TW201617733A - Active light sensitive or radiation sensitive resin composition, or radiation sensitive film, mask blank provided with active light sensitive, pattern forming method, method for manufacturing electronic device, and electronic device - Google Patents

Abstract

The present invention relates to: an active light sensitive or radiation sensitive resin composition; an active light sensitive or radiation sensitive film using the active light sensitive or radiation sensitive resin composition; a mask blank which is provided with this film; a pattern forming method; a method for manufacturing an electronic device, which comprises this pattern forming method; and an electronic device which is manufactured by this method for manufacturing an electronic device. An active light sensitive or radiation sensitive resin composition according to the present invention contains (A) an onium salt compound that contains at least one fluorine atom in the anionic component, while containing at least one nitrogen atom in the cationic component, and (B) a compound that contains at least one fluorine atom and generates an acid when irradiated with active light or radiation. The content ratio of the fluorine atoms in the compound (A) relative to the total mass of the compound (A) is higher than the content ratio of the fluorine atoms in the compound (B) relative to the total mass of the compound (B).

Description

Photosensitive ray- or radiation-sensitive resin composition, sensitizing ray-sensitive or radiation-sensitive film, blank mask including sensitized ray-sensitive or radiation-sensitive film, pattern forming method, electronic component manufacturing method, and electronic component

The present invention relates to a microlithography process suitable for use in the manufacture of a super LSI or a high-capacity microchip or another manufacturing process, and can form a highly refined pattern by electron beam or extreme ultraviolet ray. Radiation-sensitive or radiation-sensitive resin composition, sensitizing ray-sensitive or radiation-sensitive film using the same, blank mask having sensitized ray-sensitive or radiation-sensitive film, mask, pattern forming method, and manufacturing method of electronic component And electronic components. In particular, the present invention relates to a photosensitive ray-sensitive or radiation-sensitive resin composition suitable for use in a process using a substrate having a specific base film, a sensitized ray-sensitive or radiation-sensitive film using the same, and a sensitizing ray or A blank mask, a mask, a pattern forming method, a method of manufacturing an electronic component, and an electronic component of a radiation sensitive film.

Previously, in the manufacturing process of a semiconductor device such as an IC or an LSI, microfabrication was performed by using a lithography of a photoresist composition. In recent years, with the high integration of integrated circuits, it has been demanded to form ultrafine patterns of submicron regions or quarter micrometer regions. As a result, it has been found that the exposure wavelength also tends to be short-wavelength from the g-ray to the i-ray and further to the excimer laser light. Currently, lithography using electron beams or X-rays is being developed.

Electron beam or extreme ultraviolet lithography is positioned as a next-generation or next-generation patterning technique, and is widely used for reticle fabrication used in semiconductor exposure due to high resolution. For example, in the step of fabricating the mask by electron beam lithography, a photoresist layer is formed on a mask substrate on which a shielding layer containing chromium or the like as a main component is formed on a transparent substrate, and then selectively performed. After electron beam exposure, alkaline development is performed to form a photoresist pattern. Next, using the photoresist pattern as a mask, the shielding layer is etched to form a pattern on the shielding layer, whereby a mask having a shielding layer having a predetermined pattern on the transparent substrate can be obtained.

As described above, as the required pattern is miniaturized, the decrease in the resolution caused by the pattern shape becomes a problem. As a method for solving the problem of clarification, an acid generator containing a nitrogen atom in a cationic portion is disclosed in the cited document 1.

In particular, when a negative pattern is formed, the front end portion of the pattern tends to be in an expanded shape (hereinafter also referred to as a T-top shape), and there is a problem that bridging is likely to occur in the isolated space pattern. As described above, in the negative pattern, it is more difficult to improve the resolution, and a negative-type photoresist composition excellent in resolution is required.

In such a practical case, for example, Patent Document 2 discloses a negative-type photoresist composition containing an onium salt compound containing a nitrogen atom in a cationic portion; and generating an acid by irradiation with actinic rays or radiation. A compound; and a compound containing an acid crosslinkable group, whereby a negative pattern having excellent resolution can be obtained by pattern formation using an electron beam or extreme ultraviolet ray (EUV light).

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2007-230913

Patent Document 2: Japanese Laid-Open Patent Publication No. 2014-134686

By using an onium salt compound containing a nitrogen atom in the cation portion, the shape of the T-Top in the negative pattern is improved, and the shape and the resolution of the pattern are improved, but the inventors have conducted intensive studies and found that when utilizing Bridging defects and pattern collapse may cause problems in a long development process or a developing process in which the developer flow rate is fast. In particular, when an ultrafine pattern having a line width of 50 nm or less is formed, further improvement in bridging defects and pattern collapse is required.

The present invention has been made in view of such an actual situation, and an object of the present invention is to provide a sensitized 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. A sensitizing ray-sensitive or radiation-sensitive film, a blank mask including the film, a mask, and a pattern forming method are used. Another object of the present invention is to provide a method of manufacturing an electronic component including the pattern forming method and an electronic component manufactured by the method of manufacturing the electronic component.

In one aspect, the invention is as follows.

[1] A sensitizing ray-sensitive or radiation-sensitive resin composition comprising: (A) an onium salt compound containing at least one fluorine atom in an anion portion and containing at least one nitrogen atom in a cation portion; and (B) a compound containing at least one fluorine atom and generating an acid by irradiation with actinic rays or radiation, wherein the content of the fluorine atom in the compound (A) relative to the total mass of the compound (A) is greater than that of the compound (B) The content ratio of the fluorine atom in the total mass of the compound (B).

[2] The photosensitive ray-sensitive or radiation-sensitive resin composition according to [1], wherein the content ratio of the fluorine atom in the compound (A) and the content ratio of the fluorine atom in the compound (B) are the same The difference is converted into a mass percentage of 0.5% by mass or more.

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

The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of the above aspects, wherein the cation portion of the compound (A) is provided with an alkaline portion containing the nitrogen atom. .

[5] The photosensitive ray-sensitive or radiation-sensitive resin composition according to [4], wherein the basic moiety of the compound (A) contains an amine group or a nitrogen-containing heterocyclic group.

The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of the above aspects, wherein the cation portion of the compound (A) is represented by the following formula (NI) Part of the structure. [Chemical Formula 1] In the formula, 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 sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of the aspects of the present invention, wherein the compound (A) is represented by the following formula (N-II). salt. [Chemical Formula 2] In the formula, 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 are present, R ₁ may be the same or different. R represents an organic group of (o+1) valence, and when there are a plurality of R, R may be the same or different. X represents a single bond or a linking group, and when there are a plurality of X, X may be the same or different. A _N represents an alkaline moiety containing a nitrogen atom, and when there are a plurality of A _N , 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 from 1 to 10. Y ^- is an anion. At least two of R ₁ , X, R and A _N may be bonded to each other to form a ring.

The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of the above aspects, wherein the compound (A) and the compound (B) have the same anion portion.

The photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of the above aspects, wherein the compound (A) is relative to the above-mentioned sensitizing ray-sensitive or radiation-sensitive resin composition The content of all solid components in the range is from 0.1 to 20% by mass.

[10] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9] further comprising a compound containing (C) an acid crosslinkable group.

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

[12] The sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [11] further comprising a compound containing (D) a phenolic hydroxyl group.

[13] The sensitizing ray-sensitive or radiation-sensitive resin composition according to [12], wherein the compound (D) containing a phenolic hydroxyl group is a resin comprising a repeating unit represented by the following formula (II). [Chemical Formula 3] In the formula, 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 an aromatic ring group. m represents an integer of 1 or more.

[14] The sensitizing ray-sensitive 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 formula (III) . [Chemical Formula 4] In the formula, Ar ₁ represents an aromatic ring group. 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 a fluorenyl 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, the plurality of R ₁ , the plurality of R _{2 ,} and the plurality of X may be the same or different.

[15] A sensitizing ray-sensitive or radiation-sensitive film comprising the composition according to any one of [1] to [14].

[16] A blank mask comprising the sensitized ray-sensitive or radiation-sensitive film according to [15].

[17] A pattern forming method comprising the steps of: forming a sensitized ray-sensitive or radiation-sensitive film by using the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [14] The actinic ray-sensitive or radiation-sensitive linear film is irradiated with actinic rays or radiation; and the above-mentioned sensitized ray-sensitive or radiation-sensitive film irradiated with actinic rays or radiation is developed.

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

[19] A method of producing an electronic component, comprising the pattern forming method according to [17] or [18].

[20] An electronic component produced by the method of producing an electronic component according to [19].

According to the present invention, it is possible to provide a sensitized ray-sensitive or radiation-sensitive resin composition which is excellent in sensitivity and resolution, and which is excellent in bridging defects and pattern collapse, and which is used for sensitizing ray or radiation. A film, a blank mask having the film, and a pattern forming method. Further, according to the present invention, it is possible to provide a method of manufacturing an electronic component including the pattern forming method and an electronic component manufactured by the method of manufacturing the electronic component.

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

In the label of the group (atomic group) in the present specification, the label which is not labeled with a substitution and is unsubstituted includes a group having no substituent (atomic group), and further includes a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

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

In addition, unless otherwise specified, the "exposure" in this specification includes not only the use of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, EUV lights, etc., but also electron beams, ion beams, and the like. The drawing by the particle beam is also included in the exposure.

<Photosensitized ray-sensitive or radiation-sensitive resin composition>

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains at least one fluorine atom in the anion portion and at least one nitrogen atom in the cation portion. a salt compound (A) (hereinafter referred to as "sulfonium salt compound (A)" or "compound (A)"); and an acid containing at least one fluorine atom by irradiation with actinic rays or radiation Compound (B) (hereinafter referred to as "acid generator (B)" or "compound (B)"). In the composition of the present invention, the onium salt compound (A) and the acid generator (B) have the following relationship: the content of the fluorine atom in the onium salt compound (A) relative to the total mass of the onium salt compound is greater than that of the acid generator (B) The content of the fluorine atom in the total mass of the acid generator.

As described above, the present inventors have found that the T-Top shape is improved by adding a sulfonium salt compound containing a nitrogen atom in the cation portion to the sensitized ray-sensitive or radiation-sensitive resin composition, and the pattern shape and analysis are performed. The properties are improved, and in particular, when an ultrafine pattern having a line width of 50 nm or less is formed, there is room for further improvement in bridging defects and pattern collapse.

The inventors of the present invention conducted further intensive studies and found that the problem of the present invention can be solved by using the onium salt compound (A) and the acid generator (B) together, and the above-mentioned onium salt compound (A) is in the anion portion. It contains at least one fluorine atom and contains at least one nitrogen atom in the cation portion, the acid generator (B) contains at least one fluorine atom, and the content of the fluorine atom in the sulfonium salt compound (A) is greater than that of the acid. The relationship between the content ratio of fluorine atoms in the agent (B). In other words, it has been found that an ultrafine pattern having a line width of 50 nm or less excellent in bridging defects and pattern collapse can be obtained in addition to improvement in sensitivity and resolution. Further, it has been found that the effect of the present invention becomes more remarkable when a development process having a long time or a developing process with a faster developer flow rate is used, especially in a thick photoresist film having a film thickness of 100 nm or more. The reason is not necessarily clear, but it is presumed as follows.

That is, in a system in which a basic sulfonium salt compound and an acid generator are simultaneously present in a photosensitive ray-sensitive or radiation-sensitive resin composition, the basic sulfonium salt compound is hydrophilic with respect to the acid generator due to the presence of a basic group. Sex. Therefore, at the time of film formation, the basic onium salt compound is concentratedly distributed on the surface side of the substrate on which the composition is applied, and the acid generator is concentratedly distributed on the air interface side, and tends to form a non-uniform distribution. Therefore, the quenching of the acid generated in the vicinity of the surface of the photoresist film is insufficient, and it is presumed that the crosslinking reaction is performed not only in the exposed portion but also in the unexposed portion, and as a result, the occurrence of bridging and pattern collapse is promoted.

On the other hand, by using an acid generator containing a fluorine atom and a basic sulfonium salt compound having a fluorine atom content higher than that of the acid generator, the concentration of the basic sulfonium salt compound near the surface of the photoresist film can be made larger than that of the acid. The concentration of the generator. As a result, it is estimated that the quenching of the acid generated in the vicinity of the surface of the photoresist film is insufficient, and it is presumed that this further improves sensitivity and resolution, and is effective for improving the ability to suppress bridging defects and pattern collapse. In particular, when the acid generator and the basic cerium salt contain at least one fluorine atom in the anion portion thereof, the acidity of the acid generated is strong, so that the sensitized ray-sensitive or radiation-sensitive resin composition is present. The reactivity of the coupling and the deprotection reactivity become high. In such a highly reactive sensitizing ray-sensitive or radiation-sensitive resin composition, bridging defects and pattern collapse caused by uneven distribution of the above acid generator and basic sulfonium salt compound are liable to occur, and thus the present invention The effect is changing.

In one embodiment of the present invention, the composition of the present invention contains the onium salt compound (A) and the acid generator (B), and further preferably contains a compound containing a phenolic hydroxyl group. Further, the composition of the present invention further preferably contains a compound containing an acid crosslinkable group, and the form may be a form in which the above compound containing a phenolic hydroxyl group contains an acid crosslinkable group, and may also be used as a phenol. The compound of the above-mentioned hydroxyl group is different from the other compound and contains a form of a compound containing an acid crosslinkable group.

Hereinafter, each component which can be contained in the composition of the present invention will be described in further detail.

[鎓 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 cationic portion.

As described above, the onium salt compound (A) contained in the composition of the present invention has a fluorine atom content ratio higher than that of the fluorine atom in the acid generator (B) containing at least one fluorine atom described later. . Here, the content rate of the fluorine atom means the content rate of the fluorine atom in the compound represented by (the total of the mass of all the fluorine atoms contained in the compound) / (the total mass of all the atoms contained in the compound).

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

Here, the onium salt compound (A) may be contained in the anion portion as long as at least one fluorine atom, and when a plurality of fluorine atoms are contained, a part of the fluorine atom may be contained in the cation portion. In one embodiment of the present invention, the onium salt compound (A) preferably contains at least one fluorine atom in the anion portion and at least one fluorine atom in the cationic portion. When at least one fluorine atom is contained in the cationic portion, the concentration of the basic onium salt compound in the vicinity of the surface of the photoresist film can be effectively made larger than the concentration of the acid generator. This is effective for solving the quenching of the acid generated near the surface of the photoresist film.

Examples of the onium salt compound include a diazonium salt compound, an onium salt compound, an onium salt compound, and an onium salt compound. Among these, a phosphonium salt compound or a phosphonium salt compound is preferred, and a phosphonium salt compound is more preferable.

The onium salt compound typically has an alkaline moiety containing a nitrogen atom in the cationic portion. Here, the "basic site" means a site in which the pKa of the conjugate acid of the cation site of the compound (A) is -3 or more. The pKa is preferably in the range of -3 to 15, and more preferably in the range of 0 to 15. In addition, the pKa is a calculated value obtained by ACD/ChemSketch (ACD/Labs 8.00 Release Product Version: 8.08).

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

In these structures, it is preferred that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms from the viewpoint of improving alkalinity. Further, from the viewpoint of improving alkalinity, an electron-donating functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, or the like) is not directly bonded to a 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 amine group, the cationic portion preferably has a partial structure represented by the following formula (N-I).

[Chemical Formula 5]

In the formula,

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, and 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, a cyano group and the like.

The alkyl group represented by R _A or R _B may be linear or branched. The alkyl group preferably has 1 to 50 carbon atoms, more preferably 1 to 30, and further preferably 1 to 20 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, an isobutyl group, and a second. Butyl, tert-butyl, 1-ethylpentyl and 2-ethylhexyl.

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

The alkenyl group represented by R _A or R _B may be linear or branched. The alkenyl group preferably has 2 to 50 carbon atoms, more preferably 2 to 30, and further preferably 3 to 20 carbon atoms. Examples of such an alkenyl group include a vinyl group, an allyl group, and a styryl group.

As the aryl group represented by R _A or R _B , those having 6 to 14 carbon atoms are preferred. Examples of such a group include a phenyl group and a naphthyl group.

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

The heterocyclic ring contained in the above group may be a monocyclic ring or a polycyclic ring. Examples of such a heterocyclic ring include an imidazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 2H-pyrrole ring, a 3H-fluorene ring, a 1H-carbazole ring, an anthracene ring, and an isoquinoline. Ring, 4H-quinazine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, acridine ring, pyridine ring, acridine ring, brown Phytol ring, phenazine ring, acridine ring, triazine ring, benzoisoquinoline ring, thiazole ring, thiadiazine ring, azepine ring, azocine ring, isothiazole ring, different Oxazole ring and benzothiazole ring.

The lactone group represented by R _A or R _B , for example, a lactone group of a 5- to 7-membered ring may be formed by forming a bicyclic structure or a spiro ring structure on a 5- to 7-membered ring lactone group. Ring structure shrinkage. Specifically, a group having a structure shown below is preferred.

[Chemical Formula 6-1]

[Chemical Formula 6-2]

The lactone group may or may not have a substituent (Rb ₂ ). The preferred substituent (Rb ₂ ) includes the same substituents as those described above for the substituents of R _A and R _B . When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

The linking group represented by X may, for example, be a linear or branched alkyl group, a cycloalkyl group, an ether bond, an ester bond, a guanamine bond, a urethane bond, a urea bond, and the like. A group obtained by combining two or more types. X represents a group in which a single bond, an alkyl group, an alkyl group and an ether bond are combined, or a group in which an alkyl group and an ester bond are combined is more preferable. The number of atoms of the linking group represented by X is preferably 20 or less, more preferably 15 or less. The linear or branched alkylene group and the cycloalkylene group have preferably 8 or less carbon atoms, and may have a substituent. The substituent is preferably a carbon number of 8 or less, and examples thereof include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkane. An oxycarbonyl group (having 2 to 6 carbon atoms).

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 4 to 20, and may be a monocyclic ring or a polycyclic ring, or may contain an oxygen atom, a sulfur atom, a nitrogen atom, an ester bond, a guanamine bond or a carbonyl group in the ring.

When the cationic moiety of the compound (A) contains a nitrogen-containing heterocyclic group, the nitrogen-containing heterocyclic group may or may not have aromaticity. Further, the nitrogen-containing heterocyclic group may be a monocyclic ring or a polycyclic ring. 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 sulfonium salt compound (A) is preferably a compound represented by the following formula (N-II).

[Chemical Formula 7]

In the formula,

A represents a sulfur atom or an iodine atom.

R ₁ represents a hydrogen atom or an organic group. When there are a plurality of R ₁ , R ₁ may be the same or different.

R represents an organic group of (o+1) valence. When there are a plurality of Rs, R may be the same or different.

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

A _N represents an alkaline moiety containing a nitrogen atom. When there are a plurality of A _Ns , 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 from 1 to 10.

Y ^- represents an anion and contains at least one fluorine atom. The details will be described later as an anion portion 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.

The (o+1)-valent organic group represented by R may, for example, be a chain-like (linear or branched) or cyclic aliphatic hydrocarbon group, a heterocyclic hydrocarbon group or an aromatic hydrocarbon group, and may preferably be used. An aromatic hydrocarbon group is mentioned. When R is an aromatic hydrocarbon group, it is preferred to bond at the p-position (1,4-position) of the aromatic hydrocarbon group.

The meaning of the linking group represented by X is the same as the linking group represented by X in the above formula (N-I), and the same specific examples can be given.

The basic portion represented by A _N has the same meaning as the "basic moiety" contained in the cationic portion of the above compound (A), and may, for example, contain an amine group or a nitrogen-containing heterocyclic group. When the basic moiety contains an amine group, examples of the amine group include the -N(R _A )(R _B ) group in the above-mentioned general formula (NI).

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 ₁ 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 linear or branched. The alkyl group preferably has 1 to 50 carbon atoms, more preferably 1 to 30, and further preferably 1 to 20 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, an isobutyl group, and a second. Butyl, tert-butyl, 1-ethylpentyl and 2-ethylhexyl.

The alkenyl group represented by R ₁ may be linear or branched. The alkenyl group preferably has 2 to 50 carbon atoms, more preferably 2 to 30, and further preferably 3 to 20 carbon atoms. 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 a monocyclic ring or a polycyclic ring. The aliphatic cyclic group may preferably be a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group.

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

The heterocyclic hydrocarbon group represented by R ₁ may or may not be aromatic. The heterocyclic hydrocarbon group is preferably aromatic.

The heterocyclic ring contained in the above group may be a monocyclic ring or a polycyclic ring. Examples of such a heterocyclic ring include an imidazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 2H-pyrrole ring, a 3H-fluorene ring, a 1H-carbazole ring, an anthracene ring, and an isoquinoline. Ring, 4H-quinazine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, porphyrin ring, acridine ring, pyridine ring, acridine ring, phenanthroline ring, a phenazine ring, an acridine ring, a triazine ring, a benzoisoquinoline ring, a thiazole ring, a thiadiazine ring, a nitrogen ring, an axin ring, an isothiazole ring, an isoxazole ring, and a benzothiazole ring.

It is preferred that R ₁ is an aromatic hydrocarbon group or two R ₁ bonds to form a ring.

A ring 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, a 5 or 6-membered ring is more preferable, and a 5-membered ring is particularly preferable. Further, the ring skeleton may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

When the ring formed by the group represented by R ₁ or the two R ₁ bonds to each other further has a substituent, examples of the substituent include the following. In other words, examples of the substituent include a halogen atom (-F, -Br, -Cl or -I), a hydroxyl group, an alkoxy group, an aryloxy group, a decyl group, an alkylthio group, an arylthio group, and an amine group. , anthraceneoxy, amine methoxy group, alkyl sulfoxy group, aryl sulfoxy group, sulfonylthio group, decylamino group, ureido group, alkoxycarbonylamino group, aryloxycarbonyl group Amino, N-alkyl-N-alkoxycarbonylamino, N-alkyl-N-aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl- N-aryloxycarbonylamino, carbenyl, fluorenyl, carboxy, aminecarbamyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonate Acid group (-SO ₃ H) and its conjugate base (referred to as sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, aminosulfinyl group, phosphinium group ( Phosphono group) (-PO ₃ H ₂ ) and its conjugated base (called phosphonate), phosphonooxy group (-OPO ₃ H ₂ ) and its conjugated base (called phosphonate) Phosphonatooxy), cyano, nitro, aryl, alkenyl, Alkynyl, heterocyclic, decyl and alkyl.

Among these substituents, a hydroxyl group, an alkoxy group, a cyano group, an aryl group, an alkenyl group, an alkynyl group, an alkyl group or the like is preferred.

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

In one aspect, in the compound (A) represented by the formula (N-II), at least one of the n R groups in the formula is preferably an aromatic hydrocarbon group. Further, in the at least one of the o-(XA _N ) groups bonded to at least one of the aromatic hydrocarbon groups, the linking group of the X-form and the aromatic hydrocarbon group is a linking group of a carbon atom. good.

That is, in the compound (A) in the aspect, the basic moiety represented by A _N is bonded to the aromatic hydrocarbon group via a carbon atom directly bonded to the 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. Further, the aromatic ring may be a single ring type or a multiple ring type.

The aromatic ring group preferably has 6 to 14 carbon atoms. Examples of such a group include an aryl group such as a phenyl group, a naphthyl group or an anthracenyl group. When the aromatic ring group contains a hetero ring, examples of the hetero ring include a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, and a benzene. And an imidazole ring, a triazole ring, a thiadiazole ring and a thiazole ring.

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

The aromatic hydrocarbon group represented by R may further have a substituent in addition to the group represented by -(XA _N ) described below. As the substituent, for example, those which are previously referred to as a substituent in R ₁ can be used.

In this aspect, the linking group which is substituted with X in at least one -(XA _N ) group of the aromatic ring R is a carbon atom, and the bonding portion of the aromatic hydrocarbon group represented by R is a carbon atom. There is no particular limitation. The linking group includes, for example, an alkylene group, a cycloalkyl group, an extended aryl group, -COO-, -CO- or a combination thereof. The linking group may comprise the groups selected from the group consisting of -O-, -S-, -OCO-, -S(=O)-, -S(=O)2-, -OS(=O)2- And a combination of at least one of -NR'-. Here, R' represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

The alkyl group which may be contained in the linking group represented by X may be linear or branched. The alkylene group has preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of the alkylene group include a methylene group, an exoethyl group, a propyl group and a butyl group.

The cycloalkyl group which may be contained in the linking group represented by X may be a monocyclic ring or a polycyclic ring. The alkylene group has preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms. As such a cycloalkyl group, for example, a 1,4-cyclohexylene group can be mentioned.

The linking group represented by X may include a aryl group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. As such an aryl group, a phenyl group and a naphthyl group are exemplified.

At least one X is preferably represented by the following formula (N-III) or (N-IV).

[Chemical Formula 8]

In the formula,

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 each other to form a ring.

E represents a linking group or a single bond.

[Chemical Formula 9]

In the formula,

J represents an oxygen atom or a sulfur atom.

E represents a linking group or a single bond.

Examples of the respective groups represented by R ₂ and R ₃ and the substituents which may be further provided are the same as those described previously for R ₁ . Ring R ₂ and R ₃ can be bonded to form a ring, and the R ₂ and R ₃ in at least one of E can be formed with the bonding of 4 to 7-membered ring is preferred, 5-membered ring or 6-membered ring is more It is better. It is preferred that R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group.

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

The linking group represented by E is selected from an alkyl group bond, an ester bond, an ether bond, a thioether bond, a urethane bond,

[Chemical Formula 10] ,

Urea bond,

[Chemical Formula 11] ,

At least one of a guanamine bond and a sulfonamide bond is preferred. The linking group represented by E is preferably an alkyl group bond, an ester bond or an ether bond.

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

In one aspect, the compound (A) represented by the formula (N-II) is represented by the following formula (N-V).

[Chemical Formula 12]

In the formula,

The meanings of X and A _N are the same as those of the formula (N-II), and the specific examples and preferred examples are also the same.

Y ^- is an anion, comprising at least one fluorine atom. The details will be described later as an anion portion of the compound (A).

When R _{14 is} present in plural, it independently represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group or a cycloalkyl group. Group. These groups may have a substituent.

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

l represents an integer from 0 to 2.

r represents an integer from 0 to 8.

Further, in one aspect, the compound (A) represented by the formula (N-II) is represented by the following formula (N-VI).

[Chemical Formula 13]

In 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 ₁₁ may be bonded to each other to form a ring.

Ar independently represents an aromatic hydrocarbon group.

X ₁ each independently represents a divalent linking group.

R ₁₂ each 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 will be described later as an anion portion of the compound (A).

The alkyl group of R _11, an alkenyl group, an aliphatic cyclic group, an aromatic hydrocarbon group and heterocyclic hydrocarbon group Specific examples and preferred examples of the general formula (N-II) as in the alkyl group of R ₁ Specific examples and preferred examples of the alkenyl group, the aliphatic cyclic group, the aromatic hydrocarbon group and the heterocyclic hydrocarbon group are the same.

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

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

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

From the viewpoint of post-exposure heating (Post Exposure Bake: PEB) temperature dependence and Post Exposure Delay (PED) stability, X ₁ is an alkylene group (for example, methylene group) and two R ₁₂ It is especially preferable to bond each other to form a ring.

The anion portion of the compound (A) contains at least one fluorine atom. The anion contained in the compound (A) is preferably a non-nucleophilic anion containing at least one fluorine atom. Here, the non-nucleophilic anion refers to an anion having an extremely low ability to cause a nucleophilic reaction, and is capable of suppressing an anion which is decomposed by time due to a nucleophilic reaction in the molecule. Thereby, 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 sulfonimide anion, a bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl)methyl anion, and the like. .

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

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

The aliphatic moiety in the aliphatic sulfonic acid anion may be an alkyl group or a cycloalkyl group, an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms is preferable, and for example, Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, decyl, decyl, undecane , dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopropyl , cyclopentyl, cyclohexyl, adamantyl, norbornyl, fluorenyl and the like.

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

The alkyl group, the cycloalkyl group and the 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, the cycloalkyl group and the aryl group in the aliphatic sulfonic acid anion and the aromatic sulfonic acid anion include a nitro group and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), and an aryl group (having a carbon number of 6 to 14) Preferably, an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), a mercapto group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyloxy group (having preferably 2 to 7 carbon atoms) ), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), and an alkylimidosulfonyl group (having a carbon number of 2 to 15) Preferably, an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms), an alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), or a cycloalkylaryloxysulfonate a group (preferably having 10 to 20 carbon atoms), an alkoxyalkoxy group (preferably having 5 to 20 carbon atoms), and a cycloalkyl alkoxyalkoxy group (having preferably 8 to 20 carbon atoms) )Wait. The aryl group and the ring structure of each group may, for example, be an alkyl group (having preferably 1 to 15 carbon atoms).

The aliphatic moiety in the aliphatic carboxylic acid anion may, for example, be the same alkyl group or cycloalkyl group as the aliphatic sulfonic acid anion.

The aromatic group in the aromatic carboxylic acid anion may, for example, be the same aryl group as the aromatic sulfonic acid anion.

The aralkyl group in the aralkylcarboxylic acid anion is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylethyl group, and the like. .

The alkyl group, the cycloalkyl group, the aryl group and the aralkyl group in the aliphatic carboxylic acid anion, the aromatic carboxylic acid anion, and the aralkylcarboxylic acid anion may have a substituent. Examples of the substituent of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group in the aliphatic carboxylic acid anion, the aromatic carboxylic acid anion and the aralkyl carboxylic acid anion include, for example, an aromatic sulfonic acid anion. The same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group and the like.

Examples of the sulfonium imine anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl) quinone imine anion and the tris(alkylsulfonyl)methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group and a methyl group. Base, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, neopentyl, and the like. Examples of the substituent of the alkyl group include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxy group. An alkyl group substituted with a fluorine atom, such as a sulfonyl group, is preferred. Further, it is also preferred that the two alkyl groups of the bis(alkylsulfonyl) quinone imine anion are bonded to each other to form a cyclic structure. At this time, it is preferable that the formed annular structure is a 5-7 member ring.

Examples of the other non-nucleophilic anion include phosphorus fluoride, boron fluoride, and cesium fluoride.

As the non-nucleophilic anion, an aliphatic sulfonate anion in which the α-position of the sulfonic acid is substituted by a fluorine atom, an aromatic sulfonate anion substituted by a fluorine atom or a group having a fluorine atom, and an alkyl group substituted by a fluorine atom A (alkylsulfonyl) quinone imine anion and a tri(alkylsulfonyl)methide anion having an alkyl group substituted by a fluorine atom are preferred. As the non-nucleophilic anion, a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, an benzenesulfonic acid anion having a fluorine atom is more preferable, a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, and a pentafluorocarbon. An anion of benzenesulfonate and an anion of 3,5-bis(trifluoromethyl)benzenesulfonate are further preferred.

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

[Chemical Formula 14]

In the formula,

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

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

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 from 1 to 20.

y represents an integer from 0 to 10.

z represents an integer from 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. Further, an alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Xf is 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 is preferred.

R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group may have a substituent (the fluorine atom is preferred), and those having 1 to 4 carbon atoms are preferred. A perfluoroalkyl group having 1 to 4 carbon atoms is further preferred. Specific examples of the alkyl group having a substituent of R ₁ and R ₂ include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , 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 , wherein 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 -, alkylene, and extens. Cycloalkyl and alkenyl. Among these, -CONH-, -CO- or -SO ₂ - is preferred, and -CONH- or -SO ₂ - is more preferred.

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

The alicyclic group may be a monocyclic ring or a polycyclic ring. The monocyclic alicyclic group may, for example, be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a thiol group, a tricyclodecyl group, a tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group. Among them, from the viewpoint of suppressing the diffusibility in the film in the PEB (Post Exposure Bake) step and improving the MEEF (Mask Error Enhancement Factor), a thiol group, a tricyclodecyl group, a tetracyclodecyl group, and a tetracyclic group are considered. An alicyclic group having a large volume structure such as an alkyl group or an adamantyl group having 7 or more carbon atoms is preferred.

The aryl group may be a single ring type or a polycyclic type. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthracenyl group. Among them, a naphthyl group having a relatively low absorbance at 193 nm is preferred.

The heterocyclic group may be a monocyclic ring or a polycyclic ring, and the polycyclic ring is more resistant to the diffusion of an acid. Further, the heterocyclic group may or may not have aromaticity. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, and a 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 preferred. Further, examples of the lactone ring include a lactone ring exemplified for R _A and R _B in the above formula (N-1).

The above 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, a decylamino group, a urethane group, a ureido group, a thioether group, a sulfonylamino group, and Sulfonate group. The alkyl group may be linear or branched. Further, the alkyl group has preferably 1 to 12 carbon atoms. The cycloalkyl group may be a monocyclic ring or a polycyclic ring. Further, the cycloalkyl group preferably has 3 to 12 carbon atoms. The aryl group preferably has 6 to 14 carbon atoms.

It is preferred that x is from 1 to 8, wherein 1 to 4 is preferred, and 1 is particularly preferred. Y is preferably 0 to 4, and 0 is more preferable. It is preferable that z is 0 to 8, and 0 to 4 is preferable.

Further, the non-nucleophilic anion is preferably represented by, for example, the following formula (LD2).

[Chemical Formula 15]

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

The group of the fluorine atom represented by Rf may, for example, be 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.

The alkyl group, the cycloalkyl group and the aryl group may be substituted by a fluorine atom or may be substituted by another substituent containing a fluorine atom. When Rf is a cycloalkyl group having at least one fluorine atom or an aryl group having at least one fluorine atom, examples of the other substituent containing a fluorine atom include an alkyl group substituted with at least one fluorine atom.

Further, the alkyl group, the cycloalkyl group and the aryl group may be further substituted with a substituent having no fluorine atom. As the substituent, for example, those having no fluorine atom in the above description of Cy can be mentioned.

The alkyl group having at least one fluorine atom represented by Rf may, for example, be the same as those described above as an alkyl group substituted with at least one fluorine atom represented by Xf. 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 may, for example, be a perfluorophenyl group.

As a preferred aspect of the anion portion of the compound (A), in addition to the structures represented by the above formulas (LD1) and (LD2), the above-mentioned preferred anion as the photoacid generator (B) may be mentioned. Structure exemplified.

In one embodiment of the present invention, the difference between the pKa of the acid generated by the anion portion by the sulfonium salt compound (A) and the acid generator (B) described later is preferably small by irradiation with actinic rays or radiation. When the difference in pKa is small, the acid strength of the acid produced by the onium salt compound (A) and the acid generator (B) is less likely to cause unevenness, so that crosslinking reactivity or deprotection caused by the generated acid can be caused. The reactivity becomes more uniform. The difference in pKa is preferably 5 or less, more preferably 3 or less, still more preferably 1 or less, and most preferably 0.

Here, the pKa is a pKa in an aqueous solution, and is, for example, described in Chemical Notes (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, MARUZEN Co., Ltd.), the lower the value, the acid strength is indicated. The bigger. The pKa in an aqueous solution can be specifically measured by measuring the acid dissociation constant at 25 ° C using an infinitely diluted aqueous solution, and the following substituents can be calculated by calculation using the following software kit 1 and known literature. The value of the database of values. The values of pKa in this specification all indicate the values obtained by calculation using the software suite. Software Suite 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

In one embodiment of the present invention, the basic anthracene salt compound (A) and the acid generator (B) described later have the same anion structure.

Specific examples of the compound (A) are given below, but are not limited thereto.

[Chemical Formula 16-1]

[Chemical Formula 16-2]

[Chemical Formula 16-3]

[Chemical Formula 16-4]

[Chemical Formula 16-5]

[Chemical Formula 16-6]

[Chemical Formula 16-7]

[Chemical Formula 16-8]

[Chemical Formula 16-9]

[Chemical Formula 16-10]

[Chemical Formula 16-11]

The compound (A) may be used alone or in combination of two or more.

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

Further, from the viewpoint of improving the resolution, the volume of the acid produced by the compound (A) is preferably large.

[acid generator (B)]

The acid generator (B) is a compound which generates an acid by irradiation with actinic rays 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 preferred form of the acid generator is an onium salt compound. Examples of the onium salt compound include a phosphonium salt, a phosphonium salt, and an onium salt.

Further, as another preferred embodiment of the acid generator, a compound which generates a sulfonic acid, an imidic acid or a methylated acid by irradiation with actinic rays or radiation may be mentioned. Examples of the acid generator in the form include a phosphonium salt, a phosphonium salt, a phosphonium salt, an anthracenesulfonate, and a quinone imidesulfonate.

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

The acid generator which can be used in the present invention is not limited to a low molecular compound, and a group in which an acid is generated by irradiation with actinic rays or radiation in a main chain or a side chain of a polymer compound may be used. Compound.

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

In the present invention, the sulfonium compound represented by the following formula (7) or the hydrazine compound represented by the formula (8) is exemplified as the sulfonium salt compound.

[Chemical Formula 17]

In the general formula (7) and the general formula (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 hydrazine compound represented by the formula (7) and the hydrazine compound represented by the formula (8) will be further described in detail.

As described above, 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 R _a1 , R _a2 and R _a3 at least 1, and at least one R _a4 and R _a5 are the preferred aryl is based. As the aryl group, a phenyl group or a naphthyl group is preferred, and a phenyl group is further preferred.

Examples of the organic anion of X ^- in the general formulae (7) and (8) include a sulfonic acid anion, a carboxylic acid anion, a bis(alkylsulfonyl) decylamine anion, and a tris(alkylsulfonyl)methyl group. The anion and the like are preferably an organic anion represented by the following formula (9), (10) or (11), and more preferably an organic anion represented by the following formula (9).

[Chemical Formula 18]

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

Above X ^- is an organic anion by a corresponding electron beam or extreme ultraviolet actinic rays or radiation to produce the sulfonic acid i.e., imidate, methylation acid.

Examples of the organic group of R _c1 , R _c2 , R _c3 and R _c4 include an alkyl group, an aryl group or a plurality of such groups obtained by linking. Among these organic groups, an alkyl group substituted with a fluorine atom or a fluoroalkyl group at the 1-position, and a phenyl group substituted with a fluorine atom or a fluoroalkyl group are more preferred. By having a fluorine atom or a fluoroalkyl group, the acidity generated by light irradiation increases, and the sensitivity is improved. However, it is preferred that the terminal group does not contain a fluorine atom as a substituent.

In one embodiment, 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 crosslinking reactivity or the deprotection reactivity caused by the acid generated by the anion portion of the two compounds by irradiation with actinic rays or radiation becomes more uniform. In view of the above, it is preferred that the basic sulfonium salt compound (A) and the acid generator (B) have the same anionic structure or a small difference in pKa of the acid produced.

Further, in the present invention, it becomes a good viewpoint of diffusion of the non-exposed portion and the analytical pattern shape suppressing exposure of an acid, the compound (B) to generate a volume based size than 130Å ³ acid (acid more excellent) the preferred compound is the compound, to produce a volume size than 190Å ³ acids (sulfonic good others) the more excellent, more than 270Å ³ to produce a volume size acids (sulfonic good others) of a further preferred compound is generated Compounds having a volume of 400 Å ³ or more (better sulfonic acid) are particularly preferred. However, sensitivity and coating solvent solubility of the viewpoint of the volume of 2000Å ³ or less is preferred, 1500Å ³ or less is more preferred. The value of the above volume was determined using "WinMOPAC" manufactured by FUJITSU LIMITED. That is, first, the chemical structure of the acid of each compound is input, and then the structure is taken as the initial structure and the most stable solid shape of each acid is determined by using the molecular force field calculation of the MM3 method, and thereafter, for the most The stable three-dimensional shape is calculated using the molecular orbital of the PM3 method, whereby the "accessible volume" of each acid can be calculated.

Hereinafter, an acid generator which is particularly preferable in the present invention is shown. In addition, in some examples, the calculated value of the remark volume (in Å ³ ). Further, the calculated value obtained here is the volume value of the acid in which the proton is bonded to the anion portion.

[Chemical Formula 19-1]

[Chemical Formula 19-2]

[Chemical Formula 19-3]

[Chemical Formula 19-4]

Further, as the acid generator (the ruthenium compound is preferably used) used in the present invention, a group in which an acid is generated by irradiation with actinic rays or radiation can be introduced into the main chain or the side chain of the polymer compound ( A polymeric acid generator of a photoacid generating group).

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

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

[Compound containing an acid crosslinkable group]

The composition of the present invention may contain a compound (C) having an acid crosslinkable 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. Further, from the viewpoint of improving LER, the compound (C) preferably contains a methylol group.

First, a case where the compound (C) is a low molecular compound will be described (hereinafter, it is referred to as a compound (C')). The compound (C') may preferably be a hydroxymethylated or alkoxymethylated phenol compound, an alkoxymethylated melamine compound, an alkoxymethyl glycoluril compound or an alkoxy group. Methylated urea compounds. The compound (C') which is particularly preferable is a phenol derivative or an alkane which contains 3 to 5 benzene rings in the molecule and further has two or more hydroxymethyl groups or alkoxymethyl groups in total, and has a molecular weight of 1200 or less. Oxymethylglycolide derivative.

As the alkoxymethyl group, a methoxymethyl group or an ethoxymethyl group is preferred.

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

Further, as an example of another preferable compound (C'), an alkoxymethylated melamine-based compound, an alkoxymethyl-glycoluride-based compound, an alkoxymethylated urea-based compound, or the like may be further provided. A compound of N-hydroxymethyl or N-alkoxymethyl.

Examples of such a compound include hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl glycoluril, and 1,3-bismethoxymethyl-4,5-dimethoxy. Ethyl-ethylurea, bis-methoxymethylurea, and the like are disclosed in EP 0,133,216 A, West German Patent No. 3,634,671, West German Patent No. 3,711,264, EP 0,212,482 A.

Hereinafter, a specific example of the compound (C') is particularly preferred.

[Chemical Formula 20]

In the formula, 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 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 a fluorenyl 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 embodiment of the 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, and particularly preferably a methyl group, an ethyl group or a propyl group. Isopropyl.

The alkyl group represented by R ₂ and R ₅ is preferably an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms as an aryl group. For example, an aryl group having 6 to 12 carbon atoms is preferred, and as the mercapto group, for example, an alkyl group having 1 to 6 carbon atoms is preferred.

In one embodiment 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, and the like, and R ₃ and R ₄ are bonded to each other. It is preferred to form a ring as detailed below.

Examples of the ring formed by bonding R ₃ and R _{4 to} each other include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic hetero ring, or a combination of two or more of these rings. Ring condensation ring.

These rings may have a substituent, and examples of such a substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an aryl group, an alkoxymethyl group, a decyl group, an alkoxycarbonyl group, and a nitro group. , halogen atom or hydroxyl group.

Hereinafter, specific examples of the ring formed by bonding R ₃ and R _{4 to} each other will be described. * in the formula indicates a site of attachment to the phenol nucleus.

[Chemical Formula 22]

In one embodiment of the present invention, it is preferred that R ₃ and R ₄ in the formula (I) are bonded to form a polycyclic condensed ring containing a benzene ring, and a ruthenium structure is more preferable.

In the compound (C'), for example, R ₃ and R ₄ in the formula (I) are bonded to each other to form a fluorene structure represented by the following formula (Ia).

[Chemical Formula 23]

In the formula,

R ₇ and R ₈ each independently represent a substituent. The substituent may, for example, be an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an alkoxymethyl group, a decyl 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, indicating that 0 or 1 is preferable.

* indicates the site of attachment to the phenol nucleus.

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

[Chemical Formula 24]

In the formula,

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 a group of atoms required to form a ring together with a carbon atom in the formula.

The ring formed by Z together with the carbon atom in the formula is the same as the ring formed by bonding R ₃ and R _{4 to} each other in the description of the above formula (I).

In one embodiment of the present invention, the compound (C') is preferably a compound having four or more aromatic rings in the molecule and having two alkoxymethyl groups and/or a hydroxymethyl group in total.

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

The bisphenol compound which becomes the mother nucleus of the compound (C') represented by the formula (I) is usually subjected to dehydration condensation reaction in the presence of an acid catalyst by reacting a corresponding two molecules of a phenol compound with a corresponding one molecule of a ketone. To synthesize.

The obtained bisphenol is treated with paraformaldehyde and dimethylamine to carry out amine methylation, whereby an intermediate represented by the following formula (I-C) can be obtained. Next, the target acid crosslinking agent is obtained by acetylation, deacetylation, and alkylation.

[Chemical Formula 25]

In the formula, R ₁ , R ₃ , R ₄ and R _{6 have} the same meanings as in the formula (I).

In contrast to the conventional method of synthesizing a hydroxymethyl group under a basic condition (for example, JP-A-2008-273844), it is difficult to form an oligomer in the present synthesis method, and thus it has a particle formation suppressing effect.

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

[Chemical Formula 26]

In the present invention, the content of the compound (C') is preferably 3 to 65% by mass, more preferably 5 to 50% by mass, based on all solid components of the sensitizing ray-sensitive or radiation-sensitive resin composition. By setting the content of the compound (C') in the range of 3 to 65% by mass, it is possible to prevent the residual film ratio and the resolution from being lowered, and to maintain the stability of the composition of the present invention during storage.

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

For example, when a compound (C') such as the above compound having an N-alkoxymethyl group is used in addition to the above phenol derivative, the ratio of the above phenol derivative to the other compound (C') is in molar ratio. Usually 90/10~20/80, 85/15~40/60 is better, 80/20~50/50 is better.

The compound (C) containing an acid crosslinkable group may also be a form of a resin (hereinafter, also referred to as a compound (C")) containing a repeating unit having an acid crosslinkable group. In this case, since the crosslinking unit is contained in the molecular unit of the repeating unit, the crosslinking reactivity is higher than that of the conventional resin + crosslinking agent system. Therefore, a hard film can be formed and the acid can be controlled. As a result, the diffusibility of acid in the exposed portion such as an actinic ray such as an electron beam or an extreme ultraviolet ray or radiation is suppressed very well, and therefore the resolution, pattern shape, and LER are excellent in the fine pattern. Further, when the reaction point of the resin is close to the reaction point of the crosslinking group in the repeating unit represented by the following general formula (1), the composition is improved in sensitivity at the time of pattern formation.

The compound (C") may, for example, be a resin comprising a repeating unit represented by the following formula (1). The repeating unit represented by the formula (1) contains at least one hydroxymethyl group which may have a substituent. The structure.

Here, the "hydroxymethyl group" is a group represented by the following formula (M), and in one embodiment of the invention, a hydroxymethyl group or an alkoxymethyl group is preferred.

[Chemical Formula 27]

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

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

[Chemical Formula 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 other than a methylol group.

Z represents a hydrogen atom or a substituent.

m represents an integer from 0 to 4.

n represents an integer from 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 as or different from each other.

Further, 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.

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

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

[Chemical Formula 29]

In the general formulae (2) and (3),

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

Ar represents an aromatic ring.

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

Further, the repeating unit represented by the formula (1) is further preferably represented by the following formula (2') or (3').

[Chemical Formula 30]

The meanings of R ₁ , Y, Z, m and n in the above formulae (2') and (3') are the same as those in the above formula (1). The meaning of Ar in the above formula (2') is the same as Ar in the above formula (2).

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

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

In the above formulae (2') and (3'), g is 0 or 1.

Further, the general formula (2') is particularly preferably represented by any one of the following general formulae (1-a) to (1-c). The compound (C") preferably contains a repeating unit represented by any one of the following formulae (1-a) to (1-c) or a repeating unit represented by the above formula (3').

[Chemical Formula 31]

The meanings of R ₁ , Y and Z in the above formula (1-a) to (1-c) are the same as those in the above formula (1).

In the above formula (1-b) to (1-c),

Y" represents a hydrogen atom or a monovalent substituent. Among them, Y" may also be a hydroxymethyl group.

R ₄ represents a hydrogen atom or a monovalent substituent.

f represents an integer from 1 to 6.

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

The content of the repeating unit having an acid crosslinkable group in the compound (C") is preferably from 3 to 40 mol%, more preferably from 5 to 30 mol%, based on all repeating units of the compound (C"). good.

The content of the compound (C") is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, based on 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 kinds of compounds (C") may be used in combination. Further, the compound (C') and the compound (C") may also be used in combination.

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

[(D) Compound containing a phenolic hydroxyl group]

In one aspect, the composition of the present invention preferably contains a compound (D) (hereinafter, also referred to as a compound (D)) containing a phenolic hydroxyl group.

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

The composition of the present invention containing the compound (D) is used in the exposed portion by an acid generated by the acid generator (B) by irradiation with actinic rays or radiation, and a compound containing a phenolic hydroxyl group. (D) A crosslinking reaction is carried out between the above-mentioned compound (C) containing an acid crosslinkable group to form a negative pattern. In particular, when the acid generator (B) is a structure containing two or more methylol groups in the molecule of the acid produced, in addition to the crosslinking reaction between the compound (D) and the compound (C), the acid The plurality of methylol groups of the generating agent (B) also promote the crosslinking reaction, and thus the dry etching resistance, sensitivity, and resolution are further improved.

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 photoresist or a polymer compound. In addition, as the molecular photoresist, for example, a low molecular weight cyclic polyphenol compound described in JP-A-2009-173623 and JP-A-2009-173625 can be used.

From the viewpoint of reactivity and sensitivity, the compound (D) containing a phenolic hydroxyl group is preferably a polymer compound.

When the phenolic hydroxyl group-containing compound (D) 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, and is preferably a repeating unit represented by the following formula (II).

[Chemical Formula 32]

In the formula,

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 an aromatic ring group.

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 and a hydroxymethyl group.

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

As the divalent linking group of B', a carbonyl group, an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), or a sulfonyl group (-S(=O) ₂ -) Preferably, -O-, -NH- or a divalent linking group obtained by combining the two is preferred.

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

The aromatic ring of Ar' is a monocyclic or polycyclic aromatic ring, and examples thereof 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, an anthracene ring or a phenanthrene ring. Or, for example, a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, a thiazole An aromatic ring heterocyclic ring of a heterocyclic ring. Among them, a benzene ring or a naphthalene ring is preferred from the viewpoint of analytical properties, and a benzene ring is most preferable from the viewpoint of sensitivity.

An integer of m of 1 to 5 is preferred, and 1 is most preferred. When m is 1 and Ar' is a benzene ring, the substitution position of -OH can be aligned with respect to the bonding position of the benzene ring and B' (the polymer backbone when B' is a single bond) , meta or ortho, but from the viewpoint of cross-linking reactivity, the alignment and meta-position are better, and the alignment is better.

The aromatic ring of Ar' may have a substituent in addition to the group represented by the above -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, and an alkyl group. An oxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an arylcarbonyl group.

From the viewpoint of crosslinking reactivity, developability, and dry etching resistance, the repeating unit having a phenolic hydroxyl group is more preferably a repeating unit represented by the following formula (2).

[Chemical Formula 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 a hydrogen atom is preferred from the viewpoint of developability.

The meaning of Ar in the formula (2) is the same as Ar' in the above formula (II), and the preferred range is also the same. From the viewpoint of sensitivity, the repeating unit represented by the formula (2) is a repeating unit derived from hydroxystyrene (that is, in the formula (2), R ₁₂ is a hydrogen atom and Ar is a repeating unit of a benzene ring) It is better.

The compound (D) which is a polymer compound can be composed only of the above-mentioned repeating unit having a phenolic hydroxyl group. The compound (D) which is a polymer compound may have a repeating unit as described later in addition to the above-mentioned repeating unit having a phenolic hydroxyl group. In this case, the content of the repeating unit having a phenolic hydroxyl group is preferably from 10 to 98 mol%, more preferably from 30 to 97 mol%, based on all the repeating units of the compound (D) as the polymer compound, and 40 is more preferably 40. ~95 mole% is further preferred. Thereby, particularly when the ray-sensitive or radiation-sensitive film-type film is irradiated (for example, when the thickness of the sensitizing ray-sensitive or radiation-sensitive film is 10 to 150 nm), the use of the compound (D) can be more reliably reduced. The dissolution rate of the exposed portion with respect to the alkali developer in the photosensitive ray-sensitive or radiation-sensitive film of the present invention (that is, the photosensitive ray-sensitive or radiation-sensitive film using the compound (D) can be more reliably used. The dissolution rate is controlled to be the best). As a result, the sensitivity can be more reliably improved.

Hereinafter, an example of a repeating unit having a phenolic hydroxyl group will be described, but it is not limited thereto.

[Chemical Formula 34]

From the viewpoint of obtaining a high glass transition temperature (Tg) and good dry etching resistance, the hydrogen atom of the compound (D) having a phenolic hydroxyl group is grouped by a polycyclic alicyclic hydrocarbon structure having a non-acid-decomposable property. The structure substituted is preferred.

By having the above-mentioned specific structure of the compound (D), it is possible to form a photosensitive ray-sensitive or radiation-sensitive film having a high glass transition temperature (Tg) of the compound (D) and capable of controlling acid diffusibility and drying. Etch resistance. Therefore, the diffusibility of the acid on the exposed portion of the actinic ray such as the electron beam or the extreme ultraviolet ray or the radiation is suppressed very well, and therefore the resolution, pattern shape, and LER in the fine pattern are further excellent. Further, it is considered that the compound (D) having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure contributes to further improvement in dry etching resistance. Further, although the detailed mechanism is not clear, it is estimated that the hydrogen radical of the polycyclic alicyclic hydrocarbon structure is highly supplied, and when the photoacid generator is decomposed, it becomes a hydrogen source, and the decomposition efficiency of the photoacid generator is further improved, and the acid is produced. The efficiency is further increased, and it is believed that this contributes to more excellent sensitivity.

The compound (D) of the present invention may have the specific structure described above, and an aromatic ring such as a benzene ring and a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure are bonded via an oxygen atom derived from a phenolic hydroxyl group. As described above, this structure not only contributes to higher dry etching resistance, but also can increase the glass transition temperature (Tg) of the compound (D), and it is inferred that higher resolving power can be provided by the combined effects.

In the present invention, non-acid decomposability means a property which does not cause a decomposition reaction by an acid generated by a photoacid generator.

More specifically, the group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure is a group which is stable in an acid and a base. A group which is stable in an acid and a base means a group which does not exhibit acid decomposition property and alkali decomposition property. Here, the acid decomposition property means a property of causing a decomposition reaction by the action of an acid generated by a photoacid generator.

In addition, the alkali decomposition property refers to a property of causing a decomposition reaction by the action of an alkali developer, and as a group exhibiting alkali decomposition property, a resin suitable for use in a positive chemical amplification type photoresist composition is mentioned. A group (for example, a group having a lactone structure, etc.) which is decomposed by the action of a conventionally known alkali developing solution and which has a high dissolution rate in an alkali developing solution.

The group having a polycyclic alicyclic hydrocarbon structure is not particularly limited as long as it has a valence group of a polycyclic alicyclic hydrocarbon structure, and a ruthenium carbon number of 5 to 40 is preferred, and 7 to 30 is more preferred. 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 also be bridged. 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, a cyclooctyl group, etc., and a plurality of singles. The structure of the cyclic alicyclic hydrocarbon group has a plurality of such groups. The structure having a plurality of monocyclic alicyclic hydrocarbon groups preferably has 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferably 2.

Examples of the polycyclic alicyclic hydrocarbon structure include a bicyclic, tricyclic or tetracyclic structure having 5 or more carbon atoms, and a polycyclic ring structure having 6 to 30 carbon atoms is preferable, and for example, an adamantane structure is exemplified. , decalin structure, norbornane structure, norbornene structure, cedar structure, isodecane structure, decane structure, dicyclopentane structure, α-pinene structure, tricyclodecane structure, tetracyclic ten Dioxane structure, or androstane structure. Further, a part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.

Preferred examples of the polycyclic alicyclic hydrocarbon structure include an adamantane structure, a decahydronaphthalene structure, a norbornane structure, a norbornene structure, a cedarol structure, a structure having a plurality of cyclohexyl groups, and a plurality of a structure of a cycloheptyl group, a structure having a plurality of cyclooctyl groups, a structure having a plurality of cycloalkylene groups, a structure having a plurality of cyclododecyl groups, and a tricyclodecane structure, from the viewpoint of dry etching resistance, The adamantane structure is the most preferable (that is, the group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure is the group having a non-acid-decomposable adamantane structure).

The polycyclic alicyclic hydrocarbon structures (for a structure having a plurality of monocyclic alicyclic hydrocarbon groups, which are monocyclic alicyclic hydrocarbon structures corresponding to a monocyclic alicyclic hydrocarbon group) (specifically, the following formula is shown below) The chemical formula of (47)~(50) structure)).

[Chemical Formula 35]

Further, the polycyclic alicyclic hydrocarbon structure may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 6 carbon atoms) and a cycloalkyl group (having preferably 3 to 10 carbon atoms). , aryl (preferably having 6 to 15 carbon atoms), halogen atom, hydroxyl group, alkoxy group (preferably having 1 to 6 carbon atoms), carboxyl group, carbonyl group, thiocarbonyl group, alkoxycarbonyl group (number of carbon atoms) 2 to 7 are preferred), and a group in which the groups are combined (the number of carbon atoms is preferably from 1 to 30, and the number of carbon atoms is preferably from 1 to 15).

The polycyclic alicyclic hydrocarbon structure has a structure represented by any one of the above formulas (7), (23), (40), (41), and (51), and has two formulas (48) Any one of the hydrogen atoms in the structure is preferably a structure of a valence group of a bond bond, and the structure represented by any one of the above formulas (23), (40) and (51) has two Any one of the hydrogen atoms in the structure of the formula (48) has a structure as a valent group of a bond bond, and the structure represented by the above formula (40) is the most preferable.

As the group having a polycyclic alicyclic hydrocarbon structure, it is preferred that any one of the above-mentioned polycyclic alicyclic hydrocarbon structures has a hydrogen atom as a bond group.

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

[Chemical Formula 36]

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

X represents a group having a polycyclic alicyclic hydrocarbon structure which is not acid-decomposable.

Ar ₁ represents an aromatic ring.

M2 is an integer of 1 or more.

R ₁₃ in the formula (3) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferred.

Examples of the aromatic ring of Ar ₁ of the 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, an anthracene ring or a phenanthrene ring. Or include, for example, a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, a thiazole ring. An aromatic ring heterocyclic ring such as a heterocyclic ring. Among them, a benzene ring or a naphthalene ring is preferred from the viewpoint of analytical properties, and a benzene ring is most preferred.

The aromatic ring of Ar ₁ may have a substituent in addition to the group represented by the above -OX, and examples of the substituent include an alkyl group (preferably having 1 to 6 carbon atoms) and a cycloalkyl group (for example). a carbon number of 3 to 10 is preferred, 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 or an alkoxy group. A carbonyl group (having preferably 2 to 7 carbon atoms), an alkyl group, an alkoxy group or an alkoxycarbonyl group is preferred, and an alkoxy group is more preferred.

X represents a group having a polycyclic alicyclic hydrocarbon structure which is not acid-decomposable. Specific examples and preferred ranges of the group 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 following general formula (4).

An integer of m2 of 1 to 5 is preferred, and 1 is most preferred. When m2 is 1 and Ar ₁ is a benzene ring, the substitution position of -OX may be a para, meta or ortho, para or meta position relative to the bonding position of the benzene ring to the polymer backbone. For better, the alignment is better.

In the present invention, the repeating unit represented by the above formula (3) is preferably a repeating unit represented by the following formula (4).

When the polymer compound (D) having a repeating unit represented by the formula (4) is used, the Tg of the polymer compound (D) is increased, and a very hard sensitizing ray or radiation sensitive film is formed. The acid diffusibility and dry etching resistance are more reliably controlled.

[Chemical Formula 37]

In the 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.

Hereinafter, preferred examples used in the present invention will be described by repeating units represented by the above formula (4).

R ₁₃ in the formula (4) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferred.

In the formula (4), Y is preferably a divalent linking group. Preferred groups for the divalent linking group of Y are 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, or COCH ₂ -, -NH- or a divalent linking group obtained by combining the same (the number of carbon atoms is preferably from 1 to 20, and the number of carbon atoms is preferably from 1 to 10), which is a carbonyl group, -COCH ₂ Further, a sulfonyl group, -CONH-, or -CSNH- is more preferred, and a carbonyl group and -COCH ₂ - are further preferred, and a carbonyl group is particularly preferred.

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

The polycyclic alicyclic hydrocarbon group has a plurality of monocyclic alicyclic hydrocarbon groups or a polycyclic alicyclic hydrocarbon group, and may also be bridged. 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, a cyclooctyl group, and the like. And other groups. The group having a plurality of monocyclic alicyclic hydrocarbon groups is preferably 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferably 2 groups.

The polycyclic alicyclic hydrocarbon group is preferably a group having a bicyclic, tricyclic or tetracyclic structure having 5 or more carbon atoms, and a group having a polycyclic ring structure having 6 to 30 carbon atoms is preferable. For example, adamantyl, norbornyl, norbornyl, isodecyl, decyl, dicyclopentyl, α-decenyl, tricyclodecyl, tetracyclododecyl, or male甾alkyl. Further, a part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.

As the polycyclic alicyclic hydrocarbon group of the above X ₂ , adamantyl group, decahydronaphthyl group, norbornyl group, nordecenyl group, cedarol group, a group having a plurality of cyclohexyl groups, and a group having a plurality of cycloheptyl groups a group, a group having a plurality of cyclooctyl groups, a group having a plurality of cycloalkyl groups, a group having a plurality of cyclododecyl groups, a tricyclodecyl group being preferred, and a viewpoint of dry etching resistance On the top, adamantyl is the best. The chemical formula of the polycyclic alicyclic hydrocarbon structure in the polycyclic alicyclic hydrocarbon group of X ₂ may be the same as the chemical formula of the polycyclic alicyclic hydrocarbon structure in the group having the polycyclic alicyclic hydrocarbon structure. The scope is also the same. The polycyclic alicyclic hydrocarbon group of X ₂ may be a valence group having any one of the aforementioned polycyclic alicyclic hydrocarbon structures as a bonding bond.

In addition, the alicyclic hydrocarbon group may have a substituent, and the substituent may be the same as the substituent which may be possessed as a polycyclic alicyclic hydrocarbon structure.

The substitution position of -OYX ₂ in the general formula (4) may be a para, meta or ortho position relative to the bonding position of the benzene ring to the polymer main chain, and the alignment is preferred.

In the present invention, the repeating unit represented by the above formula (3) is preferably a repeating unit represented by the following formula (4').

[Chemical Formula 38]

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

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

The substitution position of the adamantyl ester group in the formula (4') may be a para, meta or ortho position with respect to the bonding position of the benzene ring to the polymer main chain, and the para position is preferred.

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

[Chemical Formula 39-1]

[Chemical Formula 39-2]

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

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

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

[Chemical Formula 40]

In the formula,

Ar ₁ represents an aromatic ring group.

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 a fluorenyl 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, the plurality of R ₁ , the plurality of R _{2 ,} and the plurality of X may be the same or different.

The aromatic ring group 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 such as a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, and a phenanthrene ring (preferably having 6 to 18 carbon atoms), and a thiophene ring, a furan ring, and a pyrrole ring. A heterocyclic aromatic heterocycle such as a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. Among them, a benzene ring or a naphthalene ring is preferred from the viewpoint of analytical properties, and a benzene ring is most preferred.

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

The aromatic ring group of 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 the like. Alkylsulfonyloxy, arylcarbonyl.

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 be bonded to each other to form a ring together with the bonded carbon atoms.

R ₁ and R ₂ each independently represent 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 alkyl group. Sulfomethoxy, arylcarbonyl.

As when R ₁ and a substituent R _2, and examples thereof include a benzyl group, a cyclohexyl group and the like.

As described above, X is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a fluorenyl group, and a hydrogen atom, an alkyl group or a fluorenyl group is preferred, and a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a carbon number is preferred. The base of 2~5 is better.

B represents a single bond or a divalent linking group.

When B represents a divalent linking group, preferred groups as a divalent linking group are a carbonyl group, an alkyl group, an aryl group, a sulfonyl group, -O-, -NH- or a combination thereof. The resulting group (for example, an ester bond, etc.).

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

When R ₃ represents an organic group, an alkyl group, a cycloalkyl group, an aryl group is preferably an organic group, and a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, and ethyl group). a cyclyl group having a carbon number of 3 to 10 (for example, a cyclopentyl group, a cyclohexyl group, a decyl group) or an aryl group having 6 to 10 carbon atoms (for example, a phenyl group or a naphthyl group). Base) is better.

The organic group may further have a substituent. Examples of the substituent include a halogen atom (a fluorine atom is preferred), a carboxyl group, a hydroxyl group, an amine group, and a cyano group. However, the substituent is not limited thereto. As a substituent, a fluorine atom and a hydroxyl group are especially 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, and more preferably a hydrogen atom.

When B represents a divalent linking group, preferred groups as a divalent linking group are a carbonyl group, an alkyl group, an aryl group, a sulfonyl group, -O-, -NH- or a combination thereof. The resulting group (for example, an ester bond, etc.).

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

[Chemical Formula 41]

In the formula (B), B ₁₂ represents a single bond or a divalent linking group. * indicates the keying key that is keyed to the main chain. ** indicates that the key is bonded to Ar ₁ .

When B ₁₂ represents a divalent linking group, as a divalent linking group, an alkyl group, an -O- group, a carbonyl bond or a group obtained by combining the same is used.

B represents a divalent linking group represented by the following formula (B-1).

[Chemical Formula 42]

In the formula (B-1), B ₂ represents a single bond or a divalent linking group. * indicates the keying key that is keyed to the main chain. ** indicates that the key is bonded to Ar ₁ .

When B ₂ represents a divalent linking group, as a divalent linking group, an alkyl group and an alkoxy group are preferred, and an alkyl group having 1 to 5 carbon atoms and a stretching number of 1 to 5 carbon atoms are preferred. The alkoxy group is more preferred. Further, when B ₂ represents an alkoxy group, the oxy group of the alkoxy group is bonded to any one of the carbon atoms constituting the benzene ring represented by the formula (B-1).

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

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

[Chemical Formula 43]

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

R ₁ and R ₂ in the 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, and preferably have a carbon number of 1 to 5. The alkyl group is more preferred.

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

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

[Chemical Formula 44]

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

R ₁ and R ₂ in the formula (I-3) each independently represent an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, and preferably have 1 to 5 carbon atoms. The alkyl group is even better.

In the general formula (I-3), n represents an integer of 1 to 5, and preferably represents an integer of 1 to 3, and further 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 ethyl group.

[Chemical Formula 45]

[Chemical Formula 46]

[Chemical Formula 47]

[Chemical Formula 48]

When the compound (D) is a polymer compound, the content of the repeating unit represented by the formula (III) is not particularly limited, and all the repeating units in the compound (D) are excellent in the resolution of the pattern. It is preferably from 1 to 60 mol%, more preferably from 3 to 50 mol%, and further preferably from 5 to 40 mol%.

In the compound (D) which is a polymer compound to be used in the present invention, a repeating unit other than the above repeating unit further preferably has a repeating unit (hereinafter also referred to as "other repeating unit").

Examples of the polymerizable monomer for forming the other repeating units include styrene, alkyl-substituted styrene, alkoxy-substituted styrene, halogen-substituted styrene, O-alkylated styrene, and O-. Deuterated styrene, hydrogenated hydroxystyrene, maleic anhydride, acrylic acid derivatives (acrylic acid, acrylate, etc.), methacrylic acid derivatives (methacrylic acid, methacrylate, etc.), N-substituted maleene Diimine, acrylonitrile, methacrylonitrile, vinyl naphthalene, vinyl anthracene, an anthracene which may have a substituent, and the like.

The compound (D) as a polymer compound may or may not contain such other repeating units, and when it is contained, the content of the other repeating units in the compound (D) as a polymer compound is relative to the composition as a polymer compound. All repeating units of the compound (D) are generally 1 to 30 mol%, preferably 1 to 20 mol%, more preferably 2 to 10 mol%.

The compound (D) which is a polymer compound can be synthesized by a known radical polymerization method, an anionic polymerization method, or a living radical polymerization method (initiation-transfer-terminator method). For example, in the anionic polymerization method, an ethylene monomer is dissolved in a suitable organic solvent, and a metal compound (such as butyllithium) is used as an initiator, and the reaction is usually carried out under cooling to obtain a polymer.

As the compound (D) of the polymer compound, a polyphenol compound produced by a condensation reaction of an aromatic ketone or an aromatic aldehyde and a compound having 1 to 3 phenolic hydroxyl groups can also be used (for example, JP-A-2008-145539) ), calixarene derivatives (for example, JP-A-2004-18421), Noria derivatives (for example, JP-A-2009-222920), and polyphenol derivatives (for example, JP-A-2008-94782) can also be reacted by a polymer. After modification, synthesis.

Further, it is preferred that the polymer (D) as a polymer compound is modified by a polymer reaction to a polymer synthesized by a radical polymerization method or an anionic polymerization method.

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

The degree of dispersion (molecular weight distribution) (Mw/Mn) of the compound (D) as the polymer compound is preferably 2.0 or less, and from the viewpoint of improving sensitivity and resolution, 1.0 to 1.80 is preferable, and 1.0 to 1.60 is more preferable. Good, 1.0~1.20 is the best. It is preferred to use a living polymerization such as living anionic polymerization to obtain a uniform dispersion degree (molecular weight distribution) of the obtained polymer compound. The weight average molecular weight and the degree of dispersion of the compound (D) as a polymer compound are defined as polystyrene-converted values obtained by GPC measurement.

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

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

[Chemical Formula 49-1]

[Chemical Formula 49-2]

[Chemical Formula 49-3]

[Chemical Formula 49-4]

[Chemical Formula 49-5]

[alkaline compound]

The composition of the present invention preferably contains a basic compound as an acid scavenger in addition to the above components. By using a basic compound, it is possible to reduce the change in performance caused by the elapse of time from exposure to post-heating. As such a basic compound, an organic basic compound is preferable, and more specifically, an aliphatic amine, an aromatic amine, a heterocyclic amine, a nitrogen-containing compound having a carboxyl group, and a sulfonyl group are mentioned. A nitrogen-containing compound, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcohol-containing nitrogen-containing compound, a guanamine derivative, a quinone imide derivative, or the like. An amine oxide compound (described in JP-A-2008-102383) or an ammonium salt (based on a hydroxide or a carboxylate) is preferably used. More specifically, from the viewpoint of LER, Preferred is tetraalkylammonium hydroxide represented by butylammonium.).

Further, a compound which is increased in alkali due to the action of an acid can also be used as one type of a basic compound.

Specific examples of the amines include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, tetradecylamine, and pentadecane. Amine, cetylamine, octadecylamine, diamine, methyloctadecylamine, dimethylundecylamine, N,N-dimethyldodecanamine, methylbisoctadecylamine , N,N-dibutylaniline, N,N-dihexylaniline, 2,6-diisopropylaniline, 2,4,6-tris(t-butyl)aniline, triethanolamine, N,N- Dihydroxyethylaniline, tris(methoxyethoxyethyl)amine; compound exemplified after column 3, line 60 of the specification of US Pat. No. 6040112, 2-[2-{2-(2, 2-Dimethoxy-phenoxyethoxy)ethyl}-bis-(2-methoxyethyl)]-amine; in paragraph <0066> of the specification of US Patent Application Publication No. 2007/0224539 A1 The exemplified compounds (C1-1) to (C3-3) and the like. Examples of the compound having a nitrogen-containing heterocyclic structure include 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, N-hydroxyethylpiperidine, and sebacic acid bis(1,2,2). 6,6-pentamethyl-4-piperidinyl), 4-dimethylaminopyridine, antipyrine, hydroxyantipyrine, 1,5-diazabicyclo[4.3 .0] anthracene-5-ene, 1,8-diazabicyclo [5.4.0]-undec-7-ene, tetrabutylammonium hydroxide, and the like.

Further, a photodecomposable basic compound may be suitably used (in the first place, a basic nitrogen atom acts as a base to exhibit alkalinity, but is decomposed by irradiation with actinic rays or radiation to produce a basic nitrogen atom and A compound having a zwitterionic compound in an organic acid group, and such a compound which is neutralized in the molecule, thereby reducing or eliminating the alkalinity. For example, Japanese Patent No. 3577743, JP-A-2001-215689, and JP-A A sulfonium salt described in JP-A-2008-102383, and a photo-basic generator (for example, a compound described in JP-A-2010-243773).

Among these basic compounds, an ammonium salt is 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 based on the total solid content of the composition, more preferably 0.03 to 5% by mass, and particularly preferably 0.05 to 3% by mass.

[Surfactant]

In order to improve coatability, the composition of the present invention may further contain a surfactant. The example of the surfactant is not particularly limited, and examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, and sorbitan fatty acid esters. A nonionic surfactant such as a polyoxyethylene sorbitan fatty acid ester, Magafac (registered trademark) F171 and Magafac F176 (manufactured by DIC Corporation) or Fluorad FC430 (manufactured by Sumitomo 3M Limited) or Surfynol E1004 (ASAHI GLASS CO.). , manufactured by OMNOVA Solutions Inc., a fluorine-based surfactant such as PF656 or PF6320, an organic siloxane polymer, or a polyoxyalkylene polymer.

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]

The composition of the present invention preferably contains an organic carboxylic acid in addition to the above components. Examples of such an organic carboxylic acid compound include an aliphatic carboxylic acid, an alicyclic carboxylic acid, an unsaturated aliphatic carboxylic acid, a hydroxycarboxylic acid, an alkoxycarboxylic acid, a ketocarboxylic acid, a benzoic acid derivative, and an orthobenzene. Dicarboxylic acid, terephthalic acid, isophthalic acid, 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, etc., when electron beam exposure is carried out under vacuum, it is possible to The surface of the photoresist film is volatilized to contaminate the drawing chamber. Therefore, preferred examples of the compound are aromatic organic carboxylic acids, among which, for example, benzoic acid, 1-hydroxy-2-naphthoic acid, and 2-hydroxy-3-naphthoic acid are suitable.

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

The composition of the present invention may further contain a dye, a plasticizer, and an acid-proliferating agent as needed (described in International Publication No. 95/29968, International Publication No. 98/24000, Japanese Patent Application Laid-Open No. Hei 8-305262, and Japanese Patent No. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. U.S. Patent No. 5,395,736, U.S. Patent No. 5,741,630, U.S. Patent No. 5,334,489, U.S. Patent No. 5,582,956, U.S. Patent No. 5,5,78, 424, U.S. Patent No. 5,453,345, U.S. Patent No. 5,445,917, European Patent No. 665,960, European Patent No. 757,628, European Patent No. 665,961, US Patent No. 5,667,943, Japanese Patent Laid-Open No. Hei 10-1508, Japanese Patent Laid-Open No. Hei 10-282642, Japanese Patent Application No. Hei 9- Bulletin No. 512498, JP-A-2000-62337, and JP-A-2005- Japanese Patent Publication No. 17730, JP-A-2008-209889, and the like. Each of the compounds described in JP-A-2008-268935 can be mentioned.

[carboxylic acid sulfonium salt]

The composition of the present invention may contain a cerium carboxylate salt. Examples of the ruthenium carboxylate salt include a ruthenium carboxylate salt, a ruthenium carboxylate salt, and an ammonium carboxylate salt. As the cerium carboxylate salt, a cerium carboxylate salt or a cerium carboxylate salt is particularly preferred. Further, in the present invention, the carboxylate residue of the cerium carboxylate salt preferably contains no aromatic group or carbon-carbon double bond. As the particularly preferred anion moiety, a linear, branched, monocyclic or polycyclic cyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferred. It is further preferred that an anion of a carboxylic acid in which a part or all of the alkyl group is substituted by fluorine is preferred. An oxygen atom may also be included in the alkyl chain. Thereby, transparency to light of 220 nm or less can be ensured, sensitivity and resolution can be improved, and the density dependence and exposure margin can be improved.

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

[acid proliferator]

The sensitizing ray-sensitive or radiation-sensitive composition of the present invention may further contain one or more compounds which are decomposed by the action of an acid to generate an acid (hereinafter also referred to as an acid proliferator). The acid produced by the acid multiplying agent is preferably a sulfonic acid, a methylated acid or a quinone acid. The content of the acid-proliferating agent is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, even more preferably from 1.0 to 20% by mass, based on the total solid content of the composition.

The ratio of the amount of the acid proliferator to the acid generator (the solid content of the acid multiplier based on all the solid components in the composition / the solid content of the acid generator based on all the solid components in the composition) There is no particular restriction, 0.01~50 is better, 0.1~20 is better, and 0.2~1.0 is especially good.

Hereinafter, examples of the acid multiplying agent which can be used in the present invention are shown, but are not limited thereto.

[Chemical Formula 50]

[solvent]

The composition of the present invention may contain a solvent as a solvent, ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME, alias 1-methoxy-2-propanol) , propylene glycol monomethyl ether acetate (PGMEA, alias 1-methoxy-2-ethoxypropane propane), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, 3-methoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, Ethyl lactate, methyl 2-hydroxyisobutyrate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, N,N-dimethylformamide, γ - Butyrolactone, N,N-dimethylacetamide, propylene carbonate, ethylene carbonate or the like is preferred. These solvents may be used singly or in combination.

The solid component of the composition of the present invention is dissolved in the above solvent, and it is preferably dissolved in an amount of 1 to 40% by mass as a solid component concentration. 1 to 30% by mass is more preferable, and 3 to 20% by mass is further preferable.

<Photosensitized ray-sensitive or radiation-sensitive film and blank mask>

The present invention also relates to a sensitizing ray-sensitive or radiation-sensitive film comprising the composition of the present invention, which is formed, for example, by applying the composition of the present invention to a support such as a substrate. The thickness of the film is preferably 0.02 to 0.1 μm. The method of applying to the substrate can be applied to the substrate by a suitable coating method such as a spin coating method, a roll coating method, a shower coating method, a dip coating method, a spray coating method, or a doctor coating method, and the spin coating is performed. Preferably, the rotation speed is preferably 1000 to 3000 rpm. The coating film is prebaked at 60 to 150 ° C for 1 to 20 minutes (pre-baking at 80 to 120 ° C for 1 to 10 minutes is preferred) to form a film.

For the material constituting the substrate to be processed and the outermost layer thereof, for example, when a semiconductor wafer is used, a ruthenium wafer can be used, and examples of the material to be the outermost layer include Si, SiO ₂ , SiN, and SiON, TiN, WSi, BPSG, SOG, organic anti-reflection film, and the like.

Further, the present invention relates to a blank mask having the sensitized ray-sensitive or radiation-sensitive film obtained as described above. In order to obtain a blank mask having such a sensitizing ray-sensitive or radiation-sensitive film, when a pattern is formed on a blank mask for photomask production, examples of the transparent substrate to be used include quartz, calcium fluoride, and the like. Transparent substrate. Generally, a light shielding film, an antireflection film, and a phase shift film are further laminated on the substrate, and a functional film such as an etching stopper film or an etching mask film is additionally required. A film of a material containing a transition metal such as ruthenium or chromium, molybdenum, zirconium, hafnium, tungsten, titanium or ruthenium as a functional film is laminated. Further, as a material used in the outermost layer, a material containing oxygen and/or nitrogen in a crucible or a crucible as a main constituent material may be exemplified; and a material further containing a transition metal in the main material may be a constituent material. Or a compound selected from the group consisting of a transition metal, particularly selected from the group consisting of chromium, molybdenum, zirconium, hafnium, tungsten, titanium, niobium, and the like, or further comprising one or more selected from the group consisting of oxygen and nitrogen The material of the element in carbon is a transition metal compound material mainly composed of a material.

The light-shielding film may be a single layer, but a multilayer structure obtained by repeatedly coating a plurality of materials is more preferable. In the case of a multilayer structure, the thickness of the film per layer is not particularly limited, and 5 to 100 nm is preferable, and 10 to 80 nm is more preferable. The thickness of the entire light-shielding film is not particularly limited, and 5 to 200 nm is preferable, and 10 to 150 nm is more preferable.

In these materials, when a material containing oxygen or nitrogen in chromium is usually formed by patterning with a photoresist composition on a blank mask of the outermost layer, it is easy to become a so-called undercut which forms a reduced diameter shape in the vicinity of the substrate ( Under-cut shape, but when the present invention is used, the undercut problem can be improved as compared with the prior art.

In the water, the actinic ray or radiation sensitive linear film is irradiated with actinic rays or radiation (electron beam, etc.) (ie, exposure), preferably for baking (usually 80 to 150 ° C, 90 to 130 ° C. Preferably, the development is carried out afterwards. Thereby, a good pattern can be obtained. Further, the pattern is used as a mask, and etching treatment, ion implantation, and the like are suitably performed, and a semiconductor fine circuit, a mold structure for imprint, and the like are produced.

In addition, the process for producing a stamping die using the composition of the present invention is described in, for example, Japanese Patent No. 4109085, Japanese Patent Laid-Open No. 2008-162101, and "Basic and Technical Development and Application of Nano Imprinting". Unfolding - Nano-imprinted substrate technology and the latest technology development - Editor: Hirai Yoshihiko (Frontier Publishing).

<pattern forming method>

The composition of the present invention can be suitably used in the formation process of the negative pattern shown below. That is, it can be preferably used in a process comprising the steps of: applying the composition of the present invention to a substrate to form a sensitized ray-sensitive or radiation-sensitive film; and irradiating the sensitized ray-sensitive or radiation-sensitive film with actinic radiation. Radiation or radiation (i.e., exposure); and development of the exposed film by using a developing solution to obtain a negative pattern. For such a process, for example, the processes described in JP-A-2008-292975, JP-A-2010-217884, and the like can be used.

The present invention also relates to a pattern forming method comprising the steps of: exposing a blank mask having the above-described sensitized ray-sensitive or radiation-sensitive film; and developing a blank mask having the exposed film. In the present invention, the above exposure is preferably carried out using an electron beam or an extreme ultraviolet ray.

In the production of a precision integrated circuit device or the like, it is preferable to first irradiate an electron beam or an extreme ultraviolet ray (EUV) to the photoresist film of the present invention in the exposure (pattern forming step) on the photoresist film. In the case of an electron beam, exposure is preferably about 0.1 to 20 μC/cm ² and about 3 to 10 μC/cm ² , and in the case of extreme ultraviolet light, it is 0.1 to 20 mJ. / cm ² or so, be 3 ~ 15mJ / cm ² was exposed to approximately the preferred embodiment. Next, on a hot plate, it is heated at 60 to 150 ° C for 1 to 20 minutes (1 to 10 minutes at 80 to 120 ° C is preferred) and then heated (exposure after exposure), followed by development, rinsing, and drying. Thereby forming a pattern. Next, 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, any of an organic developer and an alkali developer can be used. As the organic developing solution, an ester solvent (butyl acetate, ethyl acetate, methyl 2-hydroxyisobutyrate, isoamyl acetate, butyl butyrate, or the like) or a ketone solvent (2-heptanone, A polar solvent such as cyclohexanone or the like, an alcohol solvent, a guanamine solvent or an ether solvent, and a hydrocarbon solvent. The water content of the organic developing solution as a whole is preferably less than 10% by mass, and it is more preferable that the water content is substantially not contained.

As the alkali developing solution, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but in addition, an inorganic base, a primary amine, a secondary amine, a tertiary amine, an alcoholamine, or a cyclic amine can also be used. Aqueous aqueous solution. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkali developing solution for use. The alkali concentration of the alkali developer is usually 0.1 to 20% by mass. The pH of the alkali developer is usually from 10.0 to 15.0.

Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution for use.

Since the composition of the present invention is a negative-type photoresist composition used in the formation of a negative pattern, the film of the unexposed portion is dissolved, and the exposed portion is hardly dissolved in the developer due to crosslinking of the compound. With this, the target pattern can be formed on the substrate.

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

The electronic component of the present invention is suitable for being mounted on electrical and electronic equipment (home appliances, OA/media related equipment, optical equipment, communication equipment, etc.).

[Examples]

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

<Synthesis of sulfonium salt compound (A)>

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

<Synthesis of acid generator (B)>

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

<Synthesis of Compound (D) Having Acid Crosslinkable Group>

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

[Chemical Formula 51]

(Synthesis of Compound (CL-7A))

9,8-bis(4-hydroxy-3-methylphenyl)anthracene (Wako Pure Chemical Industries, Ltd.) 18.8 g, 50% aqueous dimethylamine solution 19.8 g, paraformaldehyde 6.6 g at 80 °C A mixture of 10 mL of ethanol was stirred for 2 hours. After distilling off the ethanol, 50 mL of ethyl acetate and 50 mL of water were added to carry out a liquid separation operation, and the organic layer was washed twice with 50 mL of water. The obtained organic layer was dried over magnesium sulfate, and filtered, and the solvent of the filtrate was evaporated to give 23.4 g (yield 95%) of (C-1A) as a crude product. The ¹ H-NMR (acetone-d6) chart of the compound (CL-7A) is shown in Fig. 2 .

(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 ° C for 6 hours. After allowing to cool, acetic acid and acetic anhydride were distilled off to obtain 27.1 g of the compound (D-2B). The obtained compound (CL-7B) was used for the synthesis of the compound (CL-7) without further purification.

(Synthesis of Compound (CL-7))

To 27.1 g of the compound (CL-7B) obtained above, 58 g of methanol and 6.9 g of potassium carbonate were added, and the mixture was stirred at 60 ° C for 2 hours. After allowing to cool, methanol was distilled off. 100 mL of ethyl acetate and 100 mL of water were added to carry out a liquid separation operation, and the organic layer was washed with 100 mL of a 1N aqueous hydrochloric acid solution, and then washed three times with 100 mL of water. The obtained organic layer was dried over magnesium sulfate, the dried solvent was filtered, and the solvent of the filtrate was distilled off to obtain 19.8 g of compound (CL-7) (total yield: 85%). In FIG 1 shows the compound (CL-7) in the ^{1 H-NMR (acetone-d6} ) FIG.

[鎓 salt compound (A)]

As the onium salt compound (A), the following are used. It is shown together with the fluorine atom content rate (% by mass) and the pKa value. Here, as described above, pKa represents the value calculated using the software suite 1.

[Chemical Formula 52]

[Chemical Formula 53]

[acid generator (B)]

As the acid generator (B), the following are used. It is shown together with the fluorine atom content rate (% by mass) and the pKa value. Here, as described above, pKa represents the value calculated using the software suite 1.

[Chemical Formula 54]

[Chemical Formula 55]

[Compound (C) having an acid crosslinkable group]

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

[Chemical Formula 56]

[Compound (D) containing a phenolic hydroxyl group]

As the compound (D) containing a phenolic hydroxyl group, the following are used. Hereinafter, it is shown together with a composition ratio (Morby ratio), a weight average molecular weight (Mw), and a dispersion degree (weight average molecular weight (Mw) / number average molecular weight (Mn)).

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

[Chemical Formula 57]

[Interacting Agent] W-1: PF6320 (manufactured by OMNOVA Solutions Inc.) W-2: Magafac F176 (manufactured by DIC Corporation; fluorine-based) W-3: polyoxyalkylene polymer KP-341 (Shin-Etsu Chemical Co) .,Ltd. system;

[Solvent] S1: propylene glycol monomethyl ether (1-methoxy-2-propanol) S2: propylene glycol monomethyl ether acetate (1-methoxy-2-ethoxypropane propane) S3: 2-g Ketone S4: ethyl lactate S5: cyclohexanone S6: γ-butyrolactone S7: propylene carbonate

(1) Preparation of the support

A 6-inch wafer of oxidized Cr (a material subjected to a masking film used in a usual blank mask) was prepared.

(2) Preparation of photoresist composition

The solution shown in Table 1 was dissolved in a solvent shown in the table to prepare a solution, which was filtered with a polytetrafluoroethylene filter having a pore size of 0.03 μm to prepare a photoresist composition.

[Table 1]

(3) Production of photoresist film

The photoresist composition was applied onto a 6-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron Limited., and dried on a hot plate at 100 ° C for 600 seconds to obtain a photoresist film having a film thickness of 50 nm. That is, a photoresist coated wafer is obtained.

(4) Production of negative resist pattern

Patterning was performed on the photoresist film using an electron beam drawing device (manufactured by ELIONIX INC.; ELS-7500, acceleration voltage: 50 KeV). After the irradiation, the plate was heated at 120 ° C for 60 seconds, and impregnated with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 120 seconds, and then rinsed with water for 30 seconds and dried.

(5) Evaluation of photoresist pattern

For the obtained pattern, sensitivity, resolution, pattern collapse, and bridging defects were evaluated by the following methods. The results are shown in Table 2 shown later.

<sensitivity>

The irradiation energy when the 1:1 line having a line width of 50 nm and the spatial pattern were analyzed was taken as the sensitivity (Eop). The smaller the value, the better the performance.

<L/S Analytic>

The ultimate resolution (the minimum line width separated by line and space (line: space = 1:1)) at the exposure amount of the above sensitivity (Eop) is shown as the resolution (nm).

<Isolated Space Pattern (Iso-Space) Analytic>

The ultimate resolution force (the minimum spatial width of the line-to-space separation analysis) of the isolated space (line: space = 100:1) under the above sensitivity (Eop) is obtained. Further, this value is referred to as "isolated spatial pattern resolution (nm)". The smaller the value, the better the performance.

<pattern collapse>

The minimum line width in which the pattern was analyzed in the non-collapse state when the line width was reduced by subtracting the exposure amount from the above sensitivity (Eop) was measured, and the minimum line width was used as an index for suppressing the occurrence of pattern collapse. The smaller the value, the more the fine pattern is analyzed without collapse, and the more excellent the suppression of the occurrence of pattern collapse.

<Bridge defect>

For the 1:1 line and space pattern of the line width of 50 nm formed by the above sensitivity (Eop), the defect inspection apparatus KLA2360 (trade name) manufactured by KLA-Tencor Company was used, and the pixel size of the defect inspection apparatus was set to 0.16 μm and After the threshold was set to 20 to measure the number of defects per unit area (number/cm ² ), defect pre-viewing was performed, thereby extracting bridging defects from all the defects. The number of defects per unit area is calculated by detecting the difference (number/cm ² ) of the extracted defects based on the difference between the comparison image and the pixel unit.

The smaller the value, the more excellent the bridge defect reduction performance.

[Table 2]

As is clear from the results of Table 2, the pattern obtained by the pattern forming method of the present invention is excellent in sensitivity and resolution, and bridge defects and pattern collapse are also suppressed.

no

Fig. 1 is a chart showing the NMR chart ( ¹ H NMR, acetate-d6) of the acid crosslinking agent (CL-7) synthesized in the examples. FIG 2 represents a cross-linking agent based (CL-7) Synthesis of Intermediate Example i.e. compound (CL-7A) of FIG. NMR ⁽¹ HNMR, acetone-d6) of FIG.

Claims (20)

A photosensitive ray-sensitive or radiation-sensitive resin composition comprising: (A) an onium salt compound containing at least one fluorine atom in an anion portion and containing at least one nitrogen atom in a cationic portion; and (B) comprising at least a fluorine atom and a compound which generates an acid by irradiation with actinic rays or radiation, and the sensitized ray-sensitive or radiation-sensitive resin composition is characterized by: a fluorine atom in the compound (A) relative to the compound (A) The content of the total mass is greater than the content of the fluorine atom in the compound (B) relative to the total mass of the compound (B). The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content ratio of the fluorine atom in the compound (A) and the content ratio of the fluorine atom in the compound (B) are the same. The difference is converted into a mass percentage of 0.5% by mass or more. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the compound (B) is a sulfonate compound containing at least one fluorine atom in the anion portion. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the cation portion of the compound (A) is provided with an alkaline portion containing the nitrogen atom. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein the basic portion of the compound (A) contains an amine group or a nitrogen-containing heterocyclic group. The sensitized ray-sensitive or radiation-sensitive resin composition according to the first aspect of the invention, wherein the cation portion of the compound (A) has a partial structure represented by the following formula (NI). In the formula, R _A and R _B each independently represent a hydrogen atom or an organic group; X represents a single bond or a linking group; and at least two of R _A , R _B and X may be bonded to each other to form a ring. The photosensitive ray-sensitive or radiation-sensitive resin composition according to the first or second aspect of the invention, wherein the compound (A) is an onium salt represented by the following formula (N-II), 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 are present, R ₁ may be the same or different; R represents an organic group of (o+1) valence, When there are a plurality of R, R may be the same or different; X represents a single bond or a linking group, and when there are a plurality of X, X may be the same or different; A _N represents an alkaline moiety containing a nitrogen atom, when present When a plurality of A _N , 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, 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 Form a ring. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 3, wherein the compound (A) and the compound (B) have the same anion moiety. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the compound (A) is relative to all solid components in the above-mentioned sensitized ray-sensitive or radiation-sensitive resin composition. The content ratio is in the range of 0.1 to 20% by mass. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, further comprising (C) a compound containing an acid crosslinkable group. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 10, wherein the compound (C) containing an acid crosslinkable group contains two or more hydroxymethyl groups or alkoxy groups in the molecule. methyl. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, further comprising (D) a compound containing a phenolic hydroxyl group. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 12, wherein the compound (D) containing a phenolic hydroxyl group is a resin comprising a repeating unit represented by the following formula (II). In the formula, 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 an aromatic ring group; and m represents an integer of 1 or more. The photosensitive ray-sensitive or radiation-sensitive resin composition according to claim 13, wherein the compound (D) containing a phenolic hydroxyl group is a resin further comprising a repeating unit represented by the following formula (III) , Wherein, Ar ₁ represents an aromatic ring group; R ₁ and R ₂ each independently represent an alkyl, cycloalkyl or aryl group; X represents a hydrogen atom, alkyl, cycloalkyl, aryl or 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 an integer of 2 or more is expressed, the plurality of R ₁ , the plurality of R _{2 ,} and the plurality of X may be the same or different. A sensitized ray-sensitive or radiation-sensitive film comprising the composition of claim 1 or 2. A blank mask comprising the sensitized ray-sensitive or radiation-sensitive film described in claim 15 of the patent application. A pattern forming method comprising the steps of: forming a sensitized ray-sensitive or radiation-sensitive film using the sensitizing ray-sensitive or radiation-sensitive resin composition described in claim 1; The ray-sensitive or radiation-sensitive linear film irradiates the actinic ray or radiation; and develops the above-mentioned sensitized ray-sensitive or radiation-sensitive film irradiated with actinic rays or radiation. The pattern forming method according to claim 17, wherein the irradiation of the actinic ray or the radiation is performed using an electron beam or an extreme ultraviolet ray. A method of manufacturing an electronic component, comprising the pattern forming method described in claim 17 or 18. An electronic component manufactured by the method of manufacturing an electronic component according to claim 19.