ₄ and Y ₅ contains an aromatic ring, or Y ₄ and Y ₅ are bonded to each other to form an aromatic ring. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 11, wherein the repeating unit (a) represented by the formula (1) is a repeat represented by the following formula (3) unit, In the formula (3), Y ₆ and Y ₇ each independently represent a hydrogen atom or a monovalent organic group; and L ₂ represents a divalent linking group having an atomic number of 1 between an aromatic ring and a carboxyl group; ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aliphatic cyclic group, a halogen atom, an aromatic ring group, or a heterocyclic group; M ₃ represents an organic group; and one of R ₅ and R ₆ is bonded to M ₃ Rings are not bonded to each other; n represents an integer of 0 or more. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 11, wherein the repeating unit (a) represented by the formula (1) is a repeat represented by the following formula (4) unit, In the formula (4), Y ₈ and Y ₉ each independently represent a hydrogen atom or a monovalent organic group; R ₇ represents an alkyl group having 6 or more carbon atoms, an aliphatic cyclic group, an aromatic ring group, a heterocyclic group or a halogen. Atom; R ₈ represents a hydrogen atom, or a substituent; M ₄ represents an organic group; and one of R ₇ and R ₈ and M ₄ may be bonded to each other to form a ring together with an oxygen atom in the formula; n represents 0 or 1 The above integer. A sensitized ray-sensitive or radiation-sensitive linear film formed by using the sensitized ray-sensitive or radiation-sensitive linear composition according to any one of claims 11 to 14. A method of producing an electronic component, comprising the pattern forming method according to any one of claims 1 to 10.