KR101981508B1 - Active light sensitive or radiation sensitive resin composition, active light sensitive or radiation sensitive film, mask blank provided with active light sensitive or radiation sensitive film, pattern forming method, method for manufacturing electronic device, and electronic device - Google Patents

Abstract

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film using the same, a mask blank having the film, a pattern formation method, And an electronic device manufactured by the manufacturing method of the electronic device. (A) an onium salt compound containing at least one fluorine atom in the anion moiety and at least one nitrogen atom in the cation moiety, and (B) an onium salt compound containing at least one nitrogen atom in the cation moiety, (A) relative to the total mass of the compound (A), wherein the compound (A) contains at least one fluorine atom and generates an acid upon irradiation with an actinic ray or radiation, The content of fluorine atoms in the compound (B) is larger than the content of fluorine atoms in the compound (B) with respect to the total mass of the compound (B).

Description

TECHNICAL FIELD [0001] The present invention relates to a mask blank having an actinic ray-sensitive or radiation-sensitive resin composition, an actinic radiation or radiation-sensitive film, an actinic radiation or radiation-sensitive film, a pattern formation method, SENSOR OR ORIENTATION RESIN COMPOSITION, ACTIVE LIGHT SENSITIVE OR RADIATION SENSITIVE FILM, MASK BLANK PROVIDED WITH ACTIVE LIGHT SENSITIVE OR RADIATION SENSITIVE FILM, PATTERN FORMING METHOD, METHOD FOR MANUFACTURING ELECTRONIC DEVICE, AND ELECTRONIC DEVICE}

INDUSTRIAL APPLICABILITY The present invention is suitably used for a super-microlithography process such as the manufacture of a super LSI or a high-capacity microchip or other fabrication process, and can form a pattern with high definition using an electron beam or an extreme ultraviolet ray A photomask, a photomask, a method of forming a pattern, a method of manufacturing an electronic device, a method of forming a photomask, a method of forming a photomask, a method of forming a photomask, And an electronic device. In particular, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a process using a substrate having a specific undercoat film, a sensitizing actinic ray or radiation-sensitive film employing it, A photomask, a pattern forming method, a method of manufacturing an electronic device, and an electronic device.

Conventionally, in the process of manufacturing semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition is performed. In recent years, with the increase in integration of integrated circuits, ultrafine pattern formation in a submicron region or a quarter micron region has been required. As a result, the exposure wavelength tends to be shorter in the wavelength range from g-line to i-line, and further to excimer laser light, and lithography using electron beams or X-rays is under development at present.

Electron beam or extreme ultraviolet lithography has established itself as a next-generation or next-generation pattern formation technology, and since it is high-resolution, it is widely used for manufacturing a photomask used for semiconductor exposure. For example, in the step of fabricating the photomask by electron beam lithography, a resist layer is formed on a shielding substrate provided with a shielding layer mainly composed of chromium or the like on a transparent substrate, selectively subjected to electron beam exposure, Thereby forming a resist pattern. Next, a photomask having a shielding layer having a predetermined pattern on the transparent substrate can be obtained by etching the shielding layer using this resist pattern as a mask and forming a pattern on the shielding layer.

As described above, as the required pattern becomes finer, the degradation of the resolution due to the pattern shape becomes a problem. As one method for solving the problem of resolution, Reference 1 discloses the use of an acid generator containing a nitrogen atom at the cation portion.

Particularly, in the case of forming a negative pattern, there is a problem that the shape of the pattern end portion is expanded (hereinafter also referred to as T-top shape), and a bridge is easily formed in an isolated space pattern. As described above, in a negative pattern, it is more difficult to improve the resolution and a negative resist composition excellent in resolution is required.

In such a situation, for example, in Patent Document 2, there is disclosed a method for producing a compound containing an onium salt compound containing a nitrogen atom in a cation portion, a compound capable of generating an acid upon irradiation with an actinic ray or radiation, Discloses a negative resist composition which is capable of obtaining a negative pattern having excellent resolution in pattern formation using electron beams or extreme ultraviolet rays (EUV light).

Patent Document 1: JP-A-2007-230913 Patent Document 2: JP-A-2014-134686

The use of an onium salt compound containing a nitrogen atom at the cation portion improves the shape of the T-top in the negative pattern and remarkably improves the pattern shape and resolution. As a result of intensive research conducted by the present inventors, It has been found that a problem may occur in bridge defects and pattern collapse in the case of using a development process of a high developing solution flow rate or a developing process of a high developing solution flow rate. Particularly, in the case of forming ultrafine patterns such as line widths of 50 nm or less, further improvement is required for bridge defects and pattern collapse.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming an ultrafine pattern having excellent sensitivity and resolution and further suppressing bridge defects and pattern collapse , An active ray-sensitive or radiation-sensitive film using the same, a mask blank having the film, and a pattern forming method. The present invention also provides a manufacturing method of an electronic device including the pattern forming method, and an electronic device manufactured by the manufacturing method of the electronic device.

The present invention is as follows in one aspect.

[One]

(A) an onium salt compound containing at least one fluorine atom in the anion moiety and at least one nitrogen atom in the cation moiety, and

(B) a compound which generates at least one fluorine atom and generates an acid upon irradiation with an actinic ray or radiation, wherein the radiation-sensitive or radiation-

Wherein the fluorine atom content in the compound (A) relative to the total mass of the compound (A) is larger than the fluorine atom content in the compound (B) relative to the total mass of the compound (B) .

[2]

The sensitive actinic radiation-sensitive or radiation-sensitive resin composition according to [1], wherein a difference between the content of the fluorine atom in the compound (A) and the content of the fluorine atom in the compound (B) is 0.5% by mass or more in terms of mass percentage.

[3]

The active radiation or radiation-sensitive resin composition according to [1] or [2], wherein the compound (B) is a sulfonate compound containing at least one fluorine atom in the anion moiety.

[4]

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the cation moiety of the compound (A) has a basic moiety containing the nitrogen atom.

[5]

The active radiation-sensitive or radiation-sensitive resin composition according to [4], wherein the basic moiety of the compound (A) comprises an amino group or a nitrogen-containing heterocyclic group.

[6]

The active radiation or radiation-sensitive resin composition according to any one of [1] to [5], wherein the cation moiety of the compound (A) has a partial structure represented by the following formula (N-I)

[Chemical Formula 1]

Wherein,

R _A and R _B each independently represent a hydrogen atom or an organic group.

X represents a single bond or a linking group.

At least two of R _A , R _B and X may be bonded to each other to form a ring.

[7]

The active radiation or radiation-sensitive resin composition according to any one of [1] to [6], wherein the compound (A) is an onium salt represented by the following formula (N-II).

(2)

Wherein,

A represents a sulfur atom or an iodine atom.

R ₁ represents a hydrogen atom or an organic group, and when a plurality of R _{1 s} exist, R ₁ may be the same or different.

R represents an (o + 1) -valent organic group, and when a plurality of R exists, R may be the same or different.

X represents a single bond or a linking group, and when a plurality of X exist, X may be the same or different.

A _N represents a basic site containing a nitrogen atom, and when a plurality of A _N exist, A _N may be the same or different.

When A is a sulfur atom, n is an integer of 1 to 3, and m is an integer satisfying the relationship of m + n = 3.

When A is an iodine atom, n is 1 or 2, and m is an integer satisfying the relationship of m + n = 2.

o represents an integer of 1 to 10;

Y ^- represents an anion.

At least two of R ₁ , X, R and A _N may be bonded to each other to form a ring.

[8]

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [3] to [7], wherein the compound (A) and the compound (B) have the same anion moiety.

[9]

The content of the compound (A) relative to the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition is in the range of 0.1 to 20% by mass. The active radiation ray or sensitive Radiation Resin Composition.

[10]

Sensitive photocurable resin composition according to any one of [1] to [9], further containing a compound containing an acid crosslinkable group (C).

[11]

The active radiation or radiation-sensitive resin composition according to [10], wherein the compound (C) containing an acid crosslinkable group contains two or more hydroxymethyl groups or alkoxymethyl groups in the molecule.

[12]

Sensitive functional resin composition according to any one of [1] to [11], further comprising (D) a compound containing a phenolic hydroxyl group.

[13]

The active radiation or radiation-sensitive resin composition according to [12], wherein the compound (D) containing a phenolic hydroxyl group is a resin containing a repeating unit represented by the following formula (II).

(3)

Wherein,

R ₂ represents a hydrogen atom, a methyl group which may have a substituent, or a halogen atom.

B 'represents a single bond or a divalent organic group.

Ar 'represents aromatic ventilation.

m represents an integer of 1 or more.

[14]

The active radiation or radiation-sensitive resin composition according to [13], wherein the compound (D) containing a phenolic hydroxyl group is a resin further comprising a repeating unit represented by the following general formula (III).

[Chemical Formula 4]

Wherein,

Ar ₁ represents aromatic ring.

R ₁ and R ₂ each independently represent an alkyl group, a cycloalkyl group, or an aryl group.

X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an acyl group.

R ₃ represents a hydrogen atom, an organic group or a halogen atom.

B represents a single bond or a linking group.

n represents an integer of 1 or more.

At least two of Ar ₁ , R ₁ and R ₂ may be bonded to each other to form a ring. When n represents an integer of 2 or more, a plurality of R ₁ , a plurality of R _2, and a plurality of X may be mutually the same or different.

[15]

An actinic ray-sensitive or radiation-sensitive film comprising the composition according to any one of [1] to [14].

[16]

A mask blank having the actinic ray-sensitive or radiation-sensitive film according to [15].

[17]

A step of forming a sensitizing actinic ray or radiation-sensitive film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [14]

Irradiating the actinic ray-sensitive or radiation-sensitive film with an actinic ray or radiation, and

And developing the actinic ray-sensitive or radiation-sensitive film which is irradiated with actinic rays or radiation.

[18]

The pattern forming method according to [17], wherein the actinic ray or radiation is irradiated using an electron beam or an extreme ultraviolet ray.

[19]

[17] A method of manufacturing an electronic device, comprising the pattern formation method according to [18] or [18].

[20]

The electronic device produced by the method for manufacturing an electronic device according to [19].

According to the present invention, there is provided an actinic ray-sensitive or radiation-sensitive resin composition capable of forming an ultrafine pattern having excellent sensitivity and resolution, further suppressing bridge defects and pattern collapse, It becomes possible to provide a radiation film, a mask blank having the film, and a pattern forming method. Further, according to the present invention, it becomes possible to provide an electronic device manufacturing method including the pattern forming method, and an electronic device manufactured by the electronic device manufacturing method.

1 is an NMR chart ( ¹ H NMR, acetone-d6) of an acid crosslinking agent (CL-7) synthesized in the examples.
2 is an NMR chart ( ¹ H NMR, acetone-d6) of a compound (CL-7A) which is an intermediate of the crosslinking agent (CL-7) synthesized in the examples.

Hereinafter, embodiments of the present invention will be described in detail.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes a group (atomic group) having a substituent group together with a group (atomic group) having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term " actinic ray " or " radiation " in this specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray represented by an excimer laser, extreme ultraviolet ray (EUV light), X ray, electron beam (EB) In the present invention, light means an actinic ray or radiation.

The term " exposure " in this specification refers to not only exposure by deep ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers but also exposure to particle beams such as electron beams and ion beams Is included in the exposure.

<Sensitive actinic ray or radiation sensitive resin composition>

(Hereinafter also referred to as " the composition of the present invention ") of the present invention contains at least one fluorine atom in the anion portion and further contains at least one nitrogen atom in the cation portion (Hereinafter referred to as "onium salt compound (A)" or "compound (A)") and an at least one fluorine atom (A) and the acid generator (B) (hereinafter referred to as " acid generator (B) " Has a relation that the content of fluorine atoms relative to the total mass of the onium salt compound (A) is larger than the content of fluorine atoms relative to the total mass of the acid generator (B).

As described above, by adding an onium salt compound containing a nitrogen atom to the cation moiety in the actinic ray-sensitive or radiation-sensitive resin composition, the T-top shape is improved and the pattern shape and resolution are remarkably improved. The inventors of the present invention have found that there is room for further improvement in bridging defects and pattern collapsing, particularly when ultrafine patterns such as line widths of 50 nm or less are formed.

As a result of further studies by the present inventors, it has been found that an onium salt compound (A) containing at least one fluorine atom in the anion portion and at least one nitrogen atom in the cation portion and (A) having a relationship that the content of fluorine atoms in the onium salt compound (A) is larger than the content of fluorine atoms in the acid generator (B), and the amount of the acid generator (B) It has been found that the problem of the present invention can be solved by using the generator (B) in combination. Namely, it has been found that an ultrafine pattern having a line width of 50 nm or less which is excellent in suppressing bridge defects and pattern collapse is obtained in addition to improvement in sensitivity and resolution. It has also been found that the effect of the present invention becomes more remarkable in the case of using a developing process for a long time or a developing process with a rapid developing solution flow rate, particularly for a thick resist film thickness of 100 nm or more. The reason for this is not necessarily clear, but it is assumed as follows.

That is, in a system in which a basic onium salt compound and an acid generator coexist in a sensitizing actinic ray-sensitive or radiation-sensitive resin composition, the basic onium salt compound becomes relatively hydrophilic with respect to the acid generator due to the presence of a basic group. As a result, at the time of film formation, the basic onium salt compound tends to form a non-uniform distribution on the surface side of the substrate coated with the composition, where the acid generating agent is localized on the air interface side. As a result, the generation of bridges and pattern collapse is promoted as a result of the lack of the acidity occurring near the surface of the resist film, and the crosslinking reaction progresses not only in the exposed portion but also in the unexposed portion.

On the other hand, when the concentration of the basic onium salt compound in the vicinity of the surface of the resist film is lower than the concentration of the acid generator in the vicinity of the resist film surface by using an acid generator containing a fluorine atom and a basic onium salt compound having a larger content of fluorine atoms than the acid generator, It becomes possible to make the concentration larger than the concentration. As a result, it is presumed that insufficient generation of the generated acid in the vicinity of the surface of the resist film is solved, which is effective in improving the sensitivity and resolving ability and improving the inhibition of bridge defect and pattern collapse. Particularly, when the acid generator and the basic onium salt contain at least one fluorine atom in the anion portion, since the acid strength of the acid generated from the acid generator and the basic onium salt is strong, the crosslinking in the actinic ray- The reactivity and the de-protection reactivity are enhanced. In such a highly reactive sensitizing actinic ray-sensitive or radiation-sensitive resin composition, bridge defects and pattern collapse caused by uneven distribution of the above-mentioned acid generator and basic onium salt compound are likely to occur, .

In one aspect of the present invention, it is preferable that the composition of the present invention further contains a compound containing a phenolic hydroxyl group together with the onium salt compound (A) and the acid generator (B). The composition of the present invention preferably further contains a compound containing an acid-crosslinkable group, and the form thereof may be a form in which the compound containing a phenolic hydroxyl group includes an acid-crosslinkable group, a phenolic hydroxyl group As the other compound which is different from the above-mentioned compound containing an acid-crosslinkable group.

Hereinafter, each component that may be contained in the composition of the present invention will be described in more detail.

[Onium salt compound (A)]

The onium salt compound (A) is an onium salt compound containing at least one fluorine atom in the anion portion and at least one nitrogen atom in the cation portion.

As described above, the onium salt compound (A) contained in the composition of the present invention is such that the fluorine atom content of the onium salt compound (A) is lower than the fluorine atom content in the acid generator (B) containing at least one fluorine atom Have a large relationship. Here, the content of fluorine atoms means the content of fluorine atoms in the compound represented by (the sum of the masses of all the fluorine atoms contained in the compound) / (the sum of the masses of the total atoms contained in the compound).

In one embodiment of the present invention, when the content ratio of the fluorine atom in the onium salt compound (A) and the content ratio of the fluorine atom in the acid generator (B) is converted into a mass percentage, the content is preferably 0.5% by mass or more , The difference is more preferably 1.0 mass% or more, 2.0 mass% or more, 3.0 mass% or more, 4.0 mass% or more, or 5.0 mass% or more. The upper limit of the difference is not particularly limited, but is preferably 30% by mass or less, for example.

Here, the onium salt compound (A) may contain at least one fluorine atom in the anion moiety, and when the fluorine atom includes a plurality of fluorine atoms, some fluorine atom may be contained in the cation moiety. In one aspect of the present invention, it is preferable that the onium salt compound (A) contains at least one fluorine atom in the anion portion and also contains at least one fluorine atom in the cation portion. When at least one fluorine atom is contained in the cation portion, it becomes possible to effectively increase the concentration of the basic onium salt compound in the vicinity of the surface of the resist film, rather than the concentration of the acid generator. This is effective for solving the problem of insufficient generation of the generated acid near the surface of the resist film.

Examples of the onium salt compounds include diazonium salt compounds, phosphonium salt compounds, sulfonium salt compounds, and iodonium salt compounds. Among them, a sulfonium salt compound or an iodonium salt compound is preferable, and a sulfonium salt compound is more preferable.

This onium salt compound typically has a basic portion containing a nitrogen atom in its cation portion. Here, the " basic site " means a site where the pKa of the conjugated acid at the cation site of the compound (A) becomes -3 or more. The pKa is preferably in the range of -3 to 15, more preferably in the range of 0 to 15. Also, this pKa means the calculated value obtained by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).

The basic moiety includes a structure selected from the group consisting of, for example, an amino group (a group in which one hydrogen atom is removed from ammonia, a primary amine or a secondary amine; hereinafter the same), and a nitrogen-containing heterocyclic group. The amino group is preferably an aliphatic amino group. Here, the aliphatic amino group means a group obtained by removing one hydrogen atom from an aliphatic amine.

In these structures, it is preferable that all the atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms from the viewpoint of improving the basicity. From the viewpoint of improving the basicity, it is preferable that the electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly connected to the nitrogen atom.

The onium salt compound (A) may have two or more of the above basic sites.

When the cationic portion of the compound (A) contains an amino group, the cation moiety preferably has a partial structure represented by the following general formula (N-I).

[Chemical Formula 5]

Wherein,

R _A and R _B each independently represent a hydrogen atom or an organic group.

X represents a single bond or a linking group.

At least two of R _A , R _B and X may be bonded to each other to form a ring.

Examples of the organic group represented by R _A or R _B include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic hydrocarbon group, an alkoxycarbonyl group, and a lactone group.

These groups may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group and a cyano group.

The alkyl group represented by R _A or R _B may be straight-chain or branched. The number of carbon atoms of the alkyl group is preferably from 1 to 50, more preferably from 1 to 30, still more preferably from 1 to 20. Examples of such alkyl groups include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec- Butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group.

The cycloalkyl group represented by R _A or R _B may be monocyclic or polycyclic. The cycloalkyl group is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group.

The alkenyl group represented by R _A or R _B may be straight chain or branched chain. The number of carbon atoms of the alkenyl group is preferably 2 to 50, more preferably 2 to 30, and still more preferably 3 to 20. Examples of such an alkenyl group include a vinyl group, an allyl group, and a styryl group.

The aryl group represented by R _A or R _B preferably has 6 to 14 carbon atoms. Examples of such groups include a phenyl group and a naphthyl group.

The heterocyclic hydrocarbon group represented by R _A or R _B preferably has 5 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. The heterocyclic hydrocarbon group may have aromaticity or may not have aromaticity. The heterocyclic hydrocarbon group preferably has aromaticity.

The heterocyclic ring contained in the above groups may be monocyclic or polycyclic. Examples of such heterocyclic rings include imidazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazin ring, 2H-pyrrole ring, 3H-indole ring, 1H-indazole ring, purine ring, isoquinoline ring, 4H -Quinolinine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, phenanthridine ring, acridine ring, phenanthroline ring, phenanthrene ring, , Triazine ring, benzisoquinoline ring, thiazole ring, thiadiazine ring, azepine ring, azo ring, isothiazole ring, isooxazole ring, and benzothiazole ring.

Examples of the lactone group represented by R _A or R _B include a 5 to 7-membered ring lactone group, and a 5 to 7-membered ring lactone group in which a cyclic structure or a spiro structure is formed, It is acceptable. Specifically, it is preferably a group having the structure shown below.

[Formula 6-1]

[Formula 6-2]

The lactone group may or may not have a substituent (Rb ₂ ). As the preferable substituent (Rb ₂ ), there can be mentioned the same substituent as described above for R _A and R _B. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) present may be the same or different. Further, a plurality of the substituents (Rb ₂ ) present may bond together to form a ring.

Examples of the linking group represented by X include linear or branched alkylene groups, cycloalkylene groups, ether bonds, ester bonds, amide bonds, urethane bonds, urea bonds, and groups formed by combining two or more of these . X is more preferably a group formed by combining a single bond, an alkylene group, an alkylene group and an ether bond, or a combination of an alkylene group and an ester bond. The number of atoms of the linking group represented by X is preferably 20 or less, and more preferably 15 or less. The straight-chain or branched-chain alkylene group and the cycloalkylene group are preferably a carbon number of 8 or less, and may have a substituent. The substituent is preferably an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms) And the like.

At least two of R _A , R _B and X may be bonded to each other to form a ring. The number of carbon atoms forming the ring is preferably from 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, a nitrogen atom, an ester bond, an amide bond, or a carbonyl group in the ring.

When the cationic addition of the compound (A) contains a nitrogen-containing heterocyclic group, the nitrogen-containing heterocyclic group may have aromaticity or not have aromaticity. The nitrogen-containing heterocyclic group may be monocyclic or polycyclic. The nitrogen-containing heterocyclic group is preferably a group containing a piperidine ring, a morpholine ring, a pyridine ring, an imidazole ring, a pyrazine ring, a pyrrole ring, or a pyrimidine ring.

The basic onium salt compound (A) is preferably a compound represented by the following general formula (N-II).

(7)

Wherein,

A represents a sulfur atom or an iodine atom.

R ₁ represents a hydrogen atom or an organic group. If R ₁ is present a plurality, R ₁ can be the same or different.

R represents an (o + 1) -valent organic group. When a plurality of R exists, R may be the same or different.

X represents a single bond or a linking group. When a plurality of X exist, X may be the same or different.

A _N represents a basic site containing a nitrogen atom. When A is _N plurality exist, A _N are be the same or different.

When A is a sulfur atom, n is an integer of 1 to 3, and m is an integer satisfying the relationship of m + n = 3.

When A is an iodine atom, n is 1 or 2, and m is an integer satisfying the relationship of m + n = 2.

o represents an integer of 1 to 10;

Y ^- represents an anion and contains at least one fluorine atom. The details are as described below as the anion moiety of the compound (A).

At least two of R ₁ , X, R and A _N may be bonded to each other to form a ring.

Examples of the (o + 1) -valent organic group represented by R include linear (linear, branched) or cyclic aliphatic hydrocarbon groups, heterocyclic hydrocarbon groups, and aromatic hydrocarbon groups, Is an aromatic hydrocarbon group. When R is an aromatic hydrocarbon group, it is preferably bonded to the p-side (1,4-position) of the aromatic hydrocarbon group.

The linking group represented by X is synonymous with the linking group represented by X in the above-mentioned general formula (N-I), and the same specific example can be given.

The basic moiety represented by A _N is synonymous with the " basic moiety &quot; included in the cation moiety of the above-mentioned compound (A), and may include, for example, an amino group or a nitrogen-containing heterocyclic group. , Examples of the amino group include -N (R _A ) (R _B ) groups in the general formula (NI) described above.

Examples of the organic group represented by R ₁ include an alkyl group, an alkenyl group, an aliphatic cyclic group, an aromatic hydrocarbon group, and a heterocyclic hydrocarbon group. When m = 2, two R &lt; ₁ &gt; may be bonded to each other to form a ring. These groups or rings may further have a substituent.

The alkyl group represented by R ₁ may be straight-chain or branched. The number of carbon atoms of the alkyl group is preferably from 1 to 50, more preferably from 1 to 30, still more preferably from 1 to 20. Examples of such alkyl groups include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec- Butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group.

The alkenylene group represented by R ₁ may be straight-chain or branched. The number of carbon atoms of the alkenyl group is preferably 2 to 50, more preferably 2 to 30, and still more preferably 3 to 20. Examples of such an alkenyl group include a vinyl group, an allyl group, and a styryl group.

The aliphatic cyclic group represented by R ₁ is, for example, a cycloalkyl group. The cycloalkyl group may be monocyclic or polycyclic. The aliphatic cyclic group is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group.

The aromatic hydrocarbon group represented by R ₁ preferably has 6 to 14 carbon atoms. Examples of such groups include aryl groups such as phenyl group and naphthyl group. The aromatic hydrocarbon group represented by R ₁ is preferably a phenyl group.

The heterocyclic hydrocarbon group represented by R &lt; ₁ &gt; may have an aromatic character or may not have aromatic character. The heterocyclic hydrocarbon group preferably has aromaticity.

The heterocyclic ring contained in the above groups may be monocyclic or polycyclic. Examples of such heterocyclic rings include imidazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazin ring, 2H-pyrrole ring, 3H-indole ring, 1H-indazole ring, purine ring, isoquinoline ring, 4H -Quinolinine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, phenanthridine ring, acridine ring, phenanthroline ring, phenanthrene ring, , Triazine ring, benzisoquinoline ring, thiazole ring, thiadiazine ring, azepine ring, azo ring, isothiazole ring, isooxazole ring, and benzothiazole ring.

It is preferable that R ₁ is an aromatic hydrocarbon group, or two R ₁ may combine to form a ring.

The ring which may be formed by bonding at least two of R ₁ , X, R and A _N to each other is preferably a 4- to 7-membered ring, more preferably a 5-membered or 6-membered ring, and particularly preferably a 5-membered ring. The ring skeleton may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

When the ring represented by R ₁ or the ring formed by bonding two R ₁ groups further has a substituent, examples of the substituent include the following ones. Examples of the substituent include a halogen atom (-F, -Br, -Cl or -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, An alkoxycarbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkoxycarbonylamino group, -Alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, an N-aryl-N-aryloxycarbonylamino group, a formyl group, an acyl group, a carboxyl group, a carbamoyl group, , An arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and a conjugate salt thereof (referred to as a sulfonate group), an alkoxysulfonyl group, an aryloxaphonyl group, a sulfinamoyl group, (-PO ₃ H ₂ ) and its conjugate salt apparatus (referred to as a phosphonate group), phosphonooxy group (-OPO ₃ H ₂ ) and A sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group, a sulfonyl group and a sulfonyl group.

Of these substituents, a hydroxyl group, an alkoxy group, a cyano group, an aryl group, an alkenyl group, an alkynyl group, an alkyl group and the like are preferable.

In the general formula (N-II), o is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.

The compound (A) represented by the general formula (N-II) is preferably an aromatic hydrocarbon group in at least one of the n Rs in the formula in an embodiment. And X in at least one of the o- (XA _N ) groups bonded to at least one of the aromatic hydrocarbon groups is preferably a linking group in which the bonding moiety with the aromatic hydrocarbon group is a carbon atom.

That is, in the compound (A) of this embodiment, the basic moiety represented by A _N is bonded to the aromatic hydrocarbon group through a carbon atom directly bonded to an aromatic hydrocarbon group represented by R.

The aromatic hydrocarbon group represented by R may contain a heterocyclic ring as an aromatic ring in the aromatic hydrocarbon group. The aromatic ring may be monocyclic or polycyclic.

The aromatic ring preferably has 6 to 14 carbon atoms. Examples of such groups include aryl groups such as phenyl group, naphthyl group, and anthryl group. When the aromatic ring includes a heterocyclic ring, examples of the heterocyclic ring include thiophene ring, furan ring, pyrrole ring, benzothiophen ring, benzofuran ring, benzopyrrole ring, triazin ring, imidazole ring, Imidazole ring, triazole ring, thiadiazole ring, and thiazole ring.

The aromatic hydrocarbon group represented by R is preferably a phenyl group or a naphthyl group, particularly preferably a phenyl group.

The aromatic hydrocarbon group represented by R may further have a substituent other than the group represented by - (XA _N ) described below. As the substituent, for example, those listed above as substituents in R ₁ can be used.

In this embodiment, the linking group as X in at least one - (XA _N ) group to be substituted for the aromatic ring R is not particularly limited as far as the bonding portion with the aromatic hydrocarbon group represented by R is a carbon atom . The linking group includes, for example, an alkylene group, a cycloalkylene group, an arylene group, -COO-, -CO-, or a combination thereof. -S (= O) -, -S (= O) _2- , -OS (= O) ₂ -, and -NR'- And at least one combination selected from the group consisting of Here, R 'represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group which may be included in the linking group represented by X may be linear or branched. The number of carbon atoms of the alkylene group is preferably from 1 to 20, more preferably from 1 to 10. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.

The cycloalkylene group which may be included in the linking group represented by X may be monocyclic or polycyclic. The number of carbon atoms of the alkylene group is preferably 3 to 20, more preferably 3 to 10. Examples of such a cycloalkylene group include a 1,4-cyclohexylene group.

The number of carbon atoms of the arylene group which may be included in the linking group represented by X is preferably 6 to 20, more preferably 6 to 10. Examples of such an arylene group include a phenylene group and a naphthylene group.

It is preferable that at least one X is represented by the following general formula (N-III) or (N-IV).

[Chemical Formula 8]

Wherein,

R ₂ and R ₃ represent a hydrogen atom, an alkyl group, an alkenyl group, an aliphatic cyclic group, an aromatic hydrocarbon group or a heterocyclic hydrocarbon group. R ₂ and R ₃ may be bonded to each other to form a ring. At least one of R ₂ and R ₃ may be bonded to E to form a ring.

E represents a linking group or a single bond.

[Chemical Formula 9]

Wherein,

J represents an oxygen atom or a sulfur atom.

E represents a linking group or a single bond.

Each of the groups represented by R &lt; ₂ &gt; and R &lt; ₃ &gt; and the substituent which they may further include, for example, the same groups as described for R &lt; ₁ &gt; That R ₂ and R ₃ can be formed by coupling ring, and R ₂ and R at least ring in one side can be formed in combination with the E of the _third, 4-7 membered ring is more preferable that the preferred, and 5- or 6-membered ring desirable. R ₂ and R ₃ are each independently preferably a hydrogen atom or an alkyl group.

The linking group represented by E is, for example, an alkylene group, a cycloalkylene group, an arylene group, -COO-, -CO-, -O-, -S-, -OCO-, -S (= O) ₂ -, -OS (= O) ₂ -, -NR-, or a combination thereof. Here, R represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

The linking group represented by E may be an alkylene bond, an ester bond, an ether bond, a thioether bond, a urethane bond

[Chemical formula 10]

, Urea bond

(11)

, An amide bond, and a sulfonamide bond. The linking group represented by E is more preferably an alkylene bond, an ester bond, or an ether bond.

The compound (A) may be a compound having a plurality of sites containing nitrogen atoms. For example, the compound (A) may be a compound having a structure in which at least one of R ₁ in the formula (N-II) is represented by the formula (NI).

The compound (A) represented by the formula (N-II) is represented by the following formula (N-V) in an embodiment.

[Chemical Formula 12]

Wherein,

X and A _N are each group and a consensus in general formula (N-II), and specific examples and preferred examples are also the same.

Y ^- represents an anion and contains at least one fluorine atom. The details are as described below as the anion moiety of the compound (A).

R ₁₄ each independently represents a group having 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 cycloalkyl group. These groups may have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R &lt; ₁₅ &gt; may be bonded to each other to form a ring, or an atom constituting the ring may contain a hetero atom such as an oxygen atom, a sulfur atom and a nitrogen atom. These groups may have a substituent.

and l represents an integer of 0 to 2.

r represents an integer of 0 to 8;

The compound (A) represented by the formula (N-II) is represented by the following formula (N-VI) in one embodiment.

[Chemical Formula 13]

Among the general formula (N-VI)

A represents a sulfur atom or an iodine atom.

R ₁₁ each independently represents an alkyl group, an alkenyl group, an aliphatic cyclic group, an aromatic hydrocarbon group or a heterocyclic hydrocarbon group. When m = 2, two R &lt; ₁₁ &gt; may be bonded to each other to form a ring.

Ar represents, independently of each other, an aromatic hydrocarbon group.

X ₁ each independently represents a divalent linking group.

R ₁₂ independently represents a hydrogen atom or an organic group.

When A is a sulfur atom, m is an integer of 1 to 3, and n is an integer satisfying the relationship of m + n = 3.

When A is an iodine atom, m is an integer of 1 or 2, and n is an integer satisfying the relationship of m + n = 2.

Y ^- represents an anion and contains at least one fluorine atom. The details are as described below as the anion moiety of the compound (A).

Specific examples and preferable examples of the alkyl group, alkenyl group, aliphatic cyclic group, aromatic hydrocarbon group, and heterocyclic hydrocarbon group as R _{11 include} alkyl groups, alkenyl groups, alkynyl groups, and alkyl groups as R ₁ in the general formula (N-II) Aliphatic cyclic group, aromatic hydrocarbon group, and heterocyclic hydrocarbon group.

Specific examples and preferable examples of the aromatic hydrocarbon group as Ar are the same as the specific examples and preferable examples of the aromatic hydrocarbon group as R in the above formula (N-II).

Specific examples and preferred examples of the divalent linking group as X _{1 are the same} as the specific examples and preferred examples of the linking group as X in the above general formula (N-II).

Specific examples and preferred examples of the organic group as R _{12 are the same} as the specific examples and preferable examples of the organic _group as R _A and R _{B in} the general formula (NI).

A mode in which X ₁ is an alkylene group (for example, a methylene group) and two R ₁₂ are bonded to each other to form a ring is a Post Exposure Bake (PEB) temperature dependency and Post Exposure Delay : PED) is particularly preferable from the standpoint of stability.

The anion moiety of the compound (A) contains at least one fluorine atom. The anion contained in the compound (A) is preferably an unconjugated anion containing at least one fluorine atom. Here, the non-nucleophilic anion is an anion having a remarkably low ability to cause a nucleophilic reaction, and is an anion capable of inhibiting aging degradation due to an intramolecular nucleophilic reaction. Thus, the stability with time of the composition of the present invention is improved.

Examples of the non-nucleophilic anion include a sulfonic acid anion, a carboxylic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

Examples of the sulfonic acid anion include an aliphatic sulfonic acid anion, an aromatic sulfonic acid anion, and a camphorsulfonic acid anion.

Examples of the carboxylic acid anion include an aliphatic carboxylic acid anion, an aromatic carboxylic acid anion, and an aralkyl carboxylic acid anion.

The aliphatic moiety in the aliphatic sulfonic acid anion may be an alkyl group and may be a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group , n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, , Octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, and vinyl group, and the like can be given .

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

The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonic acid anion and the aromatic sulfonic acid anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonic acid anion and the aromatic sulfonic acid anion include a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) An alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (Preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms) (Preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), an aryloxaphonyl group (preferably having 6 to 20 carbon atoms), an alkylaryloxaphonyl group (Preferably having 7 to 20 carbon atoms), a cycloalkylaryloxaphonyl group (Preferably having from 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having from 5 to 20 carbon atoms), and a cycloalkylalkyloxyalkyloxy group (preferably having from 8 to 20 carbon atoms). As the aryl group and the ring structure of each group, an alkyl group (preferably having from 1 to 15 carbon atoms) may be mentioned as a substituent.

Examples of the aliphatic moiety in the aliphatic carboxylic acid anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonic acid anion.

Examples of the aromatic group in the aromatic carboxylic acid anion include the same aryl group as in the aromatic sulfonic acid anion.

The aralkyl group in the aralkylcarboxylic acid anion is preferably an aralkyl group having 6 to 12 carbon atoms such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylvinyl group.

The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylic acid anion, aromatic carboxylic acid anion and aralkyl carboxylic acid anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylic acid anion, aromatic carboxylic acid anion and aralkylcarboxylic acid anion include halogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups An alkylthio group, and the like.

The sulfonylimide anion includes, for example, a saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, Butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group and the like. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxyl phonyl group, an aryloxyl phonyl group, a cycloalkyl aryloxyl phonyl group, Substituted alkyl groups are preferred. It is also preferable that the two alkyl groups in the bis (alkylsulfonyl) imide anion are bonded to each other to form a cyclic structure. In this case, the cyclic structure to be formed is preferably a 5- to 7-membered ring.

Examples of other non-nucleophilic anions include phosphorus fluoride, boron fluoride, and antimony fluoride.

Examples of the non-nucleophilic anion include an aliphatic sulfonic acid anion in which the alpha -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, a bis (alkylsulfonyl) imide anion in which the alkyl group is substituted with a fluorine atom , And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is preferably a perfluoro aliphatic sulfonic acid anion having 4 to 8 carbon atoms, more preferably a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutane sulfonic acid anion, Sulfonic acid anion, pentafluorobenzenesulfonic acid anion, and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

The non-nucleophilic anion is preferably represented by, for example, the following general formula (LD1).

[Chemical Formula 14]

Wherein,

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

R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group.

Each L independently represents a divalent linking group.

Cy represents a cyclic organic group.

At least one of Xf, R ₁ , R ₂ , L and Cy contains at least one fluorine atom.

x represents an integer of 1 to 20;

y represents an integer of 0 to 10;

z represents an integer of 0 to 10;

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4. It is preferable that the alkyl group substituted with at least one fluorine atom is a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Xf represents a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH _{2 CF 3, CH 2 CH 2} CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9, Or CH ₂ CH ₂ C ₄ F ₉ .

R ₁ and R ₂ are each independently a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent as R ₁ and R ₂ include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , and CH ₂ CH ₂ C ₄ F ₉ , among which CF ₃ is preferred.

L represents a divalent linking group. Examples of the divalent linking group include -COO-, -OCO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, an alkylene group, a cycloalkylene group, And alkenylene groups. Among them, -CONH-, -CO-, or -SO ₂ - is preferable, and -CONH- or -SO ₂ - is more preferable.

Cy represents a cyclic organic group. Examples of the cyclic organic group include a ring group, an aryl group, and a heterocyclic group.

The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic heterocyclic group include monocyclic cycloalkyl groups such as cyclopentyl group, cyclohexyl group, and cyclooctyl group. Examples of polycyclic cyclic groups include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like, has a bulky structure in the PEB (Post Exposure Bake) Suppression and improvement of MEEF (Mask Error Enhancement Factor).

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group and an anthryl group. Among them, a naphthyl group having a relatively low optical absorbance at 193 nm is preferable.

The heterocyclic group may be monocyclic or polycyclic, but polycondensation is more capable of inhibiting acid diffusion. The heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocycle having an aromatic group 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 tetrahydropyran ring, lactone ring, and decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable. Examples of the lactone ring include lactone rings exemplified as R _A and R _B in the general formula (N-1).

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, have. The alkyl group may be straight-chain or branched. The alkyl group preferably has 1 to 12 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 12 carbon atoms. The aryl group preferably has 6 to 14 carbon atoms.

x is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. y is preferably 0 to 4, more preferably 0. z is preferably 0 to 8, and more preferably 0 to 4.

It is also preferable that the non-nucleophilic anion is represented by, for example, the following general formula (LD2).

[Chemical Formula 15]

Xf, R ₁ , R ₂ , L, Cy, x, y and z in the general formula (LD2) are the same as those in the general formula (LD1). Rf is a group containing a fluorine atom.

Examples of the group containing a fluorine atom represented by Rf include an alkyl group having at least one fluorine atom, a cycloalkyl group having at least one fluorine atom, and an aryl group having at least one fluorine atom.

These alkyl groups, cycloalkyl groups and aryl groups may be substituted by fluorine atoms or may be substituted by other substituents including fluorine atoms. When Rf is a cycloalkyl group having at least one fluorine atom or an aryl group having at least one fluorine atom, examples of other substituents containing a fluorine atom include an alkyl group substituted by at least one fluorine atom.

The alkyl group, cycloalkyl group and aryl group may be further substituted by a substituent containing no fluorine atom. As the substituent, for example, those described above with respect to Cy include those not containing a fluorine atom.

Examples of the alkyl group having at least one fluorine atom represented by Rf include the same alkyl groups substituted by at least one fluorine atom represented by Xf, and the same ones as described above. Examples of the cycloalkyl group having at least one fluorine atom represented by Rf include a perfluorocyclopentyl group and a perfluorocyclohexyl group. The aryl group having at least one fluorine atom represented by Rf includes, for example, a perfluorophenyl group.

Preferable examples of the anion moiety of the compound (A) include a structure exemplified as the preferable anion structure of the above-mentioned photo acid generator (B) in addition to the structure represented by the general formulas (LD1) and (LD2)

In one aspect of the present invention, the onium salt compound (A) and the acid generator (B) described later preferably have a small difference in pKa of the acid generated from the anion portion by irradiation with an actinic ray or radiation. the smaller the difference in pKa is, the more unevenness occurs in the acid strength of the acid generated from the onium salt compound (A) and the acid generator (B), so that the crosslinking reactivity and the deprotection reactivity due to the generated acid are more uniform can do. The difference in pKa is, for example, preferably 5 or less, more preferably 3 or less, more preferably 1 or less, and ideally 0.

Here, pKa refers to a pKa in an aqueous solution and is described in, for example, Chemical Handbook (II) (revised edition 4, 1993, edited by The Japan Chemical Society, Maruzen Co., Ltd.) . Specifically, the pKa in the aqueous solution can be measured by measuring an acid dissociation constant at 25 캜 using an infinitely dilute aqueous solution. Further, the following software package 1 can be used to measure the pKa in the aqueous solution with a Hammett substituent constant and a known literature value A database-based value can also be obtained by calculation. The values of pKa in this specification all show values obtained by calculation using this software package. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

In one embodiment of the present invention, the basic onium salt compound (A) and the acid generator (B) described below are preferably the same in the anion structure.

Specific examples of the compound (A) are shown below, but the present invention is not limited thereto.

[Formula 16-1]

[Formula 16-2]

[Formula 16-3]

[Chemical Formula 16-4]

[Formula 16-5]

[Formula 16-6]

[Formula 16-7]

[Chemical Formula 16-8]

[Chemical Formula 16-9]

[Chemical Formula 16-10]

[Chemical Formula 16-11]

As the compound (A), one type may be used alone, or two or more types may be used in combination.

The content of the compound (A) is usually in the range of 0.001 to 20 mass%, preferably 0.1 to 20 mass%, more preferably 1 to 20 mass%, based on the total solid content in the composition have.

Also, the larger the volume of the generated acid from the compound (A) is, from the viewpoint of improving the resolution, is preferable.

[Acid generator (B)]

The acid generator (B) is a compound which generates an acid upon irradiation with an actinic ray or radiation, and is a compound containing at least one fluorine atom. As described above, the acid generator (B) contained in the composition of the present invention has a relationship that the content of fluorine atoms is smaller than the content of fluorine atoms in the above-mentioned onium salt compound (A).

A preferable example of the acid generator is an onium salt compound. Examples of such onium salt compounds include sulfonium salts, iodonium salts, and phosphonium salts.

Another preferred form of the acid generator is a compound which generates sulfonic acid, imidic acid or metaic acid by irradiation with an actinic ray or radiation. Examples of the acid generator in the form include a sulfonium salt, an iodonium salt, a phosphonium salt, an oxime sulfonate, an imide sulfonate, and the like.

In one aspect of the present invention, the acid generator (B) is preferably an onium salt compound containing at least one fluorine atom in the anion moiety and a sulfonate salt containing at least one fluorine atom in the anion moiety More preferable.

As the acid generator which can be used in the present invention, not only a low molecular compound but also a compound in which a group capable of generating an acid upon irradiation with an actinic ray or radiation is introduced into the main chain or side chain of the polymer compound can be used.

The acid generator is preferably a compound which generates an acid by irradiation with an electron beam or an extreme ultraviolet ray.

In the present invention, the preferable onium salt compounds include a sulfonium compound represented by the following general formula (7) or an iodonium compound represented by the general formula (8).

[Chemical Formula 17]

In the general formulas (7) and (8)

R _a1 , R _a2 , R _a3 , R _a4 and R _a5 each independently represent an organic group.

X ^- represents an organic anion.

At least one of R _a1 , R _a2 , R _a3 , R _a4 , R _a5 and X ^- contains at least one fluorine atom.

Hereinafter, the sulfonium compound represented by formula (7) and the iodonium compound represented by formula (8) will be described in more detail.

R _a1 , R _a2 and R _a3 in the general formula (7) and R _a4 and R _a5 in the general formula (8) each independently represent an organic group, and preferably R _a1 , R _a2 and R _a3 , and at least one of R &lt; _a4 &gt; and R &lt; _a5 &gt; are each an aryl group. The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

Examples of the organic anion of X ^- in formulas (7) and (8) include sulfonic acid anion, carboxylic acid anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) And is preferably an organic anion represented by the following general formula (9), (10) or (11), more preferably an organic anion represented by the following general formula (9)

[Chemical Formula 18]

In the general formulas (9), (10) and (11), R _c1 , R _c2 , R _c3 and R _c4 each independently represent an organic group.

The organic anion of X &lt; ^- &gt; corresponds to sulfonic acid, imidic acid, metaic acid, etc., which is generated by an actinic ray such as electron beam or extreme ultraviolet ray or radiation.

Examples of the organic group of R _c1 , R _c2 , R _c3 and R _c4 include an alkyl group, an aryl group or a group in which a plurality of these groups are connected. Of these organic groups, the phenyl group is more preferably an alkyl group substituted by a fluorine atom or a fluoroalkyl group, or a phenyl group substituted by a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity generated by the light irradiation is increased, and the sensitivity is improved. However, it is preferable that the terminal group does not contain a fluorine atom as a substituent.

In one form, the acid generator (B) is preferably an onium salt compound having an anion structure described in the basic onium salt compound (A).

As described above, in one aspect of the present invention, the basic onium salt compound (A) and the acid generator (B) are preferably used in an amount sufficient to cause crosslinking reaction It is preferable that the anion structure is the same or the difference in the pKa of the generated acid is small from the viewpoint of making the reactivity more uniform.

In the present invention, from the viewpoint of suppressing the diffusion of the exposed acid into the non-exposed portion and improving the resolution and pattern shape, the compound (B) is preferably an acid having a volume of 130 Å ³ or more Sulfonic acid), more preferably a compound which generates an acid having a size of 190 Å ³ or more (more preferably a sulfonic acid), more preferably an acid having a size of 270 Å ³ or more (more preferably, And more preferably a compound which generates an acid having a size of 400 Å ³ or more (more preferably, a sulfonic acid) in a volume of 400 Å ³ or more. However, in view of the sensitivity and the solubility in coating solvent, the volume is more preferably not more than preferably ³ 2000Å and 1500Å ³ or less. The value of the volume was obtained using "WinMOPAC" manufactured by Fujitsu Kabushiki Kaisha. In other words, first, the chemical structure of each compound is input, and then the structure is used as an initial structure to determine the most stable steric body of each acid by calculation of the molecular force field using the MM3 method, The "accessible volume" of each acid can be calculated by performing molecular orbital calculation using the PM3 method for the stable three-dimensional fundus.

In the present invention, particularly preferred acid generators are shown below. In some of the examples, the calculated value of the volume is added (unit A ³ ). The calculated value obtained here is the volume value of the acid to which the proton is bonded to the anion portion.

[Formula 19-1]

[Formula 19-2]

[Formula 19-3]

[Chemical Formula 19-4]

Examples of the acid generator (preferably an onium compound) used in the present invention include a polymeric acid generator system in which a group (photoacid generator) generating an acid by irradiation of an actinic ray or radiation is introduced into a main chain or side chain of a polymer compound Can be used.

The content of the acid generator (B) in the composition is preferably 0.1 to 40 mass%, more preferably 0.5 to 30 mass%, and still more preferably 1 to 25 mass%, based on the total solid content of the composition %to be.

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

[Compound containing acid crosslinking group]

The composition of the present invention may contain a compound (C) having an acid crosslinking group (hereinafter also referred to as "compound (C)" or "crosslinking agent"). The compound (C) is preferably a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in the molecule. From the viewpoint of improving the LER, it is preferable that the compound (C) contains a methylol group.

First, the case where the compound (C) is a low-molecular compound will be described (hereinafter referred to as a compound (C ')). The compound (C ') is preferably a hydroxymethylated or alkoxymethylated phenol compound, an alkoxymethylated melamine compound, an alkoxymethyl glycoluril compound or an alkoxymethylated urea compound. Particularly preferred compounds (C ') include phenol derivatives or alkoxymethyl glycoluril derivatives having 3 or more benzene rings in the molecule and having 2 or more hydroxymethyl groups or alkoxymethyl groups and having a molecular weight of 1,200 or less, .

As the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable.

In the examples of the compound (C '), a phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound having no corresponding hydroxymethyl group with formaldehyde under a base catalyst. The phenol derivative having an alkoxymethyl group can be obtained by reacting a phenol derivative having a corresponding hydroxymethyl group with an alcohol under an acid catalyst.

As another example of the preferable compound (C '), a compound having an N-hydroxymethyl group or an N-alkoxymethyl group, such as an alkoxymethylated melamine compound, an alkoxymethyl glycoluril compound or an alkoxymethylated urea compound, .

Examples of such compounds include hexamethoxymethylmelamine, hexaethoxymethylmelamine, tetramethoxymethylglycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethyleneurea, bismethoxymethylurea And the like are disclosed in EP 0,133,216A, West German Patent No. 3,634,671, 3,711,264, and EP 0,212,482A.

Particularly preferred among the specific examples of the compound (C ') are shown below.

[Chemical Formula 20]

In the formulas, L ₁ to L ₈ each independently represent a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group or an alkyl group having 1 to 6 carbon atoms.

In one embodiment of the present invention, the compound (C ') is preferably a compound represented by the following general formula (1).

[Chemical Formula 21]

In the general formula (I)

R ₁ and R ₆ each independently represent a hydrogen atom or a hydrocarbon group having 5 or less carbon atoms.

R ₂ and R ₅ each independently represent an alkyl group, a cycloalkyl group, an aryl group or an acyl group.

R ₃ and R ₄ each independently represent a hydrogen atom or an organic group having 2 or more carbon atoms. R ₃ and R ₄ may be bonded to each other to form a ring.

In one aspect of the present invention, R ₁ and R ₆ are preferably a hydrocarbon group having 5 or less carbon atoms, more preferably a hydrocarbon group having 4 or less carbon atoms, particularly preferably a methyl group, an ethyl group, a propyl group , And isopropyl group.

As the alkyl group represented by R ₂ and R ₅ , for example, an alkyl group having 1 to 6 carbon atoms is preferable, and a cycloalkyl group having 3 to 12 carbon atoms is preferable as the cycloalkyl group. As the aryl group, An aryl group having 6 to 12 carbon atoms is preferable, and as the acyl group, for example, the alkyl moiety preferably has 1 to 6 carbon atoms.

In one aspect of the present invention, R ₂ and R ₅ are preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

Examples of the organic group having 2 or more carbon atoms represented by R ₃ and R ₄ include an alkyl group having 2 or more carbon atoms, a cycloalkyl group, an aryl group, etc., and R ₃ and R ₄ are bonded to each other, It is preferable to form a ring which is a ring-shaped member.

Examples of the ring formed by bonding R ₃ and R ₄ to each other include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic fused rings formed by combining two or more of these rings .

These rings may have a substituent. Examples of such a substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an aryl group, an alkoxymethyl group, an acyl group, an alkoxycarbonyl group, a nitro group, And lock time.

Specific examples of the ring formed by bonding R ₃ and R ₄ to each other are shown below. * In the formulas represents the connecting site with the phenol nucleus.

[Chemical Formula 22]

In one aspect of the present invention, it is preferable that R ₃ and R ₄ in the general formula (I) bond to form a polycyclic condensed ring containing a benzene ring, more preferably a fluorene structure.

It is preferable that the compound (C ') forms, for example, a fluorene structure represented by the following general formula (Ia) by bonding R ₃ and R ₄ in the general formula (I).

(23)

Wherein,

R ₇ and R ₈ each independently represent a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an alkoxymethyl group, an acyl group, an alkoxycarbonyl group, a nitro group, a halogen atom or a hydroxyl group.

n1 and n2 each independently represent an integer of 0 to 4, preferably 0 or 1;

* Represents the connecting site with the phenol nucleus.

In one embodiment of the present invention, the compound (C ') is preferably represented by the following general formula (I-b).

&Lt; EMI ID =

Wherein,

R _1b and R _6b each independently represent an alkyl group having 5 or less carbon atoms.

R _2b and R _5b each independently represent an alkyl group having 6 or less carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.

Z represents an atomic group necessary for forming a ring with the carbon atom in the formula.

The ring formed by Z together with the carbon atom in the formula is the same as that described for the ring formed by bonding R ₃ and R ₄ together in the description of the general formula (I).

In one aspect of the present invention, it is preferable that the compound (C ') is a compound having two or more aromatic rings and at least two alkoxymethyl groups and / or hydroxymethyl groups in the molecule.

Next, a method for producing the compound (C ') represented by the general formula (I) will be described.

The bisphenol compound serving as the mother of the compound (C ') represented by the general formula (I) is generally synthesized by dehydration condensation reaction of the corresponding two molecules of the phenol compound and the corresponding one molecule of the ketone in the presence of an acid catalyst .

The obtained bisphenol compound is treated with paraformaldehyde and dimethylamine to aminomethylate to obtain an intermediate represented by the following general formula (I-C). Subsequently, acetylation, deacetylation and alkylation are carried out to obtain the intended acid crosslinking agent.

(25)

In the formulas, R ₁ , R ₃ , R ₄ and R ₆ are the same as the groups in formula (I).

This synthesis method has an effect of inhibiting particle formation because it is difficult to generate oligomers as compared with the synthesis method (for example, Japanese Patent Application Laid-Open No. 2008-273844) via a hydroxymethyl compound under conventional basic conditions.

Specific examples of the compound (C ') represented by the general formula (I) are shown below.

(26)

In the present invention, the content of the compound (C ') is preferably 3 to 65% by mass, and more preferably 5 to 50% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. When the content of the compound (C ') is in the range of 3 to 65% by mass, it is possible to prevent the residual film ratio and the resolving power from being lowered, and to maintain the stability of the composition of the present invention at a satisfactory level.

In the present invention, the compounds (C ') may be used alone or in combination of two or more. From the viewpoint of good pattern shape, it is preferable to use two or more kinds in combination.

For example, in the case of using, in addition to the above-mentioned phenol derivative, another compound (C '), for example, a compound having the above-mentioned N-alkoxymethyl group, the ratio of the phenol derivative to the other compound (C' The molar ratio is usually 90/10 to 20/80, preferably 85/15 to 40/60, and more preferably 80/20 to 50/50.

The compound (C) containing an acid-crosslinkable group may be in the form of a resin containing a repeating unit having an acid crosslinkable group (hereinafter also referred to as a compound (C ")). In such a case, It is possible to form a hard film and to control acid diffusibility and dry etching resistance. As a result, it is possible to form a hard film, The pattern shape and the LER in a fine pattern are excellent because the diffusibility of the acid in the exposed part of the actinic ray or radiation of ultraviolet rays or extreme ultraviolet rays is suppressed to a great extent. When the reaction point of the resin and the crosslinking group are close to each other as in the case of the unit, the composition having improved sensitivity at the time of pattern formation becomes a composition.

Examples of the compound (C ") include a resin containing a repeating unit represented by the following general formula (1). The repeating unit represented by the general formula (1) may be a repeating unit having at least one methylol group .

Here, the "methylol group" is a group represented by the following formula (M), and in one aspect of the present invention, it is preferably a hydroxymethyl group or an alkoxymethyl group.

(27)

In the formulas, R ₂ , R ₃ and Z are as defined in the following general formula (1).

First, the general formula (1) will be described.

(28)

In the general formula (1)

R ₁ represents a hydrogen atom, a methyl group, or a halogen atom.

R ₂ and R ₃ represent a hydrogen atom, an alkyl group or a cycloalkyl group.

L represents a divalent linking group or a single bond.

Y represents a substituent except methylol group.

Z represents a hydrogen atom or a substituent.

m represents an integer of 0 to 4;

n represents an integer of 1 to 5;

m + n is 5 or less.

When m is 2 or more, a plurality of Ys may be the same or different.

When n is 2 or more, a plurality of R ₂ , R _3, and Z may be the same or different.

Two or more of Y, R ₂ , R ₃ and Z may be bonded to each other to form a ring structure.

R ₁ , R ₂ , R ₃ , L and Y may each have a substituent.

When m is 2 or more, a plurality of Y may be bonded to each other through a single bond or a linking group to form a ring structure.

The repeating unit represented by the general formula (1) is preferably represented by the following general formula (2) or (3).

[Chemical Formula 29]

In the general formulas (2) and (3)

R ₁ , R ₂ , R ₃ , Y, Z, m and n are as defined in formula (1).

Ar represents an aromatic ring.

W ₁ and W ₂ represent a divalent linking group or a single bond.

The repeating unit represented by the general formula (1) is more preferably represented by the following general formula (2 ') or (3').

(30)

R ₁ , Y, Z, m and n in the general formulas (2 ') and (3') are the same as those in the general formula (1). In the general formula (2 '), Ar is synonymous with Ar in the general formula (2).

In the general formula (3 '), W ₃ is a divalent linking group.

In the general formulas (2 ') and (3'), f is an integer of 0 to 6.

In the general formulas (2 ') and (3'), g is 0 or 1.

The general formula (2 ') is particularly preferably represented by any one of the following general formulas (1-a) to (1-c). It is particularly preferable that the compound (C '') includes a repeating unit represented by any one of the following formulas (1-a) to (1-c) or a repeating unit represented by the above formula (3 ').

(31)

R ₁ , Y and Z in the general formulas (1-a) to (1-c) are the same as those in the general formula (1).

In the general formulas (1-b) to (1-c)

Y "represents a hydrogen atom or a monovalent substituent, provided that Y" may also be a methylol group.

R ₄ represents a hydrogen atom or a monovalent substituent.

and f represents an integer of 1 to 6.

m is 0 or 1, and n is an integer of 1 to 3.

The content of the repeating unit having an acid crosslinking group in the compound (C '') is preferably 3 to 40 mol%, more preferably 5 to 30 mol%, based on the total repeating units of the compound (C ' Do.

The content of the compound (C ") is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, of the total solid content of the negative resist composition.

The compound (C ") may contain two or more kinds of repeating units having an acid crosslinkable group, or two or more compounds (C") may be used in combination. The compound (C ') and the compound (C' ') may be used in combination.

Specific examples of the repeating unit having an acid crosslinkable group contained in the compound (C ") include a structure disclosed in, for example, International Publication No. 2014/017268 <0110>.

[(D) a compound containing a phenolic hydroxyl group]

The composition of the present invention preferably contains a compound (D) (hereinafter also referred to as a compound (D)) containing a phenolic hydroxyl group in one embodiment.

The phenolic hydroxyl group in the present invention is a group formed by substituting a hydrogen atom of an aromatic ring with a hydroxy group. The aromatic ring of the aromatic ring is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

According to the composition of the present invention comprising the compound (D), in the exposed part, by the action of an acid generated from the acid generator (B) by irradiation of actinic rays or radiation, a compound containing a phenolic hydroxyl group D) and the above-mentioned compound (C) containing an acid-crosslinkable group, a crosslinking reaction proceeds to form a negative pattern. Particularly when the acid generator (B) has a structure containing two or more methylol groups in the molecule of the generated acid, in addition to the cross-linking reaction between the compound (D) and the compound (C) ) Contributes to a plurality of methylol ATP cross-linking reactions, thereby further improving dry etching resistance, sensitivity and resolution.

The compound (D) containing a phenolic hydroxyl group is not particularly limited as long as it contains a phenolic hydroxyl group, and may be a relatively low molecular compound such as a molecular resist, or a polymer compound. As the molecular resists, for example, low molecular weight cyclic polyphenol compounds described in JP-A-2009-173623 and JP-A-2009-173625 can be used.

The compound (D) containing a phenolic hydroxyl group is preferably a polymer compound from the viewpoints of reactivity and sensitivity.

When the compound (D) containing a phenolic hydroxyl group of the present invention is a polymer compound, the polymer compound contains at least one repeating unit having a phenolic hydroxyl group. The repeating unit having a phenolic hydroxyl group is not particularly limited, but is preferably a repeating unit represented by the following general formula (II).

(32)

Wherein,

R ₂ represents a hydrogen atom, a methyl group which may have a substituent, or a halogen atom.

B 'represents a single bond or a divalent organic group.

Ar 'represents aromatic ventilation.

m represents an integer of 1 or more.

Examples of the methyl group which may have a substituent in R ₂ include a trifluoromethyl group, a hydroxymethyl group and the like.

R ₂ is preferably a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of developability.

Examples of the divalent linking group of B 'include a carbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group (-S (= O) ₂ - NH- or a divalent linking group combining these groups is preferable.

B 'represents a single bond, a carbonyloxy group (-C (= O) -O-) or -C (= O) -NH-, -O-), and a single bond is particularly preferable from the viewpoint of improving the dry etching resistance.

The aromatic ring of Ar 'is a monocyclic or polycyclic aromatic ring, an aromatic hydrocarbon ring which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring and a phenanthrene ring, Examples of the thiophene ring, furan ring, pyrrole ring, benzothiophen ring, benzofuran ring, benzopyrrole ring, triazin ring, imidazole ring, benzoimidazole ring, triazole ring, thiadiazole ring, Lt; / RTI &gt; include heterocyclic rings containing aromatic rings. Among them, a benzene ring and a naphthalene ring are preferred from the viewpoint of resolution, and a benzene ring is most preferable from the viewpoint of sensitivity.

m is preferably an integer of 1 to 5, and most preferably 1. When m is 1 and Ar 'is a benzene ring, the substitution position of -OH may be either para or meta relative to the bonding position with B' of the benzene ring (or the polymer main chain when B 'is a single bond) From the viewpoint of crosslinking reactivity, para-stearate and meta-stearate are preferable, and para-stearate is more preferable.

The aromatic ring of Ar 'may have a substituent other than the group represented by -OH, and examples of the substituent include an alkyl group, a cycloalkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, An alkylcarbonyloxy group, an alkylsulfonyloxy group, and an arylcarbonyl group.

The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (2) for reasons of crosslinking reactivity, developability and dry etching resistance.

(33)

In the general formula (2)

R ₁₂ represents a hydrogen atom or a methyl group.

Ar represents an aromatic ring.

R ₁₂ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of developability.

Ar in the general formula (2) is synonymous with Ar 'in the general formula (II), and the preferable range is also the same. The repeating unit represented by the general formula (2) is preferably a repeating unit derived from hydroxystyrene (that is, a repeating unit in which R ₁₂ is a hydrogen atom and Ar is a benzene ring in the general formula (2)), desirable.

The compound (D) as the polymer compound may be composed of only the repeating unit having a phenolic hydroxyl group as described above. The compound (D) as the polymer compound may have a repeating unit as described below in addition to the repeating unit having a phenolic hydroxyl group as described above. In this case, the content of the repeating unit having a phenolic hydroxyl group is preferably 10 to 98 mol%, more preferably 30 to 97 mol%, and more preferably 40 to 97 mol%, based on the total repeating units of the compound (D) To 95 mol%. Thus, in the case where the active radiation ray or radiation-sensitive film is a thin film (for example, the thickness of the actinic ray-sensitive or radiation-sensitive film is 10 to 150 nm), the present invention (That is, the dissolution rate of the sensitizing actinic ray-sensitive or radiation-sensitive film using the compound (D) can be controlled to be more than that of the active radiation-sensitive or radiation- It can certainly be controlled to be optimum). As a result, the sensitivity can be more reliably improved.

Examples of the repeating unit having a phenolic hydroxyl group are described below, but the present invention is not limited thereto.

(34)

The compound (D) is a group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure and has a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted. From the viewpoint that a high glass transition temperature (Tg) is obtained and dry etching resistance becomes good desirable.

When the compound (D) has the above-described specific structure, the glass transition temperature (Tg) of the compound (D) increases to form an extremely hard actinic ray-sensitive or radiation-sensitive film, The etching resistance can be controlled. Therefore, the diffusibility of the acid in the exposed part of the actinic ray or radiation such as electron beam or extreme ultraviolet ray is very suppressed, so that resolution, pattern shape and LER in a fine pattern are more excellent. It is considered that the compound (D) having a non-acid decomposable polycyclic alicyclic hydrocarbon structure contributes to further improvement in dry etching resistance. Although the details are unclear, the structure of the polycyclic alicyclic hydrocarbon has higher hydrogen radicals, becomes a hydrogen source at the decomposition of the photoacid generator, further improves the decomposition efficiency of the photoacid generator, increases the acid generation efficiency And it is thought that this contributes to better sensitivity.

The above-mentioned specific structure that the compound (D) according to the present invention may have is connected to an aromatic ring such as a benzene ring and a group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure through an oxygen atom derived from a phenolic hydroxyl group . As described above, it is presumed that this structure contributes not only to high dry etching resistance but also to increase the glass transition temperature (Tg) of the compound (D) and to provide a higher resolution due to the effect of these combinations.

In the present invention, the non-acid decomposability means a property that a decomposition reaction does not occur due to an acid generated by a photo acid generator.

More specifically, the group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure is preferably a group stable to an acid and an alkali. Acid and alkaline stable groups mean groups which do not exhibit acid decomposability and alkali decomposability. Here, the acid decomposability means a property of causing a decomposition reaction by the action of an acid generated by a photoacid generator.

The alkali decomposability means a property of causing a decomposition reaction by the action of an alkali developing solution. Examples of the group exhibiting alkali decomposability include a conventionally known alkaline developer contained in a resin suitably used in a positive chemical amplification type resist composition (For example, a group having a lactone structure) which is decomposed by the action of an alkali developing agent to increase the dissolution rate into an alkali developing solution.

The group having a polycyclic alicyclic hydrocarbon structure is not particularly limited as long as it is a monovalent group having a polycyclic alicyclic hydrocarbon structure, but preferably has a total carbon number of 5 to 40, more preferably 7 to 30. The polycyclic alicyclic hydrocarbon structure may have an unsaturated bond in the ring.

The polycyclic alicyclic hydrocarbon structure in the group having a polycyclic alicyclic hydrocarbon structure means a structure having a plurality of monocyclic alicyclic hydrocarbon groups or a polycyclic alicyclic hydrocarbon structure and may be a polycyclic structure. The monocyclic alicyclic hydrocarbon group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Having a plurality of alicyclic hydrocarbon groups has a plurality of these groups. The structure having a plurality of monocyclic alicyclic hydrocarbon groups preferably has 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferably has 2 monocyclic alicyclic hydrocarbon groups.

Examples of the polycyclic alicyclic hydrocarbon structure include a bicyclo, tricyclo, and tetracyclo structure having 5 or more carbon atoms, and a polycyclic cyclo structure having 6 to 30 carbon atoms is preferable. Examples thereof include an adamantane structure, a decalin structure, A norbornene structure, a norbornene structure, a heptal roll structure, an isobornane structure, a Bonne structure, a dicyclopentane structure, an alpha -pinene structure, a tricyclodecane structure, a tetracyclododecane structure, . In addition, a part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.

Preferable examples of the polycyclic alicyclic hydrocarbon structure include an adamantane structure, a decalin structure, a norbornene structure, a norbornene structure, a heptal structure, a structure having a plurality of cyclohexyl groups, a structure having a plurality of cycloheptyl groups, A structure having a plurality of groups, a structure having a plurality of cyclodecanyl groups, a structure having a plurality of cyclododecanyl groups, and a tricyclodecane structure, and an adamantane structure is most preferable in view of dry etching resistance (that is, It is most preferable that the group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure is a group having a non-acid-decomposable adamantane structure).

For a structure having a plurality of monocyclic alicyclic hydrocarbon groups, a monocyclic alicyclic hydrocarbon structure corresponding to a monocyclic alicyclic hydrocarbon group (specifically, the following formulas (47) to (50) ) Is shown below.

(35)

The polycyclic alicyclic hydrocarbon structure may further have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (Preferably having 1 to 6 carbon atoms), a carboxyl group, a carbonyl group, a thiocarbonyl group, an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), and a halogen atom, (Preferably 1 to 30 carbon atoms in total, more preferably 1 to 15 carbon atoms in total).

Examples of the polycyclic alicyclic hydrocarbon structure include a structure represented by any one of the formulas (7), (23), (40), (41), and (51) A structure having two bonded monovalent groups of atoms is preferable and a structure represented by any one of the formulas (23), (40) and (51) A structure having two monovalent groups bonded by hydrogen atoms is more preferable, and the structure represented by the formula (40) is most preferable.

The group having a polycyclic alicyclic hydrocarbon structure is preferably a monovalent group formed by bonding any one hydrogen atom of the polycyclic alicyclic hydrocarbon structure.

The structure in which the hydrogen atom of the phenolic hydroxyl group is substituted with the above-described non-acid decomposable polycyclic alicyclic hydrocarbon structure is a group having the above-described non-acid decomposable polycyclic alicyclic hydrocarbon structure and a structure in which the hydrogen atom of the phenolic hydroxyl group is substituted The repeating unit is preferably contained in the compound (D) as the polymer compound, more preferably in the compound (D) as the repeating unit represented by the following general formula (3).

(36)

In the general formula (3), R ₁₃ represents a hydrogen atom or a methyl group.

X represents a group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure.

Ar ₁ represents an aromatic ring.

m2 is an integer of 1 or more.

R ₁₃ in the general formula (3) represents a hydrogen atom or a methyl group, but a hydrogen atom is particularly preferable.

Examples of the aromatic ring of Ar _{1 in} the general formula (3) include an aromatic hydrocarbon ring which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring and a phenanthrene ring, For example, a thiophene ring, a furan ring, a pyrrole ring, a benzothiophen ring, a benzofuran ring, a benzopyrrole ring, a triazin ring, an imidazole ring, a benzoimidazole ring, a triazole ring, a thiadiazole ring, And an aromatic ring heterocycle including a heterocycle such as a ring. Among them, a benzene ring and a naphthalene ring are preferred from the viewpoint of resolution, and a benzene ring is most preferable.

The aromatic ring of Ar ₁ may have a substituent other than the group represented by -OX. Examples of the substituent include an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (Preferably having 6 to 15 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (preferably having 1 to 6 carbon atoms), a carboxyl group, an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms) An alkoxy group and an alkoxycarbonyl group are preferable, and an alkoxy group is more preferable.

X represents a group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure. Specific examples and preferable ranges of groups having a non-acid decomposable polycyclic alicyclic hydrocarbon structure represented by X are the same as those described above. X is more preferably a group represented by -YX ₂ in the general formula (4) to be described later.

m2 is preferably an integer of 1 to 5, and most preferably 1. and m2 is 1 when Ar ₁ is benzene sun dog, with respect to the binding position of the substitution position of the benzene ring is -OX polymer main chain, and even above the para and meta even above there is even above the ortho, meta and para-on or above are preferred, Paragraph is more preferable.

In the present invention, it is preferable that the repeating unit represented by the general formula (3) is a repeating unit represented by the following general formula (4).

When the polymer compound (D) having a repeating unit represented by the general formula (4) is used, the Tg of the polymer compound (D) is increased to form a very hard sensitive actinic ray or radiation-sensitive film, The dry etching resistance can be more reliably controlled.

(37)

In the general formula (4), R ₁₃ represents a hydrogen atom or a methyl group.

Y represents a single bond or a divalent linking group.

X ₂ represents a non-acid-decomposable polycyclic alicyclic hydrocarbon group.

As the repeating unit represented by the above general formula (4), preferred examples used in the present invention are described below.

R ₁₃ in the general formula (4) represents a hydrogen atom or a methyl group, but a hydrogen atom is particularly preferable.

In the general formula (4), Y is preferably a divalent linking group. Y is preferably a carbonyl group, a thiocarbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group, -COCH ₂ -, -NH- or (Preferably having 1 to 20 carbon atoms in total and more preferably 1 to 10 carbon atoms in total), more preferably a carbonyl group, -COCH ₂ -, sulfonyl group, -CONH-, -CSNH- More preferably a carbonyl group, -COCH ₂ -, and particularly preferably a carbonyl group.

X ₂ represents a polycyclic alicyclic hydrocarbon group and is non-acid-decomposable. The total number of carbon atoms of the polycyclic alicyclic hydrocarbon group is preferably 5 to 40, more preferably 7 to 30. The polycyclic alicyclic hydrocarbon group may have an unsaturated bond in the ring.

Such a polycyclic alicyclic hydrocarbon group may be a group having a plurality of monocyclic alicyclic hydrocarbon groups or a polycyclic alicyclic hydrocarbon group, and may be a bridged group. As the monocyclic alicyclic hydrocarbon group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group and a cyclooctyl group. . The group having a plurality of monocyclic alicyclic hydrocarbon groups preferably has 2 to 4 monocyclic alicyclic hydrocarbon groups, and it is particularly preferable that the group having two monocyclic alicyclic hydrocarbon groups have two monocyclic alicyclic hydrocarbon groups.

Examples of the polycyclic alicyclic hydrocarbon group include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and groups having a polycyclic cyclic structure having 6 to 30 carbon atoms are preferable. Examples thereof include adamantyl group, A norbornyl group, a norbornene group, an isobonyl group, a campanyl group, a dicyclopentyl group, an a-pynyl group, a tricyclododecyl group, a tetracyclododecyl group, and androstane group. In addition, a part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.

The polycyclic alicyclic hydrocarbon group of X ₂ is preferably an adamantyl group, a decalin group, a norbornyl group, a norbornenyl group, a sidolyl group, a group having a plurality of cyclohexyl groups, a group having a plurality of cycloheptyl groups, a cyclooctyl group A group having a plurality of cyclododecanyl groups, a group having a plurality of cyclododecanyl groups, and a tricyclodecanyl group, and adamantyl groups are most preferable in view of dry etching resistance. The formula of the polycyclic alicyclic hydrocarbon structure in the polycyclic alicyclic hydrocarbon group of X &lt; ₂ &gt; includes the same as the formula of the polycyclic alicyclic hydrocarbon structure in the group having the polycyclic alicyclic hydrocarbon structure, and the preferable range is also the same . The polycyclic alicyclic hydrocarbon group of X &lt; ₂ &gt; includes a monovalent group formed by bonding any one hydrogen atom in the above-mentioned polycyclic alicyclic hydrocarbon structure.

The above-mentioned alicyclic hydrocarbon group may further have a substituent. As the substituent, substituents which the polycyclic alicyclic hydrocarbon structure may have include the same ones as described above.

The substitution position of -OYX _{2 in} the general formula (4) may be para, meta or ortho, relative to the bonding position of the benzene ring with the polymer main chain, preferably para.

In the present invention, it is most preferable that the repeating unit represented by the general formula (3) is a repeating unit represented by the following general formula (4 ').

(38)

In the general formula (4 '), R ₁₃ represents a hydrogen atom or a methyl group.

R ₁₃ in the general formula (4 ') represents a hydrogen atom or a methyl group, but a hydrogen atom is particularly preferable.

The substitution position of the adamantyl ester group in the general formula (4 ') may be para, meta or ortho, relative to the bonding position of the benzene ring with the polymer main chain, preferably para.

Specific examples of the repeating unit represented by the general formula (3) include the following.

[Formula 39-1]

[Formula 39-2]

When the compound (D) is a polymer compound and contains a repeating unit having a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure, the content of the repeating unit Is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, based on the total repeating units of the compound (D) as a compound.

The compound (D) may have an acid crosslinkable group. When the compound (D) is a polymer compound, it is preferable to have a repeating unit having an acid crosslinking group.

As such a repeating unit having a crosslinkable group, a repeating unit represented by the following general formula (III) is preferable.

(40)

Wherein,

Ar ₁ represents aromatic ring.

R ₁ and R ₂ each independently represent an alkyl group, a cycloalkyl group, or an aryl group.

X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an acyl group.

R ₃ represents a hydrogen atom, an organic group or a halogen atom.

B represents a single bond or a linking group.

n represents an integer of 1 or more.

At least two of Ar ₁ , R ₁ and R ₂ may be bonded to each other to form a ring. When n represents an integer of 2 or more, a plurality of R ₁ , a plurality of R _2, and a plurality of X may be mutually the same or different.

The aromatic ring represented by Ar ₁ is preferably a group obtained by removing n + 1 hydrogen atoms from a monocyclic or polycyclic aromatic ring (n represents an integer of 1 or more).

Examples of the aromatic ring include an aromatic hydrocarbon ring (preferably having 6 to 18 carbon atoms) such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring and a phenanthrene ring, and a thiophene ring, a furan ring, a pyrrole ring, Include aromatic heterocyclic rings including heterocyclic rings such as benzene ring, benzene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzoimidazole ring, triazole ring, thiadiazole ring, and thiazole ring . Among them, a benzene ring and a naphthalene ring are preferred from the viewpoint of resolution, and a benzene ring is most preferable.

At least one of Ar ₁ and R ₁ and R ₂ may be bonded to form a ring.

The aromatic ring as Ar ₁ may have a substituent and examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, , And an arylcarbonyl group.

R ₁ and R ₂ each independently represent an alkyl group, a cycloalkyl group or an aryl group, and R ₁ and R ₂ may bond to each other to form a ring together with the carbon atom to which they are bonded.

Each of R ₁ and R ₂ independently represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

R ₁ and R ₂ each may have a substituent and examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, And an arylcarbonyl group.

Examples of R ₁ and R _{2 in the} case of having a substituent include a benzyl group and a cyclohexylmethyl group.

X is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an acyl group, and is preferably a hydrogen atom, an alkyl group or an acyl group, Is more preferable.

B represents a single bond or a divalent linking group.

When B represents a divalent linking group, a preferable group as a divalent linking group is a carbonyl group, an alkylene group, an arylene group, a sulfonyl group, -O-, -NH-, or a combination thereof (for example, an ester bond or the like) .

n represents an integer of 1 or more, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

When R ₃ represents an organic group, the organic group is preferably an alkyl group, a cycloalkyl group or an aryl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl) More preferably a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group or norbornyl group) or an aryl group having 6 to 10 carbon atoms (e.g., phenyl group or naphthyl group).

The organic group may further have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom), a carboxyl group, a hydroxyl group, an amino group, a cyano group, and the like, but are not limited thereto. As the substituent, a fluorine atom and a hydroxyl group are particularly preferable.

Examples of the organic group having a substituent include a trifluoromethyl group and a hydroxymethyl group.

R ₃ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

When B represents a divalent linking group, a preferable group as a divalent linking group is a carbonyl group, an alkylene group, an arylene group, a sulfonyl group, -O-, -NH-, or a combination thereof (for example, an ester bond or the like) .

B preferably represents a divalent linking group represented by the following general formula (B).

(41)

In the general formula (B), B ₁₂ represents a single bond or a divalent linking group. * Represents the bonding hands binding to the backbone. ** represents the bonding hands binding to Ar ₁ .

When B ₁₂ represents a divalent linking group, the divalent linking group is an alkylene group, -O-, a carbonyl bond, or a combination thereof.

It is also preferable that B represents a divalent linking group represented by the following general formula (B-1).

(42)

In the general formula (B-1), B ₂ represents a single bond or a divalent linking group. * Represents the bonding hands binding to the backbone. ** represents the bonding hands binding to Ar ₁ .

When B ₂ represents a divalent linking group, the divalent linking group is preferably an alkylene group or an alkyleneoxy group, more preferably an alkylene group having 1 to 5 carbon atoms or an alkyleneoxy group having 1 to 5 carbon atoms. When B ₂ represents an alkyleneoxy group, the oxy group of the alkyleneoxy group binds to any carbon atom constituting the benzene ring represented by the formula (B-1).

B ₁ is particularly preferably a single bond, a carbonyloxy group, a divalent linking group represented by the general formula (B) or a divalent linking group represented by the general formula (B-1).

The above-mentioned general formula (III) is also preferably the following general formula (I-2).

(43)

In the formula, the definitions of R ₁ to R ₃ , X, B ₁₂ , and n are as described above.

R ₁ and R ₂ in the general formula (I-2) each independently represent an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms desirable.

In the general formula (I-2), n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

The above-mentioned general formula (III) is also preferably the following general formula (I-3).

(44)

In the formula, the definitions of R ₁ to R ₂ , X, B ₂ , and n are as described above.

Each of R ₁ and R ₂ in the general formula (I-3) independently represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms desirable.

In the general formula (I-3), n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

Specific examples of the repeating unit represented by the formula (III) are shown below, but are not limited thereto. Me represents a methyl group, and Ac represents an acetyl group.

[Chemical Formula 45]

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(47)

(48)

The content of the repeating unit represented by the general formula (III) in the case where the compound (D) is a polymer compound is not particularly limited, but from the viewpoint of better pattern resolution, Is preferably 1 to 60 mol%, more preferably 3 to 50 mol%, and still more preferably 5 to 40 mol%.

The compound (D) as the polymer compound used in the present invention preferably further has the following repeating unit (hereinafter also referred to as " another repeating unit ") as the repeating unit other than the repeating unit.

Examples of polymerizable monomers for forming these other repeating units include styrene, alkyl substituted styrene, alkoxy substituted styrene, halogen substituted styrene, O-alkylated styrene, O-acylated styrene, hydrogenated hydroxystyrene (Methacrylic acid, methacrylic acid ester and the like), N-substituted maleimide, acrylonitrile, methacrylonitrile, vinylnaphthalene (methacrylic acid ester) , Vinyl anthracene, and indene which may have a substituent.

The compound (D) as the polymer compound may or may not contain these other repeating units. If contained, the content of these other repeating units in the compound (D) as the polymer compound is preferably such that the compound Is generally from 1 to 30 mol%, preferably from 1 to 20 mol%, and more preferably from 2 to 10 mol%, based on the total repeating units constituted.

The compound (D) as a polymer compound can be synthesized by a known radical polymerization method, an anionic polymerization method, a living radical polymerization method (an inferter method or the like). For example, in the anionic polymerization method, a polymer can be obtained by dissolving a vinyl monomer in an appropriate organic solvent and reacting under an ordinary cooling condition using a metal compound (such as butyllithium) as an initiator.

As the compound (D) as the polymer compound, a polyphenol compound (for example, JP-A-2008-145539) prepared by the condensation reaction of an aromatic ketone or an aromatic aldehyde and a compound containing 1 to 3 phenolic hydroxyl groups, (Japanese Unexamined Patent Application Publication No. 2004-18421), Noria derivatives (for example, JP-A-2009-222920), polyphenol derivatives (for example, JP-A 2008-94782) Or may be synthesized by modification with a polymer reaction.

The compound (D) as the polymer compound is preferably synthesized by modifying a polymer synthesized by a radical polymerization method or an anion polymerization method by a polymer reaction.

The weight average molecular weight of the compound (D) as the polymer compound is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 2,000 to 15,000.

The dispersity (molecular weight distribution) (Mw / Mn) of the compound (D) as the polymer compound is preferably 2.0 or less, preferably 1.0 to 1.80, more preferably 1.0 to 1.60 from the viewpoint of improvement in sensitivity and resolution , And most preferably 1.0 to 1.20. The use of living polymerization such as living anionic polymerization is preferable because the degree of dispersion (molecular weight distribution) of the obtained polymer compound becomes uniform. The weight average molecular weight and the degree of dispersion of the compound (D) as the polymer compound are defined as polystyrene reduced values by GPC measurement.

The amount of the compound (D) added to the composition of the present invention is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, and particularly preferably 50 to 85% by mass, based on the total solid content of the composition do.

Specific examples of the compound (D) are shown below, but the present invention is not limited thereto.

[Formula 49-1]

[Formula 49-2]

[Formula 49-3]

[Chemical Formula 49-4]

[Formula 49-5]

[Basic compound]

In addition to the above components, the composition of the present invention preferably contains a basic compound as an acid scavenger. By using a basic compound, it is possible to reduce a change in performance from an exposure to a post-heating over time. The basic compound is preferably an organic basic compound, and more specifically, it is preferably an organic basic compound, and more specifically, an aliphatic amine, an aromatic amine, a heterocyclic amine, a nitrogen containing compound having a carboxyl group, a nitrogen containing compound having a sulfonyl group, A nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like. An amine oxide compound (described in JP-A No. 2008-102383), an ammonium salt (preferably a hydroxide or a carboxylate, more specifically, a tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is referred to as LER ) Is also suitably used.

Further, a compound whose basicity increases due to the action of an acid can also be used as one kind of a basic compound.

Specific examples of the amines include tri-n-pentylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, tetradecylamine, pentadecyl N, N-dimethyldodecylamine, N, N-dibutyl aniline, N, N-dibutyl aniline, N, N-dibutyl aniline, N, N-dibutyl aniline, , N-dihexyl aniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline, triethanolamine, N, N-dihydroxyethylaniline, tris (methoxyethoxy Ethyl) -amine, the compound exemplified after column 3, line 60 of U.S. Patent No. 6040112, 2- [2- {2- (2,2- dimethoxy-phenoxyethoxy) (C1-1) to (C3-3) exemplified in paragraph [0076] of United States Patent Application Publication No. 2007/0224539 A1, and the like The. Examples of the compound having a nitrogen-containing heterocyclic structure include 2-phenylbenzoimidazole, 2,4,5-triphenylimidazole, N-hydroxyethylpiperidine, bis (1,2,2,6,6- 4-piperidyl) sebacate, 4-dimethylaminopyridine, antipyrine, hydroxyantipyrine, 1,5-diazabicyclo [4.3.0] nor-5-ene, 1,8- [5.4.0] -undes-7-ene, tetrabutylammonium hydroxide, and the like.

In addition, a photodegradable basic compound (initially, a basic nitrogen atom acts as a base to exhibit basicity but is decomposed by irradiation with an actinic ray or radiation to generate an amphoteric compound having a basic nitrogen atom and an organic acid moiety, Compounds in which basicity is reduced or eliminated by neutralization in the molecule. For example, Japanese Patent Publication No. 3577743, Japanese Patent Laid-Open Publication No. 2001-215689, Japanese Laid-Open Patent Publication No. 2001-166476, Japanese Patent Application Laid- 102383), photo-basic generating agents (for example, compounds described in JP-A-2010-243773) are also suitably used.

Of these basic compounds, ammonium salts are preferred from the viewpoint of improving the resolution.

The content of the basic compound in the present invention is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and particularly preferably 0.05 to 3% by mass, based on the total solid content of the composition.

[Surfactants]

The composition of the present invention may contain a surfactant for improving the coating property. Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters (Manufactured by Sumitomo 3M), Surfynol E1004 (manufactured by Asahi Glass Co., Ltd.), PF656 (manufactured by OMNOVA), and other nonionic surfactants such as Megafac (registered trademark) F171 and Megafac F176 Fluorine surfactants such as PF6320, organosiloxane polymers, and polysiloxane polymers.

When the composition of the present invention contains a surfactant, the content thereof is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total amount of the composition (excluding the solvent).

[Organic carboxylic acid]

In addition to the above components, the composition of the present invention preferably contains an organic carboxylic acid. Examples of such organic carboxylic acid compounds include aliphatic carboxylic acids, alicyclic carboxylic acids, unsaturated aliphatic carboxylic acids, oxycarboxylic acids, alkoxycarboxylic acids, ketocarboxylic acids, benzoic acid derivatives, phthalic acid, terephthalic acid, isophthalic acid, 2- 3-naphthoic acid, etc. When electron beam exposure is conducted under vacuum, there is a possibility that volatilization may occur from the surface of the resist film to contaminate the inside of the painting chamber. As preferable compounds, aromatic organic carboxylic acids, Among them, for example, benzoic acid, 1-hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid are suitable.

The blending ratio of the organic carboxylic acid is preferably 0.5 to 15% by mass, more preferably 2 to 10% by mass, based on the total solid content of the composition.

The composition of the present invention may contain, if necessary, a dye, a plasticizer, an acid growth agent (WO 95/29968, WO 98/24000, JP-A-8-305262, Japanese Patent Laid-Open Nos. 9-34106, 8-248561, 8-503082, 5,445,917, 8-503081, 5,534,393, U.S. Patent No. 5,395,736, U.S. 5,741,630, U.S. 5,334,489, U.S. 5,582,956, U.S. 5,578,424, U.S. 5,453,345, U.S. 5,445,917, Europe Patent Publication No. 665,960, European Patent Publication No. 757,628, European Patent Publication No. 665,961, US Patent No. 5,667,943, Japanese Patent Application Laid-Open No. 10-1508, Japanese Patent Application Laid-Open No. 10-282642, Japanese Patent Application Laid-Open No. 9-512498, Japanese Patent Application Laid-Open No. 2000-62337 , Japanese Laid-Open Patent Publication No. 2005-17730, Japanese Laid-Open Patent Publication No. 2008-209889 described the like) it may further contain the like. As for these compounds, all of the compounds described in JP-A-2008-268935 can be mentioned.

[Carboxylic acid onium salt]

The composition of the present invention may contain a carboxylic acid onium salt. Examples of the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt. Particularly, as the carboxylic acid onium salt, a carboxylic acid sulfonium salt or a carboxylic acid iodonium salt is preferable. Further, in the present invention, it is preferable that the carboxylate residue of the onium carboxylate does not contain an aromatic group or a carbon-carbon double bond. As a particularly preferable anion moiety, a linear, branched, monocyclic or polycyclic cyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. More preferably, an anion of a carboxylic acid in which a part or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. As a result, transparency to light of 220 nm or less is ensured, sensitivity and resolving power are improved, density dependency and exposure margin are improved.

The compounding ratio of the onium carboxylate is preferably from 1 to 15% by mass, more preferably from 2 to 10% by mass, based on the total solid content of the composition.

[Acid proliferating agent]

The actinic ray-sensitive or radiation-sensitive composition of the present invention may also contain one or more compounds (hereinafter also referred to as acid-proliferating agents) which are decomposed by the action of an acid to generate an acid. The acid in which the acid proliferator is generated is preferably a sulfonic acid, a meta acid or an imide acid. The content of the acid growth inhibitor is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%, and further preferably 1.0 to 20 mass%, based on the total solid content of the composition.

The amount ratio of the acid proliferator and the acid generator (the solid content of the acidic proliferator based on the total solid content in the composition / the solid content of the acid generator based on the total solid content in the composition) is not particularly limited, , More preferably 0.1 to 20, and particularly preferably 0.2 to 1.0.

Examples of acid proliferating agents usable in the present invention are shown below, but the present invention is not limited thereto.

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[solvent]

The composition of the present invention may contain a solvent. Examples of the solvent include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME, also referred to as 1-methoxy Propanol), propylene glycol monomethyl ether acetate (PGMEA, alias 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether propionate, propylene glycol monoethyl Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl beta -methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, But are not limited to, methyl 2-hydroxyisobutyrate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, N, N-dimethylformamide, Acetamide, Such as propylene carbonate, ethylene carbonate is preferable. These solvents may be used alone or in combination.

It is preferable that the solid content of the composition of the present invention is dissolved in the above-mentioned solvent and dissolved in an amount of 1 to 40 mass% as a solid content concentration. More preferably from 1 to 30% by mass, and still more preferably from 3 to 20% by mass.

<Sensitive actinic radiation or radiation-sensitive film formation and mask blank>

The present invention also relates to an actinic ray-sensitive or radiation-sensitive film containing the composition of the present invention. Such a film is formed, for example, by applying the composition of the present invention onto a support such as a substrate. The thickness of this film is preferably 0.02 to 0.1 mu m. As a method of coating on a substrate, it is coated on a substrate by a suitable coating method such as spin coating, roll coating, float coating, dip coating, spray coating, doctor coat, etc., but spin coating is preferable, 3000 rpm is preferable. The coated film is prebaked at 60 to 150 DEG C for 1 to 20 minutes, preferably at 80 to 120 DEG C for 1 to 10 minutes to form a thin film.

The material constituting the a processed substrate and the uppermost layer is, for example, in the case of a semiconductor wafer, it is possible to use a silicon wafer, examples of which the outermost surface layer material, Si, SiO _2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, and the like.

The present invention also relates to a mask blank provided with the actinic ray-sensitive or radiation-sensitive film obtained as described above. When a pattern is formed on a photomask blank for producing a photomask in order to obtain a mask blank having such a sensitizing actinic radiation or radiation-sensitive film, a transparent substrate such as quartz or calcium fluoride may be used as the transparent substrate to be used . In general, necessary functional films such as a light-shielding film, an antireflection film, a phase shift film, an etching stopper film, and an etching mask film are laminated on this substrate. As a material of the functional film, a film containing silicon or a transition metal such as chromium, molybdenum, zirconium, tantalum, tungsten, titanium or niobium is laminated. As the material used for the outermost layer, a material containing silicon and / or silicon as a main constituent material and a silicon compound material containing a transition metal as a main constituent material At least one element selected from the group consisting of oxygen, nitrogen and carbon, and at least one element selected from the group consisting of transition metals, particularly chromium, molybdenum, zirconium, tantalum, tungsten, titanium and niobium, A transition metal compound material in which a material is a main constituent material is exemplified.

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

Among these materials, in the case where a pattern is formed using a resist composition on a photomask blank having a top surface layer of a material containing oxygen or nitrogen in chromium in general, a so-called undercut shape However, when the present invention is used, the undercut problem can be improved compared with the conventional case.

(Usually 80 to 150 占 폚, more preferably 90 to 130 占 폚) is applied to the active ray-sensitive or radiation-sensitive film by irradiating (i.e., exposing) active rays or radiation , And develops. As a result, a good pattern can be obtained. Then, the semiconductor fine circuit and the mold structure for imprint are manufactured by appropriately performing the etching process and the ion implantation using the pattern as a mask.

The process for producing the imprint mold using the composition of the present invention is described in, for example, Japanese Patent Publication No. 4109085, Japanese Laid-Open Patent Publication No. 2008-162101, and " · Application development - Nano imprint substrate technology and latest technology development - Editing: Yoshihiko Hirai (Frontier Shotpan) ".

&Lt; Pattern formation method >

The composition of the present invention can be suitably used for the following negative pattern formation process. That is, the step of applying the composition of the present invention to a substrate to form an actinic ray-sensitive or radiation-sensitive film, a step of irradiating the actinic ray or radiation-sensitive film with an actinic ray or radiation (that is, exposure) And a step of developing a film using a developing solution to obtain a negative pattern. As such a process, for example, the processes described in JP-A-2008-292975 and JP-A-2010-217884 can be used.

The present invention also relates to a pattern forming method comprising a step of exposing a mask blank having the actinic ray-sensitive or radiation-sensitive film, and a step of developing the mask blank having the exposed film. In the present invention, it is preferable that the exposure is performed using an electron beam or an extreme ultraviolet ray.

In the exposure (pattern forming step) on the resist film in the production of a precision integrated circuit device, it is preferable that the resist film of the present invention is first subjected to electron beam or extreme ultraviolet (EUV) irradiation in the form of a pattern. The exposure dose is about 0.1 to 20 μC / cm ² , preferably about 3 to 10 μC / cm ^{2 for} electron beam and about 0.1 to 20 mJ / cm ² , preferably about 3 to 15 mJ / cm ^{2 for} extreme ultraviolet light . Subsequently, post exposure baking (postexposure baking) is performed on a hot plate at 60 to 150 ° C for 1 to 20 minutes, preferably at 80 to 120 ° C for 1 to 10 minutes, and then development, rinsing and drying are performed to form a pattern do. Subsequently, development is carried out by a conventional method such as a dip method, a puddle method or a spray method using a developing solution for 0.1 to 3 minutes, preferably 0.5 to 2 minutes.

As the developer, both an organic developer and an alkaline developer can be used. Examples of the organic developing solution include ester solvents (such as butyl acetate, ethyl acetate, methyl 2-hydroxyisobutyrate, etc.), ketone solvents (such as 2-heptanone and cyclohexanone) A polar solvent such as a solvent, an amide solvent or an ether solvent, and a hydrocarbon solvent may be used. The water content of the organic developing solution as a whole is preferably less than 10 mass%, more preferably substantially water-free.

As the alkali developing solution, a quaternary ammonium salt represented by tetramethylammonium hydroxide is usually used, but in addition, an aqueous alkali solution such as an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine or a cyclic amine can be used . In addition, alcohols and surfactants may be added to the alkali developing solution in an appropriate amount. The alkali concentration of the alkali developing solution is usually 0.1 to 20 mass%. The pH of the alkali developing solution is usually from 10.0 to 15.0.

Alcohols and surfactants may be added to the alkaline aqueous solution in an appropriate amount.

Since the composition of the present invention is a negative resist composition used for forming a negative pattern, the film of the unexposed portion is dissolved, and the exposed portion is hardly dissolved in the developer by crosslinking of the compound. By using this, a desired pattern can be formed on a substrate.

The present invention also relates to a method of manufacturing an electronic device including the pattern forming method of the present invention and an electronic device manufactured by the method.

INDUSTRIAL APPLICABILITY The electronic device of the present invention is suitably mounted in electric and electronic devices (such as home appliances, OA and media-related devices, optical devices, and communication devices).

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

&Lt; Synthesis of onium salt compound (A) >

The onium salt compounds (A-1) to (A-9) described below were synthesized by a known method.

&Lt; Synthesis of acid generator (B) >

The acid generators (B-1) to (B-7) described below were synthesized by a known method.

&Lt; Synthesis of compound (D) having acid-crosslinkable group >

Synthesis Example 3: Synthesis of Compound (CL-7)

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(Synthesis of Compound (CL-7A)

A mixture of 18.8 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (Wako Junyaku), 19.8 g of 50% dimethylamine aqueous solution, 6.6 g of paraformaldehyde and 10 mL of ethanol was stirred at 80 ° C for 2 hours did. Ethanol was distilled off, and 50 mL of ethyl acetate and 50 mL of water were added to separate the solution, and the organic layer was washed twice with 50 mL of water. The obtained organic layer was dried with magnesium sulfate and filtered, and the solvent of the filtrate was distilled off to obtain 23.4 g (yield 95%) of (C-1A) as a crude product (crude product). Fig. 2 shows a ¹ H-NMR (acetone-d6) chart of the compound (CL-7A).

(Synthesis of Compound (CL-7B)

To 23.4 g of the compound (CL-7A) obtained above, 37.2 g of acetic anhydride was added and the mixture was stirred at 80 占 폚 for 6 hours. After cooling, acetic acid and acetic anhydride were distilled off to obtain 27.1 g of a compound (D-2B). Compound (CL-7B) thus obtained was used for synthesis of compound (CL-7) without further purification.

(Synthesis of Compound (CL-7)

58 g of methanol and 6.9 g of potassium carbonate were added to 27.1 g of the compound (CL-7B) obtained above, and the mixture was stirred at 60 DEG C for 2 hours. After cooling, the methanol was distilled off. 100 mL of ethyl acetate and 100 mL of water were added and the liquid separation operation was carried out. The organic layer was washed with 100 mL of 1N hydrochloric acid aqueous solution, and further washed three times with 100 mL of water. The obtained organic layer was dried with magnesium sulfate, and the drying agent was filtered, and the solvent of the filtrate was distilled off to obtain 19.8 g of a compound (CL-7) (total yield: 85%). 1 shows a ¹ H-NMR (acetone-d6) chart of the compound (CL-7).

[Onium salt compound (A)]

As the onium salt compound (A), the following compounds were used. The fluorine atom content (mass%) and pKa value are shown together. Here, pKa represents a value calculated using the software package 1 as described above.

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[Acid generator (B)]

The following acid generators (B) were used. The fluorine atom content (mass%) and pKa value are shown together. Here, pKa represents a value calculated using the software package 1 as described above.

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[Compound (C) having an acid crosslinkable group]

As the compound (C) having an acid crosslinkable group, the following compounds were used.

(56)

[Compound (D) containing a phenolic hydroxyl group]

As the compound (D) containing a phenolic hydroxyl group, the following compounds were used. The compositional ratio (molar ratio), the weight average molecular weight (Mw) and the degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) are shown below.

Here, the weight average molecular weight Mw (in terms of polystyrene), the number average molecular weight Mn (in terms of polystyrene) and the dispersion degree Mw / Mn were calculated by GPC (solvent: THF) measurement. The composition ratio (molar ratio) was calculated by ¹ H-NMR measurement.

(57)

〔Surfactants〕

W-1: PF6320 (manufactured by OMNOVA)

W-2: Megafac F176 (manufactured by DIC Corporation; fluorine-based)

W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co.,

〔solvent〕

S1: Propylene glycol monomethyl ether (1-methoxy-2-propanol)

S2: Propylene glycol monomethyl ether acetate (1-methoxy-2-acetoxypropane)

S3: 2-heptanone

S4: Ethyl lactate

S5: cyclohexanone

S6:? -Butyrolactone

S7: Propylene carbonate

(1) Preparation of Support

A 6-inch wafer (subjected to a shielding film treatment used for a normal photomask blank) with Cr oxide deposition was prepared.

(2) Preparation of resist composition

The components shown in Table 1 were dissolved in a solvent shown in the table to prepare a solution. The solution was filtered with a polytetrafluoroethylene filter having a pore size of 0.03 m to prepare a resist composition.

[Table 1]

(3) Preparation of resist film

A resist composition was coated on the 6-inch wafer using a spin coater Mark 8 manufactured by Tokyo Electron and dried on a hot plate at 100 캜 for 600 seconds to obtain a resist film having a thickness of 50 nm. That is, a resist-coated wafer was obtained.

(4) Fabrication of negative resist pattern

The resist film was subjected to pattern irradiation using an electron beam imaging apparatus (ELS-7500, manufactured by Elionix Co., Ltd., acceleration voltage: 50 KeV). After the irradiation, the substrate was heated on a hot plate at 120 DEG C for 60 seconds, immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 120 seconds, and rinsed with water for 30 seconds.

(5) Evaluation of resist pattern

The obtained pattern was evaluated for sensitivity, resolution, pattern collapse, and bridge defect by the following method. The results are shown in Table 2 below.

<Sensitivity>

The irradiation energy at the time of resolving a 1: 1 line-and-space pattern having a line width of 50 nm was determined as the sensitivity (Eop). The smaller this value is, the better the performance is.

<L / S resolution>

(Minimum line width at which lines and spaces (line: space = 1: 1) are separated and resolved) in the exposure amount representing the sensitivity (Eop) is defined as resolution (nm).

<Isolation Space Pattern (Iso-Space) Resolution>

(The minimum space width in which lines and spaces are separated and resolved) of the isolated space (line: space = 100: 1) in the sensitivity (Eop). This value was defined as " isolated space pattern resolution (nm) ". The smaller this value is, the better the performance is.

<Pattern collapse>

When the line width was narrowed by reducing the exposure amount from the above sensitivity (Eop), the minimum line width at which the pattern was not collapsed and resolved was measured, and this minimum line width was used as an index for suppressing the occurrence of pattern collapse. A smaller value indicates that a thinner pattern is resolved without collapsing, and exhibits excellent suppressing ability of occurrence of pattern collapse.

<Bridge Defect>

A 1: 1 line-and-space pattern having a line width of 50 nm formed with the above sensitivity (Eop) was measured with a defect inspection apparatus KLA2360 (trade name) manufactured by K.L.A. Further, the threshold value was set to 20, the number of defects per unit area (number / cm ² ) was measured, and defect review was performed to extract bridge defects from all the defects. The number of defects (number / cm ² ) extracted from the difference caused by the overlapping of the comparison image and the pixel unit was detected, and the number of defects per unit area was calculated.

The smaller this value is, the better the bridging defect reduction performance is.

[Table 2]

From the results shown in Table 2, it can be seen that the pattern obtained by the pattern forming method of the present invention is excellent in sensitivity and resolution and also suppresses bridge defects and pattern collapse.

Claims (27)

(A) an onium salt compound containing at least one fluorine atom in the anion portion and at least one nitrogen atom in the cation portion,
(B) a compound containing at least one fluorine atom, which generates an acid by irradiation with an actinic ray or radiation, and
(D) a compound containing a phenolic hydroxyl group, wherein the light sensitive or radiation-
The content of the fluorine atom in the compound (A) relative to the total mass of the compound (A) is higher than the content of the fluorine atom in the compound (B) relative to the total mass of the compound (B) ) Is a resin containing a repeating unit represented by the following general formula (3).

[In the general formula (3), R ₁₃ represents a hydrogen atom or a methyl group.
X represents a group having a non-acid decomposable polycyclic alicyclic hydrocarbon structure.
Ar ₁ represents an aromatic ring.
m2 is an integer of 1 or more] The method according to claim 1,
Wherein the difference between the content of the fluorine atom in the compound (A) and the content of the fluorine atom in the compound (B) is 0.5% by mass or more in terms of a mass percentage. The method according to claim 1 or 2,
Wherein the compound (B) is a sulfonate compound containing at least one fluorine atom in the anion moiety. The method according to claim 1 or 2,
The positive-ion moiety of the compound (A) has a basic moiety containing the nitrogen atom. The method of claim 4,
Wherein the basic moiety of the compound (A) contains an amino group or a nitrogen-containing heterocyclic group. The method according to claim 1 or 2,
The cation moiety of the compound (A) has a partial structure represented by the following general formula (NI), wherein the cation moiety of the compound (A) is a sensitizing actinic ray or radiation sensitive resin.
[Chemical Formula 1]

Wherein,
R _A and R _B each independently represent a hydrogen atom or an organic group.
X represents a single bond or a linking group.
At least two of R _A , R _B and X may be bonded to each other to form a ring. The method according to claim 1 or 2,
Wherein the compound (A) is an onium salt represented by the following general formula (N-II).
(2)

Wherein,
A represents a sulfur atom or an iodine atom.
R ₁ represents a hydrogen atom or an organic group, and when a plurality of R _{1 s} exist, R ₁ may be the same or different.
R represents an (o + 1) -valent organic group, and when a plurality of R exists, R may be the same or different.
X represents a single bond or a linking group, and when a plurality of X exist, X may be the same or different.
A _N represents a basic site containing a nitrogen atom, and when a plurality of A _N exist, A _N may be the same or different.
When A is a sulfur atom, n is an integer of 1 to 3, and m is an integer satisfying the relationship of m + n = 3.
When A is an iodine atom, n is 1 or 2, and m is an integer satisfying the relationship of m + n = 2.
o represents an integer of 1 to 10;
Y ^- represents an anion.
At least two of R ₁ , X, R and A _N may be bonded to each other to form a ring. The method of claim 3,
Wherein the compound (A) and the compound (B) have the same negative ion moiety. The method according to claim 1 or 2,
Wherein the content of the compound (A) relative to the total solid content in the resin composition having the actinic ray-sensitive or radiation-sensitive actinic ray is in the range of 0.1 to 20 mass%. The method according to claim 1 or 2,
(C) a compound containing an acid-crosslinkable group. The method of claim 10,
The resin composition (C) containing an acid-crosslinkable group contains two or more hydroxymethyl groups or alkoxymethyl groups in the molecule. delete The method according to claim 1 or 2,
The resin composition (D) containing a phenolic hydroxyl group is a resin containing a repeating unit represented by the following general formula (II).
(3)

Wherein,
R ₂ represents a hydrogen atom, a methyl group which may have a substituent, or a halogen atom.
B 'represents a single bond or a divalent organic group.
Ar 'represents aromatic ventilation.
m represents an integer of 1 or more. 14. The method of claim 13,
The resin (D) containing a phenolic hydroxyl group is a resin further comprising a repeating unit represented by the following general formula (III).
[Chemical Formula 4]

Wherein,
Ar ₁ represents aromatic ring.
R ₁ and R ₂ each independently represent an alkyl group, a cycloalkyl group, or an aryl group.
X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an acyl group.
R ₃ represents a hydrogen atom, an organic group or a halogen atom.
B represents a single bond or a linking group.
n represents an integer of 1 or more.
At least two of Ar ₁ , R ₁ and R ₂ may be bonded to each other to form a ring. When n represents an integer of 2 or more, a plurality of R ₁ , a plurality of R _2, and a plurality of X may be mutually the same or different. A light sensitive actinic radiation or radiation sensitive film comprising the composition of claim 1 or 2. A mask blank having the actinic ray-sensitive or radiation-sensitive film according to claim 15. A step of forming an actinic ray-sensitive or radiation-sensitive film by using the resin composition which is sensitive to actinic ray or radiation radiation according to claim 1 or 2,
Irradiating the actinic ray-sensitive or radiation-sensitive film with an actinic ray or radiation, and
And developing the actinic ray-sensitive or radiation-sensitive film which is irradiated with actinic rays or radiation. 18. The method of claim 17,
Wherein the actinic ray or radiation is irradiated using an electron beam or an extreme ultraviolet ray. A method of manufacturing an electronic device comprising the pattern forming method according to claim 17. delete The method of claim 6,
X is a group formed by combining an alkylene group, an alkylene group and an ether linkage, or a group formed by combining an alkylene group and an ester linkage. The method of claim 6,
Wherein the onium salt compound (A) is a sulfonium salt compound or an iodonium salt compound,
The S ⁺ in the sulfonium salt compound or I ⁺ in the iodonium salt compound is not contained in the partial structure represented by the general formula (N-1), and is contained in the remainder of the cation moiety to which the partial structure binds, Or radiation-sensitive resin composition. The method of claim 7,
X is a group formed by combining a single bond, an alkylene group, an alkylene group and an ether bond, or a group formed by combining an alkylene group and an ester bond.


The method according to claim 1 or 2,
Ar ₁ is an aromatic hydrocarbon ring having 6 to 18 carbon atoms which may have a substituent, and is a sensitizing radiation-sensitive or radiation-sensitive resin composition. The method according to claim 1 or 2,
m2 &lt; / RTI &gt; is an integer from 1 to 5. &lt; RTI ID = 0.0 &gt; The method according to claim 1 or 2,
Wherein the compound (A) contains at least one nitrogen atom having a non-covalent electron pair not participating in the? -Conjugation in the cation moiety. delete

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