TW201910918A - Active-light-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and method for manufacturing electronic device - Google Patents

Abstract

Provided are: an active-light-sensitive or radiation-sensitive resin composition with which a resist film having excellent EL performance and a pattern having excellent LWR performance can be obtained; a resist film using the active-light-sensitive or radiation-sensitive resin composition; a pattern formation method; and a method for manufacturing an electronic device. The active-light-sensitive or radiation-sensitive resin composition includes: a resin having at least one type of repeating unit selected from the group consisting of repeating unit represented by general formula (1), and the repeating unit represented by general formula (2); and a photoacid generator.

Description

Photosensitive ray- or radiation-sensitive resin composition, resist film, pattern forming method, and method for producing electronic component

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

In the manufacturing process of a semiconductor element such as an IC (Integrated Circuit) or an LSI (Large Scale Integrated Circuit), a photosensitive ray-sensitive or radiation-sensitive resin composition is used. Microfabrication of lithography. For example, Patent Document 1 discloses a radiation-sensitive resin composition containing a polymer having an acid-dissociable group having a predetermined repeating unit. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-052182

The present inventors have found out that the sensitized ray-sensitive or radiation-sensitive resin composition specifically described in the first embodiment of Patent Document 1 has been found to be composed of the above-mentioned sensitized ray-sensitive or radiation-sensitive resin. The exposure latitude (EL: Exposure Latitude) of the resist film and the fluctuation of the pattern line width of the pattern (LWR: Line Width Roughness) have room for improvement.

An object of the present invention is to provide a photosensitive ray-sensitive or radiation-sensitive resin composition which can obtain a resist film excellent in EL performance and a pattern excellent in LWR performance. Further, an object of the present invention is to provide a resist film, a pattern forming method, and a method for producing an electronic component using the above-described sensitized ray-sensitive or radiation-sensitive resin composition.

The inventors of the present invention have conducted intensive studies to achieve the above problems, and as a result, have found that the above problems can be solved by using a resin containing a repeating unit having a specific structure, and have completed the present invention. That is, it has been found that the above problems can be solved by the following configuration.

[1] A photosensitive ray-sensitive or radiation-sensitive resin composition comprising a group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2); a resin of at least one repeating unit, and a photoacid generator. [2] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [1], wherein the content of the resin is 10% by mass based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive resin composition. the above. [3] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein at least one of R ₃ and R ₄ in the following formula (2) is an organic group. [4] The sensitized ray-sensitive or radiation-sensitive resin composition according to any one of the above-mentioned [1], wherein at least one of R ₁ and R ₂ in the following general formula (1) It is a group represented by the following general formula (R), and in the following general formula (2), at least one of R ₃ and R ₄ is a group represented by the following general formula (R). [5] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [4], wherein, in the following general formula (1), R ₅ represents an alkali-decomposable group. The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of the above-mentioned items (1), wherein the L ₁ -based group may have a substituent. An alkyl group having an ether group or an alkyl group having two groups represented by the formula (A) described later, and an alkyl group having an ether group in which the L ₂ group may have a substituent in the following formula (2) Or an alkylene group having two groups represented by the following formula (A). [7] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [4] or [6], wherein, in the following formula (1), R ₁ and R ₂ are represented by the following formula (R) Further, the L ₁ group has two groups represented by the group represented by the following formula (A). The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of the above aspects, wherein the resin has a repeating unit represented by the following formula (3). The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of the above aspects, wherein the resin further has a repeating unit selected from the group consisting of a lactone group, and has no acid. At least one repeating unit of the group consisting of a repeating unit of any one of a decomposing group and a polar group. [10] A resist film formed by using the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9]. [11] A pattern forming method, comprising: a resist film forming step of forming a resist film using the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9]; An exposure step of exposing the resist film; and a developing step of developing the exposed resist film using a developing solution. [12] A method of producing an electronic component, comprising the pattern forming method according to [11]. [Effect of the invention]

According to the present invention, it is possible to provide a photosensitive ray-sensitive or radiation-sensitive resin composition which can obtain a resist film excellent in EL performance and a pattern excellent in LWR performance. Moreover, according to the present invention, it is possible to provide a resist film, a pattern forming method, and a method of producing an electronic component using the above-described sensitized ray-sensitive or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, for the label of a group (atomic group), a label which is not labeled with a substituent and which is not substituted includes a group having no substituent, and also includes a group having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, "organic group" means a group having at least one carbon atom. In the present specification, "actinic ray" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light: Extreme Ultraviolet), an X-ray, and an electron beam (EB). :Electron Beam) and so on. In the present specification, "light" means actinic rays or radiation. In the present specification, "exposure" includes not only the bright line spectrum of a mercury lamp, but also the ultraviolet light, extreme ultraviolet rays, X-rays, and EUV light represented by excimer lasers, unless otherwise specified. Draw by a particle beam such as an electron beam or an ion beam. In the present specification, "to" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

In the present specification, "(meth) acrylate" means acrylate and methacrylate. In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (also referred to as molecular weight distribution) (Mw/Mn) of the resin are defined as GPC (Gel Permeation). Chromatography)) GPC measurement of the apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 ° C , Flow rate: 1.0 mL/min, detector: Refractive Index Detector). The bonding direction of the divalent group (for example, -COO-) labeled in the present specification is not limited unless otherwise specified. For example, when M is -COO- in the compound represented by the formula "LMN", the position at which the bond is bonded to the L side is *1 and the position at which the bond is bonded to the N side is set. *2, then M can be *1-O-CO-*2 or *1-CO-O-*2. In the present specification, an organic group means a group having a carbon atom. For example, a hydrocarbon group and a hydrocarbon group having a hetero atom can be cited.

[Photosensitive ray-sensitive or radiation-sensitive resin composition] The sensitized ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also simply referred to as "composition" or "composition of the present invention") will be described. The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkaline development, or may be a resist composition for organic solvent development. The composition of the present invention is typically a chemically amplified resist composition.

The characteristic point of the composition of the present invention includes a resin having a repeating unit represented by the following general formula (1) or (2). By the composition of the present invention containing the above-mentioned resin, it is possible to form a resist film excellent in EL performance and a pattern excellent in LWR performance (hereinafter, this property of the composition of the present invention is also simply referred to as "the effect of the present invention". ). Although the details of this mechanism are not clear, they are speculated as follows. The repeating unit represented by the following formula (1) or (2) which is contained in the resin of the composition of the present invention reduces the motility of the main chain by introducing the ring structure into the main chain of the resin, and improves the activity. Glass transfer point (Tg). Further, by having a certain number or more of polar groups containing a hetero atom in the main chain and the side chain, the interaction between the groups becomes large, and the effect of improving Tg becomes larger. As a result, the solubility of the resin is lowered, and it is easy to appropriately suppress the diffusion of the acid generated from the photo-acid generator by the exposure. As a result, it is estimated that the resist film composed of the composition of the present invention exhibits excellent development contrast and can exhibit excellent development contrast. The effect of the present invention is achieved.

Hereinafter, the components contained in the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention will be described in detail.

<Resin (A)> The composition of the present invention contains a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2).

[Chemical Formula 1]

(R ₁ , R ₂ , R ₃ and R ₄ ) In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, a group represented by the formula (A) or in addition to the above formula (A) In the organic group other than the group represented by the group, at least one of R ₁ and R ₂ represents a group represented by the above formula (A).

*-C(=O)-O-R(A) In the formula (A), R represents a hydrocarbon group or a hydrogen atom which may have a hetero atom. * indicates the bonding position.

At least one of R ₁ and R ₂ is a group represented by the above formula (A), and any one of R ₃ and R ₄ may be a group represented by the above formula (A), or two All are groups represented by the above formula (A). When only one of R ₁ and R ₂ is a group represented by the above formula (A), the other one represents a hydrogen atom or an organic group other than the group represented by the formula (A). Further, both of R ₁ and R ₂ are a group represented by the above formula (A), and when the group represented by L ₁ described later has one hetero atom, two of the above formula (A) At least one of the two Rs in the group represented by the formula represents a hydrocarbon group having a hetero atom.

Examples of the above hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, a ruthenium atom, a phosphorus atom, a ruthenium atom, and a boron atom. Among them, an oxygen atom, a nitrogen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

It is preferred that R ₁ and R ₂ are each a hydrogen atom and the other is a group represented by the formula (A) or both are represented by the formula (A). The group represented by the formula (A) is more preferable.

In the formula (2), R ₃ and R ₄ each independently represent a hydrogen atom or an organic group. R ₃ and R ₄ at least one organic group is preferably based, any of R ₃ and R ₄ may be one of an organic group, both of which are also be an organic group.

As the organic group represented by R ₃ and R ₄ , a hydrocarbon group having a hetero atom is preferred. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, a ruthenium atom, a phosphorus atom, a ruthenium atom, and a boron atom. Among them, an oxygen atom, a nitrogen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Further, it is preferred that an oxygen atom and a carbon atom form an ester group together, and it is preferred that the ester group is directly bonded to a main chain of a repeating unit represented by the formula (2). Further, it is preferred that a hydrogen atom or another organic group is bonded to the above main chain via the above ester group. As the other organic group bonded to the main chain via an ester group, a hydrocarbon group which may have a hetero atom is preferred. That is, as the organic group represented by R ₃ and R ₄ , a group represented by the formula (A) is preferred. In addition, both of R ₃ and R ₄ are groups represented by the above formula (A), and when the group represented by L ₂ described later has one hetero atom, the two are represented by the above formula ( It is preferred that at least one of the two Rs in the group represented by A) represents a hydrocarbon group having a hetero atom.

In the general formula (A), examples of the hydrocarbon group which may have a hetero atom represented by R include an alkyl group which may have a hetero atom, an alkenyl group which may have a hetero atom, and an alkynyl group which may have a hetero atom. Further, the alkyl group, the alkenyl group and the alkynyl group may be either linear or branched. A carbon number of 1 to 20 is preferred. The above alkyl group, alkenyl group and alkynyl group may have a cyclic structure or may have no cyclic structure. Among them, from the viewpoint of suppressing the decrease in the Tg of the resin and further improving the effects of the present invention, when R has an alicyclic group, the alicyclic group is preferably a part of the acid-releasing group.

Among them, the group represented by the formula (A) is preferably a group represented by the formula (R) shown below. At least one of R ₁ and R ₂ is a group represented by the formula (R), and at least one of R ₃ and R ₄ is preferably a group represented by the formula (R). In other words, the composition of the present invention preferably comprises a resin (A) having a group selected from the group consisting of R ₁ and R ₂ and having a group represented by the formula (R), that is, a formula (1) The repeating unit represented, and at least one of R ₃ and R ₄ is at least one selected from the group consisting of the group represented by the formula (R), that is, the repeating unit represented by the formula (2) Repeat unit. In the formula (1), R ₁ and R ₂ are each preferably a group represented by the formula (R).

*-C(=O)-OR ₅ (R) * indicates the bonding position.

In the formula (R), R ₅ represents a hydrogen atom, an alkali-decomposable group or an acid-dissociable group. More specifically, R ₅ represents a hydrogen atom, a group which may have a hydrocarbon group of a hetero atom and which exhibits alkali decomposability, or a group which may have a hydrocarbon group of a hetero atom and which exhibits acid detachability. Among them, the R ₅ -based alkali-decomposable group or acid-desorbable group is preferred from the viewpoint of further excellent LWR properties of the pattern. Moreover, from the viewpoint of further excellent sensitivity of the resist film, an R ₅ -based hydrogen atom or an alkali-decomposable group is preferred. That is, the R ₅ -based alkali-decomposable group is more preferably.

In the present specification, the alkali-decomposable group means a group which is decomposed by the action of an alkaline solution and has an increased solubility in an alkaline solution. For example, a group having a lactone group (for example, a hydrocarbon group having a lactone group), a group having a sultone group (for example, a hydrocarbon group having a sultone group), and a group having a carbonate group may be mentioned ( For example, a hydrocarbon group having a carbonate group (preferably a cyclic carbonate group), a group having an acid anhydride group (for example, a hydrocarbon group having an acid anhydride group), a group having a lactone group, and having a sultone group A group or a group having a carbonate group (preferably a cyclic carbonate group) is preferred.

When R ₅ is an alkali-decomposable group, the group represented by the formula (R) is preferably a group represented by the formula (R ́) below.

*-C(=O)-O-Ab-V(R ́) * indicates the bonding position.

Ab-V in the formula (R ́) corresponds to R ₅ in the formula (R). Ab represents a single bond, an alkylene group, a monocyclic or polycyclic alicyclic group, an ether group, an ester group, a carbonyl group or a combination of these two valent linking groups. Among them, Ab is preferably a single bond or an alkylene group (preferably having a carbon number of 1 to 2).

V represents a lactone group, a sultone group or a cyclic carbonate group.

As the lactone group, a lactone group of a 5- to 7-membered ring is preferred. Among them, a group having a ring in the form of a bicyclic ring or a spiro ring in the 5- to 7-membered ring lactone group and having another ring is more preferable. Specifically, a group obtained by removing one hydrogen atom from the lactone structure represented by any one of the general formulae (LC1-1) to (LC1-21) shown below can be used. Structure removal represented by formula (LC1-1), formula (LC1-4), formula (LC1-5), formula (LC1-8), formula (LC1-16) or formula (LC1-21) A group derived from one hydrogen atom is preferred. As the sultone group, a sultone group of a 5- to 7-membered ring is preferred. Among them, a group having a ring of another ring in a 5- to 7-membered cyclic sultone group in the form of a bicyclic ring or a spiro ring is more preferable. Specifically, a group obtained by removing one hydrogen atom from the sultone structure represented by any one of the general formulae (SL1-1) to (SL1-3) shown below may be mentioned. A group obtained by removing the hydrogen atom by the structure represented by the formula (SL1-1) is preferred.

[Chemical Formula 2]

The above lactone and sultone group may have a substituent (Rb ₂ ) or may have no substituent (Rb ₂ ). The substituent (Rb ₂ ), an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, or a carboxyl group; A halogen atom, a hydroxyl group, a cyano group or the like is preferable, and an alkyl group having 1 to 4 carbon atoms or a cyano group is more preferable. 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. Further, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring. Further, the lactone group and the sultone group may have an acid-decomposable group described below as a substituent (Rb ₂ ).

As the cyclic carbonate group, a group in which one hydrogen atom is removed from the structure represented by the following formula is preferred.

[Chemical Formula 3]

In the above formula, n represents an integer of 0 or more. R _A ² represents a substituent. When n is 2 or more, R _A ² each independently represents a substituent. A represents a single bond or a divalent linking group. Z represents an atomic group which forms a monocyclic group or a polycyclic group together with a group represented by -OC(=O)-O- in the formula. Z-alkylene is preferred. The above alkylene group may be linear or branched, or may have a cyclic structure. Among them, the above alkylene group is preferably linear. The carbon number of the above alkyl group is preferably from 1 to 4, more preferably from 2 to 3, and still more preferably 2.

Explicitly indicated in the formula -C (= O) -O- and R ₅ together form an acid-decomposable group is also more excellent effect of the present invention of the viewpoint, the group represented by the general formula (R) are preferred. Further, in the present specification, the acid-decomposable group refers to a group which is decomposed by the action of an acid and whose polarity is increased. The structure in which the acid-decomposable group has a group in which a polar group is decomposed by a action of an acid and is detached (acid-off group) is preferred. In other words, from the viewpoint of further excellent effects of the present invention, R ₅ is preferably an acid-cleavable group, and in this case, an acid-decomposable group is formed from a group represented by the formula (R). Among them, when the acid-decomposable group is formed from the group represented by the general formula (R), the sensitivity of the formed resist film tends to decrease, so care should be taken. When the acid-decomposable group is formed from the group represented by the formula (R), the group represented by the formula (R) is preferably a group represented by the following formula (R ́ ́).

*-C(=O)-OR _c (R ́ ́) * indicates the bonding position.

In the formula (R ́ ́), R _c corresponds to R _{5 of the} formula (R). Further, the above -R _c represents -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ) or -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ).

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 and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group.

The alkyl group having 1 to 8 carbon atoms represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably a methyl group, an ethyl group, a propyl group, a n-butyl group or a second butyl group. Hexyl and octyl and so on. The cycloalkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be a single ring or a polycyclic ring. The cycloalkyl group having a monocyclic ring is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include adamantyl group, thiol group, isodecyl group, fluorenyl group, dicyclopentyl group, and α-decenyl group ( Pinel group), tricyclic fluorenyl group, tetracyclododecyl group and androstanyl group. Further, at least one or more carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom. The aryl group having 6 to 10 carbon atoms represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferable, and examples thereof include a phenyl group, a naphthyl group and an anthracenyl group. The aralkyl group having 7 to 12 carbon atoms represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferable, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group. The alkenyl group having 2 to 8 carbon atoms represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferable, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group. As the ring in which R ₃₆ and R ₃₇ are bonded to each other, a cycloalkyl group (monocyclic or polycyclic) is preferred. As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecylalkyl group, a tetracyclododecyl group or an adamantyl group is preferred. .

Specific examples of the group represented by the formula (R ́ ́) are shown. In addition, in the following illustration, * represents the bonding position with a main chain.

[Chemical Formula 4]

(L ₁ and L ₂ ) In the general formula (1), L ₁ and L _{2 each} have a divalent linking group of one or more hetero atoms, and L ₁ represents an alkylene group which may have a substituent. A part of the carbon atom in the above alkyl group may be substituted by a group having a hetero atom. The substituent may have a hetero atom. Here, the group represented by L ₁ has one or more hetero atoms. Further, as described above, both of R ₁ and R ₂ in the formula (1) are groups represented by the above formula (A), and when the group represented by L ₁ has a hetero atom of 1 In the case of at least one of the two groups represented by the above formula (A), at least one of the groups R represents a hydrocarbon group having a hetero atom. In other words, both of R ₁ and R ₂ in the formula (1) are groups represented by the above formula (A), and two of the R groups represented by the above formula (A) are both When a hydrocarbon group having no hetero atom is represented, the group represented by L ₁ has two or more hetero atom systems. L ₁ and L ₂ may be a linking group in which an alkylene group and an alkylene group are bonded via a hetero atom. L ₂ in the formula (2) represents an alkylene group which may have a substituent. A part of the carbon atom in the above alkyl group may be substituted by a group having a hetero atom. The substituent may have a hetero atom. Among them, the group represented by L ₂ has one or more hetero atoms. The alkylene groups represented by L ₁ and L ₂ are bonded to the two carbon atoms represented by the formula at the respective terminals, and form a cyclic group. Further, as a group having a hetero atom, it may be a hetero atom itself.

L ₁ and L ₂ are preferably a divalent linking group containing a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a halogen atom, wherein the hetero atom contained in L ₁ and L ₂ is an oxygen atom or nitrogen. An atom, a sulfur atom or a fluorine atom is preferred. There is no limitation on the fact that the group represented by L ₁ and L ₂ has a hetero atom, and a part of the carbon atom in the chain of the alkyl group may be substituted by a group having a hetero atom, and the alkyl group has a substitution. The group may have a hetero atom. Examples of the group having a hetero atom include an ether group (-O-), a thioether group (-S-), a carbonyl group (-C(=O)-), and an ester group (-C(=O)O-- ), amidino group (-NHC(=O)-) and sulfonyl (-S(=O) ₂ -). From the viewpoint of more excellent LWR properties of the pattern, when a group having a hetero atom is present in the chain of the alkyl group, a group having a hetero atom is preferred. When the substituent has a hetero atom, it is preferred that the hetero atom and the carbon atom form an ester group, and it is more preferable to form a group represented by the above formula (A). The carbon number of the alkylene group is preferably 2 to 10, more preferably 2 to 6, and still more preferably 2. Further, the above carbon number does not include the number of hetero atoms which the alkylene group has in the chain and the number of carbon atoms which the substituent of the alkyl group has. Further, the number of atoms constituting the ring does not include the number of atoms of the substituent.

The aspect in which the alkylene group has a substituent includes a case where a part of the hydrogen atom in the alkyl group is substituted with a substituent. The kind of the substituent is not particularly limited, and as described above, it may have a hetero atom. Examples of the kind of the substituent include a halogen atom (-F, -Cl, -I, etc.), an alkyl group, -S(=O) ₂ -alkyl group, an alkoxy group, an aryl group, a hydroxyl group, a cyano group or The group represented by the above formula (A) and the like. Among them, a group represented by the formula (A) is preferable as a substituent from the viewpoint of further excellent LWR performance of the pattern. When the alkylene group has a group represented by the general formula (A), the alkyl group having 2 or more (preferably 2 to 4) alkyl groups represented by the general formula (A) is more preferable, and has 2 It is further preferred. Further, a plurality of groups represented by the general formula (A) may be the same or different. Further, from the viewpoint that the effect of the present invention is more excellent, when the alkylene group has two groups represented by the general formula (A), R ₁ and R ₂ (or R ₃ and R ₄ ) are represented by the formula ( The group represented by R) is more preferred. In other words, in the formula (1), R ₁ and R ₂ are groups represented by the formula (R), and it is preferred that the group L ₁ has two groups represented by the formula (A). . Further, in the formula (2), R ₃ and R ₄ are a group represented by the formula (R), and a group having two groups represented by the formula (A) in the L ₂ system is also preferred. . Further, when the alkylene group has a group represented by the general formula (A), the R group in the general formula (A) may preferably have a hydrocarbon group having a hetero atom. A preferred aspect of the hydrocarbon group which may have a hetero atom is as described above, and an alkali-decomposable group or an acid-desorbable group as represented by R ₅ in the formula (R) may be formed.

The alkylene group which may have a substituent represented by L ₁ and L ₂ is preferably represented by the following formula (L).

*-(CH ₂ ) _n -Z-(CH ₂ ) _n -* (L) * indicates the bonding position.

In the general formula (L), n each independently represents an integer of 0 or more, 0 to 4 is preferable, 0 to 1 is more preferable, and 1 is further more preferable. Further, at least one of the two n represents an integer of 1 or more.

Z represents a group having a hetero atom. Examples of Z include an ether group (-O-), a thioether group (-S-), a carbonyl group (-C(=O)-), an ester group (-C(=O)O-), and a decylamine. Base (-NHC(=O)-), sulfonyl (-S(=O) ₂ -), -C(Y ₁ )(Y ₂ )-, and -N(Y ₃ )-. Y ₁ , Y ₂ and Y ₃ each independently represent a hydrogen atom or a substituent. At least one of Y ₁ and Y ₂ represents a substituent having a hetero atom. The substituents represented by Y ₁ , Y ₂ and Y ₃ are each independently a halogen atom (-F, -Cl, -I, etc.), an alkyl group, -S(=O) ₂ -alkyl or a general formula. The group represented by (A) is preferably a -S(=O) ₂ -alkyl group or a group represented by the formula (A) is more preferable. Further, the alkyl group which Y ₁ , Y ₂ and Y ₃ may have (including the Y ₁ , Y ₂ and Y ₃ alkyl groups themselves) is preferably a carbon number of 1 to 2, and may have a substituent (more Preferably, it is a halogen atom, more preferably -F). Z-ether group or Y ₁ and Y ₂ are preferably -C(Y ₁ )(Y ₂ )- of the group represented by the formula (A), and are -C(Y ₁ )(Y ₂ )- and Y ₁ and Y ₂ are more preferably a group represented by the formula (A). Further, when Z-C(Y ₁ )(Y ₂ )-, and Y ₁ and Y ₂ are a group represented by the general formula (A), a plurality of groups represented by the general formula (A) may be respectively the same It can also be different. Further, the R group in the formula (A) which can be represented by Y ₁ , Y ₂ and Y ₃ is preferably a hydrocarbon group having a hetero atom. A preferred aspect of the hydrocarbon group which may have a hetero atom is as described above, and an alkali-decomposable group or an acid-releasing group such as represented by R ₅ in the formula (R) may be formed.

The resin (A) may have a single repeating unit represented by the formula (1) or (2), or may be used in combination of two or more. The content of the repeating unit represented by the formula (1) or (2) is not particularly limited, but from the viewpoint of the effect of the present invention being more excellent, 5 to 70 mols based on all the repeating units in the resin (A). % is preferably, more preferably 5 to 60 mol%, and still more preferably 10 to 50 mol%. Further, when the resin (A) contains both the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2), the above content is the total amount of these.

The repeating unit represented by the formula (1) or (2) is preferably, for example, a repeating unit derived from a monomer which can be cyclized. More specifically, it is obtained, for example, by cyclization polymerization of a diene monomer. Further, the resin (A) may have other repeating units than the repeating unit represented by the general formula (1) or (2).

(Repeating unit having an acid-decomposable group represented by the formula (3)) The resin (A) further preferably has a repeating unit having an acid-decomposable group represented by the following formula (3).

[Chemical Formula 5]

In the formula (3), R ₆ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 20 carbon atoms is preferred. The alkyl group may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom). Among them, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and a methyl group is further more preferred.

In the formula (3), L ₃ represents a divalent linking group which may have a substituent. L ₃ is an alkyl group, an aryl group, a carbonyl group, an ester group or a combination of such a divalent linking group, preferably a carbonyl group, a -alkyl group - a carbonyl group, a - aryl group - a carbonyl group - More preferably, - ester group - alkylene group - carbonyl group, and carbonyl group is further preferred. Further, the above alkylene group and the extended aryl group may have a substituent, and as the substituent, a halogen atom is preferred.

X represents an acid-releasing group, and has the same meaning as R _c described in the above formula (R ́ ́), and the preferred range is also the same.

In the general formula (3), examples of the -L ₃ -OX include a group which is a specific example of the group represented by the above formula (R ́ ́).

Further, the following groups may also be exemplified as -L ₃ -OX.

[Chemical Formula 6]

The resin (A) may have a single repeating unit represented by the formula (3), or may be used in combination of two or more.

The content of the repeating unit having the acid-decomposable group represented by the general formula (3) is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%, based on all the repeating units of the resin (A), and more preferably 30 ～80 mol% is further preferred.

(Repeating unit having a lactone group, a sultone group or a carbonate group) The resin (A) has a group containing at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group. A repeating unit is preferred. Here, the repeating unit having a lactone group as used herein means a repeating unit represented by the above formula (1) or (2) unless otherwise specified, and is a repeating unit other than having a lactone group (especially A repeating unit other than a repeating unit having a group represented by the formula (R ́).

The lactone group and the sultone group are the same as the lactone group and the sultone group which can form V as described in the formula (R ́), and the preferred range is also the same.

As the repeating unit having a lactone group or a sultone group, the following repeating unit represented by the formula (III) is preferred.

[Chemical Formula 7]

In the above formula (III), A represents an ester group (-COO-) or a guanamine group (-CONH-). n represents an integer of 0 to 5, 0 or 1 is preferred, and 0 is more preferred. R ₀ represents an alkylene or cycloalkyl group which may have a substituent or a combination thereof. When there are a plurality of R ₀ , R ₀ may be the same or different. Z represents a single bond, an ether group, an ester group, a decylamino group, a urethane group or a urea group. When there are multiple Zs, Z may be the same or different. As Z, an ether group or an ester group is preferred, and an ester group is more preferred. R ₈ represents a lactone group or a sultone group. R ₇ represents a hydrogen atom, a halogen atom or an organic group (preferably a methyl group).

The resin (A) may contain a repeating unit having a carbonate group. As the carbonate group, a cyclic carbonate group is preferred. As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following formula (A-1) is preferred.

[Chemical Formula 8]

In the formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom or an organic group (preferably a methyl group). n represents an integer of 0 or more. R _A ² represents a substituent. When n is 2 or more, R _A ² each independently represents a substituent. A represents a single bond or a divalent linking group. Z represents an atomic group which forms a monocyclic group or a polycyclic group together with a group represented by -OC(=O)-O- in the formula.

The resin (A) has the repeating unit described in paragraphs <0370> to <0414> of the specification of the US Patent Application Publication No. 2016/0070167A1 as having a group selected from the group consisting of a lactone group, a sultone group, and a carbonate group. Repeating units of at least one group are also preferred.

The resin (A) may have a single repeating unit containing at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group, or may be used in combination of two or more kinds.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and the specific monomer corresponding to the repeating unit represented by the general formula (A-1) are listed below, but the present invention is not limited thereto. Specific examples. The following specific examples correspond to the case where R ₇ in the general formula (III) and R _A ¹ in the general formula (A-1) are a methyl group, but R ₇ and R _A ¹ can be arbitrarily derived from a hydrogen atom or a halogen atom. Or an organic group substitution.

[Chemical Formula 9]

In addition to the above monomers, the monomers shown below can also be suitably used as a raw material of the resin (A).

[Chemical Formula 10]

The content of the repeating unit having a group selected from at least one of the group consisting of a lactone group, a sultone group, and a carbonate group is 5 to 70 mol% with respect to all the repeating units in the resin (A). Preferably, 10 to 65 mol% is more preferred, and 20 to 60 mol% is further preferred. Further, when there are a plurality of repeating units having a group selected from at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group, the above content is a total amount.

(Repeating unit having a polar group) The resin (A) may have a repeating unit containing a polar group in addition to the repeating unit represented by the formula (1) or (2). Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, or a fluorinated alcohol group. As the repeating unit having a polar group, a repeating unit having an alicyclic group substituted with a polar group is preferred. Among them, the resin (A) is a repeating unit having a polar group, and a repeating unit having no acid-decomposable group is preferable. As the alicyclic group in the alicyclic group substituted with a polar group, an adamantyl group or a norbornyl group is preferred.

Specific examples of the monomer corresponding to the repeating unit having a polar group are listed below, but the present invention is not limited to these specific examples.

[Chemical Formula 11]

In addition, as a specific example of the repeating unit having a polar group, a repeating unit disclosed in paragraphs <0415> to <0433> of the specification of the US Patent Application Publication No. 2016/0070167A1 can be cited. The resin (A) may have a single repeating unit containing a polar group, or may be used in combination of two or more. The content of the repeating unit having a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, even more preferably from 10 to 25 mol%, based on all the repeating units in the resin (A). .

(Repeating unit having no acid-decomposable group or polar group) The resin (A) is preferably a repeating unit having no acid-decomposable group or a polar group. It is preferred that the repeating unit having no acid-decomposable group or a polar group has an alicyclic group. The repeating unit described in paragraphs <0236> to <0237> of the specification of the US Patent Application Publication No. 2016/0026083A1 is exemplified as the repeating unit having no acid-decomposable group or a polar group. Preferred examples of the monomer corresponding to the repeating unit having no acid-decomposable group and polar group are shown below.

[Chemical Formula 12]

In addition, as a specific example of the repeating unit which does not have an acid-decomposable group and a polar group, the repeating unit disclosed in the paragraph <0433> of the specification of the US patent application publication No. 2016/0070167A1 is mentioned. The resin (A) may have a single repeating unit having no acid-decomposable group or a polar group, or may be used in combination of two or more kinds. The content of the repeating unit having no one of the acid-decomposable group and the polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, based on all the repeating units in the resin (A). 5 to 25 mol% is further preferred.

In addition to the above repeating unit, the resin (A) can also adjust the dry etching resistance, the standard developer suitability, the substrate adhesion, the resist profile, or the properties generally required for the resist, that is, the resolution and heat resistance. There are various repeating units for the purpose of sensitivity or the like. Examples of such a repeating unit include a repeating unit corresponding to a predetermined monomer, but are not limited thereto.

The predetermined monomer is, for example, one selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. A compound which adds a polymerizable unsaturated bond or the like. In addition to this, an addition polymerizable unsaturated compound which can be copolymerized with a monomer corresponding to the above various repeating structural units can also be used. In the resin (A), the molar ratio of each repeating structural unit can be appropriately set in order to adjust various properties.

When the composition of the present invention is used for ArF exposure, it is preferred that the resin (A) does not substantially have an aromatic group from the viewpoint of transmittance of ArF light. More specifically, for all the repeating units in the resin (A), the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and most preferably 0 mol%. That is, it is further preferred that the repeating unit having no aromatic group is contained. Further, it is preferred that the resin (A) has a monocyclic or polycyclic alicyclic group.

In the resin (A), the acrylate-based repeating unit is preferably 50% by mole or less based on all the repeating units of the resin (A).

When the composition of the present invention is used for KrF exposure, EB exposure or EUV exposure, the resin (A) preferably contains a repeating unit having an aromatic hydrocarbon group. The resin (A) preferably contains a repeating unit having a phenolic hydroxyl group. Examples of the repeating unit having a phenolic hydroxyl group include a hydroxystyrene repeating unit or a hydroxystyrene (meth)acrylate repeating unit. When the composition of the present invention is used for KrF exposure, EB exposure or EUV exposure, the resin (A) has a structure in which a hydrogen atom of a phenolic hydroxyl group is decomposed and desorbed by an action of an acid (acid-releasing group). It is better. The content of the repeating unit having the aromatic hydrocarbon group contained in the resin (A) is preferably from 30 to 100 mol%, more preferably from 40 to 100 mol%, based on all the repeating units in the resin (A), and more preferably 50. ～100 mol% is further preferred.

The weight average molecular weight of the resin (A) 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, and particularly preferably from 3,000 to 11,000. The degree of dispersion (Mw/Mn) is usually 1.0 to 3.0, 1.0 to 2.6 is preferred, 1.0 to 2.0 is more preferred, and 1.1 to 2.0 is further preferred.

The resin (A) may be used alone or in combination of two or more. The content of the resin (A) in the total solid content of the composition of the present invention is not particularly limited, and is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 40 to 99.5% by mass, and 60 to 99%. The mass % is more preferably, and 80 to 97% by mass is further more preferable.

<Photoacid generator (C)> The composition of the present invention contains a photoacid generator (hereinafter also referred to as "photoacid generator (C)"). The photoacid generator is a compound which generates an acid by irradiation with actinic rays or radiation. As the photoacid generator, a compound which generates an organic acid by irradiation with actinic rays or radiation is preferred. For example, an onium salt compound, an onium salt compound, a diazonium salt compound, an onium salt compound, a quinone imide sulfonate compound, an oxime sulfonate compound, a diazodiamine compound, a diterpene compound, and an o-nitrobenzylsulfonate can be mentioned. Acid salt compound.

As the photoacid generator, a known compound which generates an acid by irradiation with actinic rays or radiation can be appropriately selected as a single or a mixture thereof. For example, paragraphs <0125> to <0319> of the specification of US Patent Application Publication No. 2016/0070167A1, paragraphs <0086> to <0094> of the specification of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016 A known compound disclosed in paragraphs <0323> to <0402> of the specification of 0237190A1 is used as the photoacid generator (C).

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

[Chemical Formula 13]

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The carbon number of the organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is usually from 1 to 30, and preferably from 1 to 20. Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group. Examples of the group formed by the two bonds in R ₂₀₁ to R ₂₀₃ include an alkyl group (for example, a butyl group, a pentyl group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - . Z ^- represents an anion.

Preferred examples of the cation in the general formula (ZI) include the compounds (ZI-1), the compound (ZI-2), the compound (ZI-3), and the compound (ZI-4) described later. Group. Further, the photoacid generator (C) may also be a compound having a plurality of structures represented by the formula (ZI). For example, it may be a compound having a structure in which at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the formula (ZI) and R ₂₀₁ to R of another compound represented by the formula (ZI) At least one of ₂₀₃ is bonded via a single bond or a linking group.

First, the compound (ZI-1) will be described. The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ of the above formula (ZI) is an aryl group, that is, a compound having an arylsulfonium as a cation. In the arylsulfonium compound, all of R ₂₀₁ to R _{203 may} be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group and the remainder may be an alkyl group or a cycloalkyl group. Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an arylbicycloalkylsulfonium compound.

As the aryl group contained in the arylsulfonium compound, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom or a sulfur atom. Examples of the heterocyclic ring structure include a pyrrole residue, a furan residue, a thiophene residue, an anthracene residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, two or more aryl groups may be the same or different. The aryl sulfonium compound has an alkyl group or a cycloalkyl group having a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms as needed. Preferable examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a secondary butyl group, a tertiary butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

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

Next, the compound (ZI-2) will be described. The compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represent an organic group having no aromatic ring. Here, the aromatic ring further contains an aromatic ring having a hetero atom. The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ is usually a carbon number of from 1 to 30 and a carbon number of from 1 to 20 is preferred. R ₂₀₁ to R ₂₀₃ are each independently an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkane. More preferably, an oxycarbonylmethyl group is a linear or branched 2-oxoalkyl group.

The alkyl group and the cycloalkyl group of R ₂₀₁ to R _{203 are} a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, or butyl group). A cycloalkyl group having a carbon number of 3 to 10 (for example, a cyclopentyl group, a cyclohexyl group and a norbornyl group) is preferred. R ₂₀₁ to R ₂₀₃ may be further substituted by a halogen atom, an alkoxy group (for example, a carbon number of 1 to 5), a hydroxyl group, a cyano group or a nitro group.

Next, the compound (ZI-3) will be described. The compound (ZI-3) is a compound represented by the following formula (ZI-3) and having a benzamidine methyl phosphonium salt structure.

[Chemical Formula 14]

In the formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group or an alkylcarbonyloxy group. A cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x and R _x and R _y may each bond to form a ring structure, and the ring structure may contain respectively Independently an oxygen atom, a sulfur atom, a ketone group, an ester bond or a guanamine bond. Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic fused ring in which two or more of these rings are combined. As the ring structure, it is usually a 3-member ring to a 10-member ring, and a 4-member ring to an 8-member ring is preferable, and a 5-member ring or a 6-member ring is more preferable.

Examples of the group formed by bonding any two or more of R _1c to R _5c and R _6c and R _7c and R _x and R _y include a butyl group and a pentyl group. The group formed by bonding R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylidene group. Zc ^- represents an anion.

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

[Chemical Formula 15]

In the formula (ZI-4), l represents an integer of 0 to 2. r represents an integer from 0 to 8. R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or a group having a cycloalkyl group. These groups may have a substituent. R ₁₄ represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group or a group having a cycloalkyl group. These groups may have a substituent. When there are a plurality of R ₁₄ , they may be the same or different. R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, a hetero atom such as an oxygen atom or a nitrogen atom may be contained in the ring skeleton. In one aspect, it is preferred that two R ₁₅ are an alkylene group and bonded to each other to form a ring structure. Z ^- represents an anion.

In the formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, an n-butyl group or a third butyl group.

Next, the general formulae (ZII) and (ZIII) will be described. In the general formulae (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group. As the aryl group of R ₂₀₄ to R ₂₀₇ , a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom or a sulfur atom. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, anthracene, benzofuran, and benzothiophene. The alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ , a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, or butyl group) A cycloalkyl group or a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group or a norbornyl group) is preferred.

The aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ each independently have a substituent. The aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent, and examples thereof include an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), and an aryl group. (e.g., carbon number: 6 to 15), alkoxy group (e.g., carbon number: 1 to 15), a halogen atom, a hydroxyl group, a phenylthio group, and the like. Z ^- represents an anion.

General formula (ZI) in the Z ^-, of the general formula (ZII) of Z ^-, of the general formula (ZI-3) in Zc ^- and the general formula (ZI-4) in the Z ^-, represented by the following general formula The anion represented by (3) is preferred.

[Chemical Formula 16]

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

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. Further, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. A fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is preferred, and a fluorine atom or CF ₃ is more preferred. In particular, both of the Xf-based fluorine atoms are further preferred.

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

L represents a divalent linking group. When there are multiple Ls, L may be the same or different. Examples of the divalent linking group include -COO-(-C(=O)-O-), -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ - And an alkyl group (preferably having a carbon number of 1 to 6), a cycloalkyl group (preferably having a carbon number of 3 to 15), an alkenyl group (preferably having a carbon number of 2 to 6), and a plural number thereof A two-valent linking group obtained by combination. Wherein -COO-, -CONH-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene- or -NHCO- The alkyl group is preferred, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene- is more preferred.

W represents an organic group having a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be a single ring type or a polycyclic ring type. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecyl group, a tetracyclo dodecanyl group, and an adamantyl group. Among them, an alicyclic group having a bulky structure such as a thiol group, a tricyclic fluorenyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group having a carbon number of 7 or more is preferable.

The aryl group may be a single ring type or a polycyclic type. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthracenyl group. The heterocyclic group may be a monocyclic ring or a polycyclic ring. Polycyclic rings are more capable of inhibiting the diffusion of acid. Further, the heterocyclic group may or may not have aromaticity. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include a lactone group and a sultone group exemplified in the above resin. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is preferred.

The above cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be any of a linear chain and a branched chain, preferably 1 to 12 carbon atoms), and a cycloalkyl group (which may be monocyclic or polycyclic (for example, further included) Any of the spiro rings, preferably having 3 to 20 carbon atoms, an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, a decylamino group, or a urethane group. , ureido, thioether, sulfonamide and sulfonate groups. Further, the carbon atom constituting the cyclic organic group (the carbon atom contributing to the formation of the ring) may be a carbon atom forming a carbonyl group.

As an anion represented by the general formula (3), SO ₃ ^- -CF ₂ -CH ₂ -OCO-(L)q'-W, SO ₃ ^- -CF ₂ -CHF-CH ₂ -OCO-(L)q' -W, SO ₃ ^- -CF ₂ -COO-(L)q'-W, SO ₃ ^- -CF ₂ -CF ₂ -CH ₂ -CH ₂ -(L)qW or SO ₃ ^- -CF ₂ -CH( CF ₃ )-OCO-(L)q'-W is preferred. Among them, L, q and W have the same meanings as in the formula (3). q' represents an integer from 0 to 10.

In one aspect, the general formula (ZI) in the Z ^-, of the general formula (ZII) of Z ^-, of the general formula (ZI-3) in Zc ^- and the general formula (ZI-4) in the Z ^-, An anion represented by the following formula (4) is also preferred.

[Chemical Formula 17]

In the formula (4), X ^B1 and X ^B2 each independently represent a hydrogen atom or an organic group having no fluorine atom. The X ^B1 and X ^B2 hydrogen atoms are preferred. X ^B3 and X ^B4 each independently represent a hydrogen atom or an organic group. At least one type fluorine atom or an organic group having fluorine atoms is preferred X ^B3 and X ^B4 is, X ^B3 and X ^B4 both type fluorine atom or an organic group having fluorine atoms is preferred. It is further preferred that both of X ^B3 and X ^B4 are alkyl groups substituted by fluorine atoms. L, q and W have the same meanings as in the formula (3).

General formula (ZI) in the Z ^-, of the general formula (ZII) in the Z ^-, of the general formula (ZI-3) in Zc ^- and the formula Z (ZI-4) ^- The acid may be an anion, A benzenesulfonic acid anion substituted with a branched alkyl group or a cycloalkyl group is preferred.

General formula (ZI) in the Z ^-, of the general formula (ZII) of Z ^-, of the general formula (ZI-3) in Zc ^- and the general formula (ZI-4) in the Z ^-, represented by the following general formula The aromatic sulfonic acid anion represented by (SA1) is also preferred.

[Chemical Formula 18]

In the formula (SA1), Ar represents an aryl group, and may have a substituent other than the sulfonate anion and the (D-B) group. Examples of the substituent which may be contained include a fluorine atom, a hydroxyl group and the like.

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

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

B represents a hydrocarbon group.

Preferably, D is a single bond and a B is an aliphatic hydrocarbon structure. B is preferably isopropyl or cyclohexyl.

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

[Chemical Formula 19]

Preferred examples of the general formula (ZI), the anion Z ^- in the formula (ZII), Zc ^{- in the} formula (ZI-3), and Z ^- in the formula (ZI-4) are shown below.

[Chemical Formula 20]

The above cations and anions can be arbitrarily combined and used as a photoacid generator.

The photoacid generator may be in the form of a low molecular compound or may be incorporated into a portion 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. The photoacid generator is preferably a form of a low molecular compound. When the photoacid generator 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 photoacid generator is in a form of being incorporated into a part of the polymer, a part of the aforementioned resin (A) may be incorporated, or may be incorporated into a resin different from the resin (A). The photoacid generator may be used singly or in combination of two or more. In the composition, the content of the photoacid generator (in total of the plurality of species) is preferably from 0.1 to 35% by mass, more preferably from 0.5 to 25% by mass, more preferably from 3 to 20, based on the total solid content of the composition. The mass % is further preferably, and 3 to 7 mass% is particularly preferable. When the compound represented by the above formula (ZI-3) or (ZI-4) is contained as a photoacid generator, the content of the photoacid generator contained in the composition (in the case of a plurality of species) The total solid content of the composition is preferably from 5 to 35% by mass, more preferably from 7 to 30% by mass.

<Resin (B)> When the composition of the present invention contains a crosslinking agent (G) to be described later, the composition of the present invention contains an alkali-soluble resin (B) having a phenolic hydroxyl group (hereinafter, also referred to as "resin (B)" ) is better. The resin (B) preferably contains a repeating unit having a phenolic hydroxyl group. At this time, typically, a negative pattern can be preferably formed. The crosslinking agent (G) may be in the form of being supported on the resin (B). The resin (B) may have the aforementioned acid-decomposable group.

The repeating unit represented by the following formula (II) is preferred as the repeating unit having a phenolic hydroxyl group which the resin (B) has.

[Chemical Formula 21]

In the formula (II), R ₂ represents a hydrogen atom, an alkyl group (preferably a methyl group) or a halogen atom (preferably a fluorine atom). B' represents a single bond or a divalent linking group. Ar' represents an aromatic ring group. m represents an integer of 1 or more. The resin (B) may be used alone or in combination of two or more. The content of the resin (B) in the total solid content of the composition of the present invention is not particularly limited, but is usually 30% by mass or more, preferably 40 to 99% by mass, and more preferably 50 to 90% by mass. 50 to 85% by mass is further preferred. As the resin (B), a resin disclosed in paragraphs <0142> to <0347> of the specification of the US Patent Application Publication No. 2016/0282720A1 is preferably exemplified.

<Acid Diffusion Control Agent (D)> The composition of the present invention preferably contains an acid diffusion controlling agent (D). The acid diffusion controlling agent (D) functions as a quencher for capturing an acid generated from a photoacid generator or the like during exposure, and suppressing the reaction of the acid-decomposable resin in the unexposed portion due to excessive acid generation. For example, a basic compound (DA), a basic compound (DB) which is reduced or disappeared by alkali by irradiation with actinic rays or radiation, and a bismuth salt (DC) which is relatively weak acid with respect to the acid generator can be used. An acid diffusion controlling agent is used as a low molecular compound (DD) having a nitrogen atom and having a group desorbed by an action of an acid, or a phosphonium salt compound (DE) having a nitrogen atom in a cationic portion. A known acid diffusion controlling agent can be suitably used in the composition of the present invention. For example, paragraphs <0627> to <0664> of the specification of US Patent Application Publication No. 2016/0070167A1, paragraphs <0095> to <0187> of the specification of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016 A known compound disclosed in paragraphs <0403> to <0423> of the specification of the specification No. 0237190A1, and paragraphs <0259> to <0328> of the specification of the US Patent Application Publication No. 2016/0274458A1 is used as the acid diffusion controlling agent (D).

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

[Chemical Formula 22]

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

The alkyl group in the formulae (A) and (E) may have a substituent or may be unsubstituted. The alkyl group is preferably an alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms. The alkyl group in the general formulae (A) and (E) is not substituted more preferably.

As the basic compound (DA), hydrazine, aminopyrrolidine, pyrazole, pyrazoline, piperidine, aminomorpholine, aminoalkylmorpholine or piperidine, etc., preferably having an imidazole structure, diazo a heterobicyclic structure, a ruthenium hydroxide structure, a ruthenium carboxylate structure, a trialkylamine structure, a compound of an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, or a hydroxyl group and/or an ether An aniline derivative or the like of the bond is more preferable.

A basic compound (DB) (hereinafter, also referred to as "compound (DB)") which is reduced or disappeared by alkali by irradiation with actinic rays or radiation. It has a proton-receptive functional group and is actinized by actinic A compound which decomposes by irradiation of radiation or radiation and which has reduced proton acceptability, disappears, or becomes acidic by proton acceptability.

A proton acceptor functional group refers to a group capable of electrostatically interacting with a proton or a functional group having an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether or a non-functional π-conjugated The functional groups of the nitrogen atom sharing the electron pair. The nitrogen atom having an unshared electron pair which does not contribute to π conjugate means, for example, a nitrogen atom having a partial structure represented by the following formula.

[Chemical Formula 23]

The preferred partial structure of the proton acceptor functional group may, for example, be a crown ether structure, an azacrown ether structure, a primary amine to a tertiary amine structure, a pyridine structure, an imidazole structure or a pyridinium structure.

The compound (DB) produces a compound which is decomposed by irradiation with actinic rays or radiation to reduce or disappear the proton acceptor property or change from proton acceptor to acidity. Among them, the decrease or disappearance of proton acceptor or the change from proton acceptor to acid refers to the change of proton acceptor caused by proton addition at the proton acceptor functional group, specifically, When a compound (DB) having a proton acceptor functional group and a proton form a proton adduct, the equilibrium constant in the chemical equilibrium is reduced. Proton acceptability can be confirmed by performing pH measurement.

The compound having the compound (DB) decomposed by the irradiation of actinic rays or radiation has an acid dissociation constant pKa satisfying pKa<-1, preferably -13<pKa<-1, and satisfying -13<pKa. <-3 is further preferred.

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, for example, as defined by Chemical Fact (II) (Revision 4, 1993, edited by the Chemical Society of Japan, Maruzen Company, Limited). The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution was measured by measuring the acid dissociation constant at 25 ° C using an infinitely diluted aqueous solution. Alternatively, the value of the database of the Hammett's substituent constant and the known literature value can be obtained by calculation using the software kit 1 described below. The values of pKa described in the present specification all represent values obtained by calculation using the software package.

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

In the composition of the present invention, an onium salt (DC) which is a relatively weak acid with respect to a photoacid generator can be used as an acid diffusion controlling agent. When a photoacid generator is used in combination and an antimony salt which is a relatively weak acid acid with respect to an acid produced by a photoacid generator, an acid produced by a photoacid generator by irradiation with actinic rays or radiation When it collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to form a phosphonium salt having a strong acid anion. In this process, the strong acid is exchanged to a weak acid which is lower in the catalyst, so that the acid is deactivated in appearance and the acid diffusion can be controlled.

The onium salt which is a relatively weak acid with respect to the photoacid generator is preferably a compound represented by the following formulas (d1-1) to (d1-3).

[Chemical Formula 24]

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (wherein a fluorine atom on a carbon adjacent to S is unsubstituted), R ⁵² An organic group, Y ³ is a linear, branched or cyclic alkyl or aryl group, Rf is a hydrocarbon group having a fluorine atom, and M ^{+ is} independently an ammonium cation, a phosphonium cation or a phosphonium cation.

Preferable examples of the phosphonium cation or the phosphonium cation represented by M ⁺ include an anthracene cation exemplified by the formula (ZI) and a phosphonium cation exemplified by the formula (ZII).

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

[Chemical Formula 25]

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

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a ring. An alkylaminocarbonyl group, an arylaminocarbonyl group, and the like. It is preferably an alkyl group, a cycloalkyl group or an aryl group.

The L _{1 of the} divalent linking group may, for example, be a linear or branched alkyl group, a cycloalkyl group, an extended aryl group, a carbonyl group, an ether bond, an ester bond, a guanamine bond or a urethane. A bond, a urea bond, a combination of two or more such groups, and the like, an alkyl group, an aryl group, an ether bond, an ester bond or a combination of two or more of these groups is preferred.

A low molecular compound (DD) having a nitrogen atom and having a group desorbed by an action of an acid (hereinafter, also referred to as "compound (DD)") has a function of being desorbed by an acid at a nitrogen atom. Amine derivatives of the group are preferred. As the group which is detached by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxy group or a half amine acetal group is preferred, and a urethane group is preferred. Or a semi-amine acetal ether group is more preferred. The compound (DD) has a molecular weight of preferably from 100 to 1,000, more preferably from 100 to 700, even more preferably from 100 to 500. The compound (DD) may also have a urethane group having a protective group on a nitrogen atom. The protective group constituting the urethane group is represented by the following formula (d-1).

[Chemical Formula 26]

In the formula (d-1), R _b each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), and an aryl group. It is a carbon number of 3 to 30), an aralkyl group (preferably having a carbon number of 1 to 10) or an alkoxyalkyl group (preferably having a carbon number of 1 to 10). R _b may also be bonded to each other to form a ring. The alkyl group, the cycloalkyl group, the aryl group and the aralkyl group represented by R _b may be independently independently a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group or an oxo group. Alkoxy or halogen atom substitution. The alkoxyalkyl group represented by R _{b is} also the same.

As R _b , a linear or branched alkyl group, a cycloalkyl group or an aryl group is preferred, and a linear or branched alkyl group or a cycloalkyl group is more preferred. Examples of the ring in which two R _b are bonded to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, and a derivative thereof. The specific structure of the group represented by the formula (d-1) is as disclosed in the paragraph <0466> of the specification of the US Patent Publication No. 2012/0135348A1, but is not limited thereto.

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

[Chemical Formula 27]

In the formula (6), l represents an integer of 0 to 2, and m represents an integer of 1 to 3, and satisfies l+m=3. R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two R _a may be the same or different, and two R _a may be bonded to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula. R _b has the same meaning as R _b in the above formula (d-1), and preferred examples are also the same. In the formula (6), the alkyl group, the cycloalkyl group, the aryl group or the aralkyl group as R _a may be independently substituted with the same group as the above-mentioned group of the following group, and the group is used as The alkyl group, cycloalkyl group, aryl group and aralkyl group of R _b may be substituted groups.

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

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic portion containing a nitrogen atom in the cation portion. The basic portion is preferably an amine group, and the aliphatic amine group is more preferably. It is further preferred that all of the atoms adjacent to the nitrogen atom in the basic portion are hydrogen atoms or carbon atoms. Further, from the viewpoint of improvement in alkalinity, an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly bonded to a nitrogen atom. A preferred example of the compound (DE) is a compound disclosed in paragraph <0203> of the specification of the US Patent Application Publication No. 2015/0309408 A1, but is not limited thereto.

Preferred examples of the acid diffusion controlling agent (D) are shown below.

[Chemical Formula 28]

[Chemical Formula 29]

In the composition of the present invention, the acid diffusion controlling agent (D) may be used alone or in combination of two or more. The content of the composition of the acid diffusion controlling agent (D) (in total of a plurality of kinds) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass based on the total solid content of the composition.

<Hydrophobic Resin (E)> The composition of the present invention may contain a hydrophobic resin (E). Further, the hydrophobic resin (E) is preferably a resin different from the resin (A) and the resin (B). The composition of the present invention contains a hydrophobic resin (E) whereby the static and/or dynamic contact angle on the surface of the resist film can be controlled. Thereby, it is possible to improve the development characteristics, suppress degassing, improve the liquid immersion liquid followability at the time of immersion exposure, and reduce liquid immersion defects and the like. The hydrophobic resin (E) is preferably formed locally on the surface of the resist film, but unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule, and it may not help to uniformly mix the polar substance and the non- Polar substance.

The hydrophobic resin (E) contains a group having a structure selected from a "fluorine atom", a "deuterium atom", and a "CH ₃ moiety structure contained in a side chain portion of the resin" from the viewpoint of being on the surface layer of the film. A resin of at least one of the repeating units is preferred. When the hydrophobic resin (E) has a fluorine atom and/or a ruthenium atom, the fluorine atom and/or the ruthenium atom in the hydrophobic resin (E) may be contained in the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin (E) has a fluorine atom, it is preferably a resin having a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom or an aryl group having a fluorine atom.

The hydrophobic resin (E) preferably has at least one group selected from the group consisting of the following (x) to (z). (x) acid group (y) base decomposable group (z) group decomposed by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamino group, a sulfonyl fluorenylene group, or an alkyl sulfonyl group. Methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indolyl, bis(alkylsulfonyl) a methylene group, a bis(alkylsulfonyl) fluorenylene group, a tris(alkylcarbonyl)methylene group, a tris(alkylsulfonyl)methylene group, and the like. As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group or a bis(alkylcarbonyl)methylene group is preferred.

Examples of the alkali-decomposable group (y) which the hydrophobic resin may have include a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C(O)OC(O)-), and a cerium. Amine (-NHCONH-), carboxylic acid thioester (-COS-), carbonate (-OC(O)O-), sulfate (-OSO ₂ O-) and sulfonate (-SO) ₂ O-) or the like, a lactone group or a carboxylate group (-COO-) is preferred. The repeating unit containing these groups is, for example, a repeating unit in which the groups are directly bonded to the main chain of the resin, and examples thereof include a repeating unit composed of an acrylate and a methacrylate. In the repeating unit, the groups may also be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced to the end of the resin by polymerization using a polymerization initiator or a chain transfer agent having the groups. The repeating unit having a lactone group may, for example, be the same repeating unit as the repeating unit having a lactone structure described in the previous section of the resin (A).

The content of the repeating unit having the alkali-decomposable group (y) is preferably from 1 to 100 mol%, more preferably from 3 to 98 mol%, more preferably from 5 to 95, based on all the repeating units in the hydrophobic resin (E). Molar% is further preferred.

The repeating unit having a group (z) which is decomposed by the action of an acid in the hydrophobic resin (E) may be the same repeating unit as the repeating unit having an acid-decomposable group exemplified in the resin (A). The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a ruthenium atom. The content of the repeating unit having the group (z) decomposed by the action of an acid is preferably from 1 to 80 mol%, and from 10 to 80 mol%, based on all the repeating units in the hydrophobic resin (E). More preferably, 20 to 60 mol% is further preferred. The hydrophobic resin (E) may further have another repeating unit different from the above repeating unit.

The repeating unit having a fluorine atom is preferably from 10 to 100 mol%, more preferably from 30 to 100 mol%, based on all the repeating units in the hydrophobic resin (E). Further, the repeating unit having a ruthenium atom is preferably from 10 to 100 mol%, more preferably from 20 to 100 mol%, based on all the repeating units in the hydrophobic resin (E).

On the other hand, particularly in the case where the hydrophobic resin (E) has a CH ₃ partial structure in the side chain portion, the hydrophobic resin (E) is preferably not substantially in the form of a fluorine atom or a ruthenium atom. Further, it is preferable that the hydrophobic resin (E) is substantially constituted only by a repeating unit composed of only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom.

The standard polystyrene-equivalent weight average molecular weight of the hydrophobic resin (E) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000.

The total content of the residual monomer and/or oligomer component contained in the hydrophobic resin (E) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. Further, the degree of dispersion (Mw/Mn) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.

As the hydrophobic resin (E), a known resin can be appropriately selected and used as a single or a mixture thereof. For example, it is known to use the disclosures of paragraphs <0451> to <0704> of the specification of US Patent Application Publication No. 2015/0168830A1, and paragraphs <0340> to <0356> of the specification of US Patent Application Publication No. 2016/0274458 A1. The resin is used as the hydrophobic resin (E). Further, the repeating unit disclosed in the paragraphs <0177> to <0258> of the specification of the US Patent Application Publication No. 2016/0237190A1 is also preferable as the repeating unit constituting the hydrophobic resin (E).

Preferred examples of the monomer corresponding to the repeating unit constituting the hydrophobic resin (E) are shown below.

[Chemical Formula 30]

[Chemical Formula 31]

The hydrophobic resin (E) may be used alone or in combination of two or more. It is preferable to use two or more types of hydrophobic resins (E) having different surface energies from the viewpoint of the liquid immersion liquid followability and development characteristics in the immersion exposure. The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content of the composition of the present invention.

<Solvent (F)> The composition of the present invention may contain a solvent. A well-known resist solvent can be used suitably in the composition of this invention. For example, paragraphs <0665> to <0670> of the specification of US Patent Application Publication No. 2016/0070167A1, paragraphs <0210> to <0235> of the specification of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016 A well-known solvent disclosed in paragraphs <024> to <0426> of the specification of the specification No. 0237190A1, and paragraphs <0357> to <0366> of the specification of the US Patent Application Publication No. 2016/0274458A1. Examples of the solvent which can be used in the preparation of the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, and alkyl alkoxypropionate. a cyclic lactone (preferably having a carbon number of 4 to 10), a monoketone compound which may have a ring (preferably having a carbon number of 4 to 10), an alkylene carbonate, an alkyl alkoxyacetate, and an alkyl pyruvate. An organic solvent such as a base ester.

As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group can be used. As the solvent having a hydroxyl group and a solvent having no hydroxyl group, the above-exemplified compounds can be appropriately selected. As the solvent having a hydroxyl group, an alkylene glycol monoalkyl ether or an alkyl lactate or the like is preferred, and propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or Ethyl lactate is more preferred. Further, as a solvent having no hydroxyl group, an alkyl glycol monoalkyl ether acetate, an alkyl alkoxy propionate, a monoketone compound having a ring, a cyclic lactone or an alkyl acetate may be used. More preferably, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate is more preferred, propylene glycol Further preferred is monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone. As the solvent having no hydroxyl group, propylene carbonate is also preferred. The mixing ratio (mass ratio) of the solvent having a hydroxyl group to the solvent having no hydroxyl group is usually from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferred in terms of coating uniformity. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a solvent of propylene glycol monomethyl ether acetate alone or a mixed solvent of two or more types of propylene glycol monomethyl ether acetate.

<Crosslinking Agent (G)> The composition of the present invention may contain a compound (hereinafter also referred to as a crosslinking agent (G)) which crosslinks the resin by the action of an acid. As the crosslinking agent (G), a known compound can be suitably used. For example, it is known to use the disclosures of paragraphs <0379> to <0431> of the specification of the US Patent Application Publication No. 2016/0147154A1, and paragraphs <0064> to <0141> of the specification of the US Patent Application Publication No. 2016/0282720A1. The compound acts as a crosslinking agent (G). The crosslinking agent (G) is a compound having a crosslinkable group capable of crosslinking a resin, and examples of the crosslinkable group include a methylol group, an alkoxymethyl group, a decyloxymethyl group, and an alkoxymethyl ether. A group, an oxirane ring group, an oxetane ring group, and the like. A crosslinkable group is preferably a methylol group, an alkoxymethyl group, an oxirane ring group or an oxetane ring group. The crosslinking agent (G) is preferably a compound having two or more crosslinkable groups (including a resin). The crosslinking agent (G) is preferably a hydroxymethyl group or an alkoxymethyl group, a phenol derivative, a urea compound (a compound having a urea structure) or a melamine compound (a compound having a melamine structure). The crosslinking agent may be used alone or in combination of two or more. The content of the crosslinking agent (G) is preferably from 1 to 50% by mass, more preferably from 3 to 40% by mass, even more preferably from 5 to 30% by mass, based on the total solid content of the resist composition.

<Interacting Agent (H)> The composition of the present invention may contain a surfactant, and when a surfactant is contained, a fluorine-based and/or a lanthanoid surfactant (specifically, a fluorine-based surfactant, a lanthanide interface) An active agent or a surfactant having both a fluorine atom and a ruthenium atom is preferred.

The composition of the present invention contains a surfactant, whereby when an exposure light source of 250 nm or less, particularly 220 nm or less is used, a pattern having less adhesion and development defects is obtained with good sensitivity and resolution. As the fluorine-based and/or lanthanoid surfactant, the surfactant described in paragraph <0276> of the specification of the US Patent Application Publication No. 2008/0248425 can be mentioned. Further, other surfactants than the fluorine-based and/or lanthanoid-based surfactants described in paragraph <0280> of the specification of the US Patent Application Publication No. 2008/0248425 may 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 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. On the other hand, the content of the surfactant is 10 ppm or more with respect to the total solid content of the composition, whereby the surface bias of the hydrophobic resin (E) is improved. Thereby, the surface of the resist film can be made more hydrophobic, and the water followability at the time of liquid immersion exposure can be improved.

(Other Additives) The composition of the present invention may further contain an acid multiplier, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, a dissolution promoter, and the like.

<Preparation method> The total solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7 % by mass, still more preferably 2.0 to 5.3 % by mass. The solid content concentration means the mass percentage of the mass of the components other than the solvent with respect to the total mass of the composition.

In addition, from the viewpoint of improving the resolution, the film thickness of the resist film composed of the composition of the present invention is preferably 20 nm or less, more preferably 15 nm or less. The lower limit of the film thickness of the resist film is preferably 20 nm or more, more preferably 40 nm or more. The film thickness can be set by setting the solid content concentration in the composition to an appropriate range and having an appropriate viscosity to adjust the coatability or film formability.

In the composition of the present invention, the above-mentioned components are preferably dissolved in a predetermined organic solvent, and the mixture is filtered, and then applied to a predetermined support (substrate). The pore size of the filter used in the filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. As the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferred. In the filter filtration, for example, as disclosed in Japanese Laid-Open Patent Publication No. 2002-062667, it is possible to carry out cyclic filtration, or to filter a plurality of filters in series or in parallel. Further, the composition may be subjected to plural filtrations. Further, the composition may be subjected to a degassing treatment or the like before and after the filter is filtered.

<Application> The composition of the present invention relates to a sensitized ray-sensitive or radiation-sensitive resin composition in which the properties are changed by irradiation with actinic rays or radiation. More specifically, the composition of the present invention relates to a semiconductor manufacturing step such as an IC, a circuit substrate such as a liquid crystal or a thermal head, a die structure for imprinting, and other photo-etching processing steps. Or lithographic printing plates. The pattern using the composition of the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, or a MEMS (Micro Electro Mechanical Systems).

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

The pattern forming method of the present invention has the following steps: (i) a step of forming a resist film on a support using the above-described sensitized ray-sensitive or radiation-sensitive resin composition (film forming step (resist film forming step) (ii) a step of exposing the resist film (irradiating actinic rays or radiation) (exposure step), and (iii) a step of developing the exposed resist film using a developing solution ( Development step).

The pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii) described above, and may have the following steps. In the pattern forming method of the present invention, (ii) the exposure method in the exposure step may also be immersion exposure. In the pattern forming method of the present invention, it is preferred to include (iv) a pre-bake (PB: PreBake) step before (ii) the exposure step. In the pattern forming method of the present invention, it is preferred to include (v) Post Exposure Bake (PE) after the (ii) exposure step and before the (iii) development step. In the pattern forming method of the present invention, a plurality of (ii) exposure steps may be included. In the pattern forming method of the present invention, a plurality of (iv) pre-baking steps may be included. In the pattern forming method of the present invention, a plurality of (v) post-exposure baking steps may be included.

In the pattern forming method of the present invention, the above (i) film forming step, (ii) exposure step, and (iii) developing step can be carried out by a generally known method. Further, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and an anti-reflection film may be formed between the resist film and the support. ). As the material constituting the resist underlayer film, a known organic or inorganic material can be suitably used. A protective film (top coat layer) may be formed on the upper layer of the resist film. A well-known material can be used suitably as a protective film. For example, the specification of US Patent Application Publication No. 2007/0178407, the specification of US Patent Application Publication No. 2008/0085466, the specification of US Patent Application Publication No. 2007/0275326, and the specification of US Patent Application Publication No. 2016/0299432 can be preferably used. A composition for forming a protective film disclosed in the specification of the US Patent Application Publication No. 2013/0244438, and the specification of the International Patent Application Publication No. 2016/157988A. The protective film forming composition containing the acid diffusion controlling agent is preferably a composition for forming a protective film. A protective film may be formed on the upper layer of the resist film containing the above hydrophobic resin.

The support is not particularly limited, and a substrate that is generally used in other photolithographic etching lithography steps, in addition to a manufacturing step of a semiconductor such as an IC or a manufacturing step of a circuit substrate such as a liquid crystal or a thermal head, can be used. Specific examples of the support include inorganic substrates such as ruthenium, SiO ₂ and SiN.

The heating temperature is preferably 70 to 130 ° C and more preferably 80 to 120 ° C in any of the (iv) prebaking step and the (v) post-exposure baking step. The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds in any of the (iv) prebaking step and the (v) post-exposure baking step. . The heating can be carried out by a mechanism provided in the exposure device and the developing device, or can be performed using a heating plate or the like.

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

(iii) In the developing step, the developing solution may be an alkaline developing solution or a developing solution containing an organic solvent (hereinafter also referred to as an organic developing solution).

As the alkaline developing solution, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, and an alkali aqueous solution such as an inorganic base, a primary amine to a tertiary amine, an alcoholamine or a cyclic amine can also be used. Further, the alkaline developing solution may contain an appropriate amount of an alcohol and/or a surfactant. The alkali concentration of the alkaline developer is usually from 0.1 to 20% by mass. The pH of the alkaline developer is usually from 10 to 15. The development time using an alkaline developer is usually 10 to 300 seconds. The alkali concentration, pH, and development time of the alkaline developing solution can be appropriately adjusted in accordance with the formed pattern.

The organic developing solution is preferably a developing solution containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, an ether solvent, and a hydrocarbon solvent.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, and 1-hexyl. Ketone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetamidine acetone, acetone acetone, ionone , diacetone alcohol, acetamethanol, acetophenone, methyl naphthyl ketone, isophorone and propylene carbonate.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, and propylene glycol monomethyl ether. Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxy Butyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate And butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate and butyl propionate.

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

The above solvent may be mixed in plural kinds, or may be mixed with a solvent other than the above or water. The water content of the entire developing solution is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably no moisture is contained. The content of the organic solvent relative to the organic developer is preferably 50 to 100% by mass based on the total amount of the developer, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass. % is especially good.

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

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

The organic developer may contain the above acid diffusion controlling agent.

As a 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 a method of depositing a developing solution on the surface of the substrate by a surface tension and allowing it to stand for a certain period of time (dip) a method of spraying a developing solution onto a surface of a substrate (spraying method); or a method of continuously ejecting a developing solution while ejecting a developing solution at a constant speed on a substrate rotating at a constant speed while being ejected at a constant speed (dynamic dispensing method) )Wait.

It is also possible to combine a step of developing with an aqueous alkali solution (alkaline developing step) and a step of developing using a developing solution containing an organic solvent (organic solvent developing step). Thereby, it is possible to form a pattern only by not dissolving the region of the intermediate exposure intensity, and thus it is possible to form a finer pattern.

(iii) After the developing step, a step (rinsing step) including washing with a rinsing liquid is preferred.

The rinsing liquid used in the rinsing step after the development step using the alkaline developing solution can use, for example, pure water. Pure water may contain a suitable amount of surfactant. Further, after the developing step or the rinsing step, the treatment of removing the developing solution or the rinsing liquid adhering to the pattern by the supercritical fluid may be added. Further, the heat treatment may be performed in order to remove moisture remaining in the pattern after the rinsing treatment or the treatment based on the supercritical fluid.

The rinse liquid used in the rinsing step after the development step using the developer containing the organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a usual organic solvent can be used. As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent is preferably used. Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent include the same examples as those described for the developer containing the organic solvent. As the rinsing liquid used for the rinsing step at this time, a rinsing liquid containing a monovalent alcohol is more preferable.

The monovalent alcohol used in the rinsing step may, for example, be a linear, branched or cyclic monovalent alcohol. Specific examples thereof include 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 1-hexanol, and 4-methyl group. 2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and methyl isobutyl methanol. Examples of the monovalent alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl iso Butyl methanol and the like.

Each component may be mixed in a plurality of types, or may be used in combination with an organic solvent other than the above. The water content in the rinse liquid when the solution containing the organic solvent is used as the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The rinsing liquid when the solution containing the organic solvent is used as the rinsing liquid may contain an appropriate amount of the surfactant. In the rinsing step at this time, the substrate which is developed using the organic developing solution is subjected to a cleaning treatment using a rinsing liquid containing an organic solvent. The method of the cleaning treatment is not particularly limited, and examples thereof include a method of continuously ejecting a rinse liquid on a substrate rotating at a constant speed (spin coating method); and immersing the substrate in a tank filled with a rinse liquid for a certain period of time The method (dipping method); or a method of spraying a rinsing liquid onto the surface of the substrate (spraying method) or the like. Among them, it is preferable to perform a cleaning treatment by a spin coating method and to rotate the substrate at a rotation speed of 2,000 to 4,000 rpm after washing to remove the rinse liquid from the substrate. Also, it is preferred to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing liquid remaining between the patterns and inside the pattern are removed by the heating step. In the heating step after the rinsing step, the heating temperature is usually 40 to 160 ° C, preferably 70 to 95 ° C, and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The various materials used in the composition of the present invention and the pattern forming method of the present invention (for example, a developer, a rinse liquid, an antireflection film-forming composition, or a top coat layer-forming composition) do not contain a metal component or a different one. Impurities such as structures and residual monomers are preferred. The content of the impurities contained in the various materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and is substantially not contained (below the detection limit of the measuring device).

As a method of removing impurities such as metals from various materials, for example, filtration using a filter can be mentioned. The pore diameter of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter can also be used by washing with an organic solvent in advance. In the filter filtration step, a plurality of filters may be connected in series or in parallel for use. When a plurality of filters are used, it is also possible to use a filter having a different aperture and/or material. Moreover, the various materials may be subjected to multiple filtrations, and the step of performing the plurality of filtrations may also be a cyclic filtration step. As the filter, a filter having a reduced amount of eluted matter disclosed in Japanese Laid-Open Patent Publication No. 2016-201426 is preferable. In addition to filter filtration, the removal of impurities by the adsorbent material can also be carried out, and the filter filter and the adsorbent material can also be used in combination. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as tannin or zeolite, or an organic adsorbent such as activated carbon can be used. As the metal adsorbent, for example, a metal adsorbent disclosed in JP-A-2016-206500 can be cited. In addition, as a method of reducing impurities such as metals contained in the above various materials, a method of selecting a raw material having a small metal content as a raw material constituting each material, filtering a raw material constituting each material, or a device may be mentioned. A method in which distillation is carried out under the conditions of contamination as much as possible by using TEFLON (registered trademark) for lining or the like. The preferred conditions for filter filtration of the raw materials constituting the various materials are the same as those described above.

In order to prevent the incorporation of the above-mentioned various materials, it is preferable to store the container described in the specification of the U.S. Patent Application Publication No. 2015/0227049 or the Japanese Patent Publication No. 2015-123351.

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

[Method of Manufacturing Electronic Component] The present invention also relates to a method of manufacturing an electronic component including the above-described pattern forming method. The electronic component manufactured by the method of manufacturing an electronic component of the present invention is suitably mounted on an electric and electronic device (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc. ). [Examples]

Hereinafter, the present invention will be further described in detail based on examples. The materials, the amounts, the ratios, the processing contents, the processing steps, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the invention should not be construed as being limited by the embodiments shown below. [Photosensitive ray-sensitive or radiation-sensitive resin composition]

The components used in the production of the photosensitive ray-sensitive or radiation-sensitive resin composition tested in the examples and the comparative examples are described below.

<Resin (A)> (Synthesis Example of Resin (A-2)) The resin (A-2) was synthesized according to the scheme shown below.

[Chemical Formula 32]

An aqueous solution of sodium hydroxide (14.1 g) and water (127 g) was cooled to 0 ° C, and Compound A (manufactured by NIPPON SHOKUBAI CO., LTD.) (50 g) was added while stirring. After the aqueous solution was warmed to room temperature (23 ° C), it was further stirred for 4 hours. Then, the aqueous solution was cooled to 0 ° C, and a 1N aqueous HCl solution (500 mL) was added dropwise. The obtained aqueous solution was extracted twice with dichloromethane (300 mL), and the extracted organic phase was dried over sodium sulfate. The dried organic phase was filtered and further concentrated to obtain a crude product containing Compound B as a main component.

When a mixed solution consisting of dimethylacetamide (460 mL), 2,6-di-t-butyl-4-methylphenol (50 mg), and potassium carbonate (48.6 g) was stirred, it was added dropwise. Compound B is a crude product of the main component. Then, α-bromo-γ-butyrolactone (52.8 g) was added dropwise to the mixed solution, and after the completion of the dropwise addition, the mixed solution was heated to 40 ° C and stirred for 5 hours to cause a reaction. After completion of the reaction, ethyl acetate (400 mL) and water (100 mL) were added to the mixture. After the mixed solution was washed with a saturated aqueous sodium hydrogencarbonate solution (200 mL), the organic phase was extracted. The remaining aqueous phase was extracted twice with ethyl acetate (200 mL) and the organic phase was further collected. The obtained organic phase was washed twice with a saturated aqueous solution of ammonium chloride (100 mL), and the organic phase was dried over sodium sulfate. The dried organic phase was filtered and further concentrated to obtain a crude product containing the monomer A. The crude product containing the monomer A was purified by a silica gel column to obtain a high purity product (36.6 g) of the monomer A (2 steps, yield: 51%).

The result of the monomer A obtained by ¹ H-NMR (Nuclear Magnetic Resonance) measurement was as follows. ¹ H-NMR, 400 MHz, δ ((CDCl ₃ ) ppm: 2.30-2.40 (1H, m), 2.71-2.73 (1H, m), 4.01-4.10 (2H, m), 4.22 (2H, s), 4.33 (1H, q), 4.50 (1H, t), 5.21 (1H, d), 5.31 (1H, d), 5.50 (1H, t), 5.85-6.00 (1H, m), 6.02 (1H, s), 6.42 (1H, s).

The cyclohexanone (4.95 parts by mass) was heated to 85 ° C under a nitrogen stream. Monomer A (2.26 parts by mass), monomer B (1.96 parts by mass) shown in the above scheme, cyclohexanone (9.19 parts by mass), and polymerization initiator AIBN (azobisisobutyronitrile) (0.046 parts by mass) The mixed solution was added dropwise to the liquid over 4 hours while stirring. After the completion of the dropwise addition, the mixture was further stirred at 85 ° C for 2 hours. After the reaction solution was allowed to stand for cooling, reprecipitation treatment was carried out using a large amount of methanol/water (mass ratio: 9:1). The precipitated solid was taken out and further subjected to vacuum drying, whereby Resin (A-2) (2.62 parts by mass) was obtained.

The other resins (A-1) (A-3) to (A-13) and (A-15) to (A-20) shown below were synthesized in the same manner. Further, the resin (A-14) was synthesized in accordance with a usual method. Further, in the following tests, resins (A-1) to (A-13) and (A-18) to (A-20) were used in the examples, and a resin (A-14) was used in the comparative example. ~ (A-17).

The repeating unit of the resin (A) used in the examples and the comparative examples is shown below. Further, the numerical values indicated on the side of each repeating unit indicate the content (% by mole) of each repeating unit in each resin.

[Chemical Formula 33]

[Chemical Formula 34]

The values of the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the resins (A-1) to (A-20) are shown below.

[Table 1]

<Photoacid generator> The structure of the photoacid generator (C) used in the examples and the comparative examples is shown below.

[Chemical Formula 35]

<Acid Diffusion Control Agent> The structure of the acid diffusion controlling agent (D) used in the examples and the comparative examples is shown below.

[Chemical Formula 36]

<Hydrophilic Resin> The structures of the hydrophobic resin (E) used in the examples and the comparative examples are shown below.

[Chemical Formula 37]

Further, the hydrophobic resin (1b) had a weight average molecular weight (Mw) of 7,000, a degree of dispersion (Mw/Mn) of 1.30, and a molar ratio of each repeating unit of 50/45/5 from the left. The weight average molecular weight (Mw) of the hydrophobic resin (2b) was 18,600, and the degree of dispersion (Mw/Mn) was 1.57, and the molar ratio of each repeating unit was 40/40/20 from the left.

<Solvent> The solvent (F) used in the examples and the comparative examples is shown below. SL-1: Propylene glycol monomethyl ether acetate (PGMEA) SL-2: Propylene glycol monomethyl ether (PGME) SL-3: Cyclohexanone SL-4: γ-butyrolactone

<Interacting Agent> The surfactant (H) used in the examples and the comparative examples is shown below. W-1: Poly Fox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based surfactant)

[Preparation of a sensitizing ray-sensitive or radiation-sensitive resin composition] Each of the components shown in the following Table 2 was prepared so that the solid content concentration was 3.8% by mass. At this time, the solid content was blended so as to have a mass ratio shown in Table 2. In addition, the solid content as used herein means all components except the solvent (F). The prepared mixed solution was filtered through a polyethylene filter having a pore size of 0.1 μm. The obtained liquid was used as a sensitizing ray-sensitive or radiation-sensitive resin composition, and was evaluated in Examples and Comparative Examples.

[Evaluation] <Formation of Pattern> A composition for forming an organic antireflection film, ARC29SR (manufactured by Nissan Chemical Industries, Ltd.), was applied onto a tantalum wafer, and heated at 205 ° C for 60 seconds to form a film thickness. 95nm anti-reflection film. The sensitized ray-sensitive or radiation-sensitive resin composition of the examples and the comparative examples was applied onto the obtained antireflection film, and heated at 100 ° C for 60 seconds (PB: Prebake) to form a film. A 85 nm thick resist film. An ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, Nesigma 0.812, XY deflection) was used, and a 1:1 line and space pattern with a line width of 44 nm was used. A 6% halftone mask was used to expose the resist film on the obtained wafer. Ultrapure water was used as the liquid immersion liquid. Then, after the exposed resist film was heated at 105 ° C for 60 seconds (PEB: Post Exposure Bake), a negative developing solution (organic developing solution, butyl acetate) was used by the liquid coating method. The development was carried out for 30 seconds, and further rinsed with a rinse solution (methyl isobutylmethanol (MIBC)) by a coating method for 30 seconds. Next, the tantalum wafer was spin-dried at a rotational speed of 4000 rpm for 30 seconds to form a pattern of a 1:1 line and space having a line width of 44 nm.

<Line width roughness (LWR, nm)> A pattern of a 1:1 line and space of 44 nm obtained was observed from the upper portion of the pattern using a length-measuring scanning electron microscope (manufactured by Hitachi, Ltd., S-8840). At this time, the line width was measured at 50 points in the range of 2 μm in the longitudinal direction of the line pattern, and the standard deviation (3σ) was calculated for the measured deviation of the measured line width. The smaller the coefficient, the better the LWR performance. The results are shown in Table 2 below.

<Exposure latitude (EL, %)> The exposure amount of the 1:1 line and space mask pattern having a reproduction line width of 44 nm was determined, and this was set as the optimum exposure amount Eopt. Next, the exposure amount of the line width of the line was ±10% of the target value of ±10% (that is, 39.6 nm and 48.4 nm). Using the value of the obtained exposure amount, the exposure latitude (EL) defined by the following formula is calculated. The larger the value of EL is, the smaller the change in line width caused by the change in exposure amount is, and the better the EL performance of the resist film is. EL (%) = [[(Line line width becomes exposure amount of 48.4 nm) - (line width of line is 39.6 nm)] / Eopt] × 100 The results are shown in Table 2 below.

<Sensitivity (mJ/cm ² )> The optimum exposure amount Eopt obtained in the evaluation of the above exposure latitude was taken as the sensitivity (mJ/cm ² ) of each resist film. It is shown that the smaller the value, the more excellent the sensitivity of the resist film. The results are shown in Table 2 below.

The results of the evaluation of the blending of the sensitizing ray-sensitive or radiation-sensitive resin composition and the LWR and EL in each of the examples and the comparative examples are shown in Table 2 below. In Table 2, the value in parentheses in the column of each solid component indicates the ratio (mass ratio) of the amounts of the solid components to each other. The value in parentheses in the column of the solvent indicates the ratio (mass ratio) of the amount of each solvent. In addition, as described above, the total amount of the solvent added is such that the solid content concentration of each of the sensitizing ray-sensitive or radiation-sensitive resin composition is 3.8% by mass. In Table 2, the column of the formula (R) indicates that the resin (A) contained in the sensitizing ray-sensitive or radiation-sensitive resin composition has a repeating unit represented by the formula (1) or (2). In the case of the above, the group represented by the formula (R) in the above repeating unit is present. In the column of "acid-releasing group", in the case where the repeating unit represented by the formula (1) or (2) in the resin (A) has a group represented by the above formula (R), Whether or not there is an acid-releasing group in the group equivalent to R ₅ . In Table 2, the column of "ether group" indicates that the resin (A) contained in the sensitized ray-sensitive or radiation-sensitive resin composition has a repeating unit represented by the formula (1) or (2). Whether or not the ether group in the alkyl group in the group represented by L ₁ or L ₂ in the above repeating unit is present. In Table 2, the column of the formula (A) × 2 indicates that the resin (A) contained in the sensitized ray-sensitive or radiation-sensitive resin composition has a repeat represented by the formula (1) or (2). In the case of the unit, in the alkyl group of the group represented by L ₁ or L ₂ in the above repeating unit, there are _two groups represented by the formula (A).

[Table 2]

As is apparent from Table 2, by using the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention, a resist film excellent in EL performance and a pattern excellent in LWR performance can be obtained. In addition, it was confirmed that the repeating unit represented by the formula (1) or (2) which the resin (A) contained in the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention has the general formula (R) In the case of the groups indicated, the effects of the present invention which are more excellent (comparison of Examples 2 and 6 to 17 with other examples) can be obtained. When the repeating unit represented by the formula (1) or (2) is further an alkyl group having an ether group of L ₁ or L ₂ , the LWR performance of the pattern is more excellent (Examples 2, 7 to 8) And the results of 11 to 14). Further, it was confirmed that the repeating unit represented by the formula (1) or (2) is a patterned LWR when L ₁ or L ₂ has two alkyl groups represented by the group represented by the formula (A). The tendency to be more excellent (the results of Examples 15 to 17). It is confirmed that the group corresponding to R ₅ of the group represented by the formula (R) in the repeating unit represented by the formula (1) or (2) is a group other than the acid-releasing group. The sensitivity of the etchant film was more excellent (comparison of Examples 14 and 17 with other examples).

It has been confirmed that even when the resist film formed in the above-described embodiment is subjected to ArF exposure, and the exposed film is subjected to alkali development, a resist film excellent in EL performance and excellent LWR performance can be obtained. The pattern. It is also confirmed that even in the case where the resist film formed in the above embodiment is subjected to KrF exposure, electron beam exposure or EUV exposure, and the exposed film is subjected to alkali development or organic solvent development, it is also obtained. A resist film with excellent EL performance and a pattern with excellent LWR performance.

Claims (12)

A photosensitive ray- or radiation-sensitive resin composition comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2) Resin, and photoacid generator, In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, a group represented by the formula (A) or an organic group other than the group represented by the formula (A), and R ₁ and At least one of R ₂ represents a group represented by the formula (A), L ₁ represents an alkylene group which may have a substituent, and a part of a carbon atom in the alkylene group represented by L ₁ may be hetero Substituted by a group of an atom, the substituent may have a hetero atom, wherein the group represented by L ₁ has one or more hetero atoms, and both R ₁ and R ₂ are represented by the formula (A). In the case of one of the hetero atomic groups possessed by the group represented by L ₁ , at least one of the two R groups of the two groups represented by the general formula (A) has Hydrocarbon group of a hetero atom, *-C(=O)-OR (A) In the formula (A), R represents a hydrocarbon group or a hydrogen atom which may have a hetero atom, * represents a bonding position, and in the formula (2), R ₃ and R ₄ each independently represent a hydrogen atom or an organic group, L ₂ represents a substituent of the alkylene group, part of the carbon atoms of the alkylene group represented by the L ₂ may A group having the hetero atom substituted, the hetero atom may have a substituent group, wherein the group represented by L ₂ having the one or more hetero atoms. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the resin is 10% by mass or more based on the total solid content of the sensitized ray-sensitive or radiation-sensitive resin composition. . The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein at least one of R ₃ and R ₄ is an organic group. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein at least one of R ₁ and R ₂ is a group represented by the formula (R), R ₃ and R ₄ At least one of them is a group represented by the formula (R), *-C(=O)-OR ₅ (R) In the formula (R), R ₅ represents a hydrogen atom, an alkali-decomposable group or an acid detachment. Sex base, * indicates the bond position. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein R ₅ represents an alkali-decomposable group. The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the L ₁ group may have a substituent, an alkyl group having an ether group or have 2 The alkyl group of the group represented by the formula (A), the L ₂ group may have a substituent, an alkyl group having an ether group or two groups having a group represented by the formula (A) alkyl. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein R ₁ and R ₂ are a group represented by the formula (R), and the L ₁ system has two The group of the group represented by the formula (A). The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of the items 1 to 5, wherein the resin further has a repeating unit represented by the formula (3), In the formula (3), R ₆ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, L ₃ represents a divalent linking group which may have a substituent, and X represents an acid-releasing group. The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the resin further has a repeating unit selected from the group consisting of a lactone group, and has neither an acid The decomposable group also does not have at least one repeating unit of the group consisting of repeating units of polar groups. A resist film formed by using the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9. A pattern forming method, comprising: a resist film forming step of forming a resist film using the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9; An exposure step of exposing the resist film; and a developing step of developing the exposed resist film using a developing solution. A method of manufacturing an electronic component, comprising the pattern forming method according to claim 11 of the patent application.