JP2018189758A - Active ray-sensitive or radiation-sensitive composition, resist film, mask blank, pattern forming method, and method for manufacturing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active ray-sensitive or radiation-sensitive composition from which a pattern extremely excellent in sensitivity and resolution of an isolated space pattern can be formed in the technology of pattern formation using a crosslinking negative resist composition, and a resist film, a mask blank, a pattern forming method and a method for manufacturing an electronic device.SOLUTION: The active ray-sensitive or radiation-sensitive composition comprises a specific onium salt compound (A) and a crosslinking agent (C). The present invention discloses a resist film formed of the above active ray-sensitive or radiation-sensitive composition, a mask blank including the resist film, a pattern forming method comprising irradiating the resist film with active rays or radiation and developing the film irradiated with the active rays or radiation, and a method for manufacturing an electronic device including the above pattern forming method.SELECTED DRAWING: None

Description

  The present invention forms a high-definition pattern using an electron beam, extreme ultraviolet light, or the like, which is suitably used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other photofabrication processes. The present invention relates to an actinic ray-sensitive or radiation-sensitive composition to be obtained, a resist film, a mask blank, a pattern forming method, and an electronic device manufacturing method.

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, the trend of shortening the exposure wavelength from g-line to i-line and further to excimer laser light has been observed, and at present, development using lithography using electron beams and X-rays is also progressing.

  In particular, electron beam and extreme ultraviolet lithography are positioned as next-generation or next-generation pattern formation techniques, and are widely used for manufacturing photomasks used for semiconductor exposure because of their high resolution. For example, in the photomask fabrication process using electron beam lithography, a resist layer is formed on a shielding substrate provided with a shielding layer mainly composed of chromium or the like on a transparent substrate, and then selectively exposed to electron beams. Thereafter, alkali development is performed to form a resist pattern. Next, by etching the shielding layer using this resist pattern as a mask to form a pattern in the shielding layer, a photomask having a shielding layer having a predetermined pattern on the transparent substrate can be obtained.

As a resist composition used for the resist layer, a positive resist composition is widely known, but a negative chemically amplified resist composition in pattern formation by alkali development has also been developed. This is because there is a demand for pattern formation having various shapes such as lines, trenches, and holes in the manufacture of semiconductor elements and the like, but there are patterns that are difficult to form with current positive resist compositions. .
However, in pattern formation using a conventional negative resist composition, a further improvement in resolution has been demanded with the recent demand for finer patterns.

  In order to further improve the resolution, Reference 1 discloses a negative resist composition containing an onium salt compound containing a nitrogen atom in the cation moiety in addition to a photoacid generator and a crosslinking agent. It is disclosed.

JP 2014-134686 A

  By the way, when the resist film is exposed, a so-called “fogging” in which light is irradiated to an unintended region at the time of exposure usually occurs. In particular, in the case of electron beam exposure, the resist film is removed. The influence of “fogging” by backscattered light from the instructed substrate is also great. Such “fogging” leads to the generation of residue in the negative pattern forming method. In particular, a resist pattern such as an isolated space pattern surrounded by a resist film and having a small space width is used as a negative pattern. In the case of forming by a mold pattern forming method, the generation of residue tends to greatly affect the resolution. Such a tendency tends to become more prominent when a negative resist composition containing a crosslinking agent (so-called crosslinked negative resist composition) is used, and further improvement is required. It was.

  The present invention has been made in view of the above, and an object of the present invention is to provide an actinic ray-sensitive material capable of forming a pattern excellent in sensitivity and isolated space pattern resolving power in a pattern forming technique using a crosslinked negative resist composition. Another object of the present invention is to provide a radiation-sensitive composition, a resist film, a mask blank, a pattern forming method, and an electronic device manufacturing method.

  For example, the present invention is as follows.

[1]
An actinic ray-sensitive or radiation-sensitive composition containing an onium salt compound (A) represented by the following general formula (1) and a crosslinking agent (C).

In the general formula (1),
M represents an onium cation, and X represents an organic group.

[2]
The actinic ray-sensitive or radiation-sensitive composition according to [1], further comprising a compound (B) containing a phenolic hydroxyl group.
[3]
The actinic ray-sensitive or radiation-sensitive composition according to [1] or [2], further comprising a photoacid generator (D) different from the onium salt compound (A).

[4]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [3], wherein X in the general formula (1) is a group having an alicyclic structure.

[5]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [4], wherein X in the general formula (1) is a group having a polycyclic alicyclic structure.

[6]
The actinic ray-sensitive property according to any one of [1] to [5], wherein the volume of the acid generated from the onium salt compound (A) upon irradiation with actinic rays or radiation is 210 ³ or more. Radiation sensitive composition.

[7]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [1] to [6], wherein the onium salt compound (A) is an onium salt compound represented by the following general formula (2): .

In the general formula (2),
M represents an onium cation, and Y represents a hydrogen atom or an organic group.

[8]
The actinic ray-sensitive or radiation-sensitive composition according to [7], wherein Y in the general formula (2) is a group having a polycyclic alicyclic structure.

[9]
The actinic ray-sensitive or radiation-sensitive composition according to any one of [2] to [8], wherein the compound (B) containing the phenolic hydroxyl group does not have an acid-decomposable group.

[10]
[1] A resist film formed from the actinic ray-sensitive or radiation-sensitive composition according to any one of [9].

[11]
Mask blanks provided with the resist film as described in [10].

[12]
A pattern forming method comprising irradiating the resist film according to [10] with actinic rays or radiation and developing the film irradiated with the actinic rays or radiation.

[13]
The manufacturing method of an electronic device containing the pattern formation method as described in [12].

[14]
[10] A resist pattern forming method, comprising: irradiating a mask blank provided with the resist film according to [10] with actinic rays or radiation; and developing the mask blanks irradiated with the actinic rays or radiation.

  According to the present invention, in a pattern forming technique using a cross-linked negative resist composition, an actinic ray-sensitive or radiation-sensitive composition, resist film, and mask blank that can form a pattern that is extremely excellent in sensitivity and isolated space pattern resolution. , A pattern forming method, and an electronic device manufacturing method can be provided.

Hereinafter, the present invention will be described in detail.
In the description of groups and atomic groups in this specification, when substitution or non-substitution is not clearly indicated, both those having no substituent and those having a substituent are included. For example, an “alkyl group” that does not explicitly indicate substitution or unsubstituted includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). I will do it.

In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, a deep ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, an ion beam or other particle beam. Means. In the present invention, “light” means actinic rays or radiation.
In addition, the term “exposure” in the present specification is not limited to exposure to far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light) and the like represented by mercury lamps and excimer lasers. It is also assumed that drawing by particle beams such as.

<Actinic ray-sensitive or radiation-sensitive composition>
The actinic ray-sensitive or radiation-sensitive composition of the present invention (hereinafter also referred to as “the composition of the present invention”) includes an onium salt compound (A) represented by the following general formula (1) and a crosslinking agent (C ).

In the general formula (1),
M represents an onium cation, and X represents an organic group.

The reason why the above-described effect is obtained by the configuration of the present invention is not clear, but the present inventor presumes as follows.
First, the onium salt compound (A) is a compound that generates sulfinic acid represented by XSO ₂ H as a weak acid by irradiation with actinic rays or radiation.
Further, in order to carry out the crosslinking reaction with the crosslinking agent (C) as a chemical amplification reaction in the exposed portion of the resist film, the composition of the present invention typically contains a photoacid generator (D) described in detail later. The acid strength of the sulfinic acid is lower than the acid strength of the photoacid generator, and the proton in the photoacid generator (D) and the cation of the onium salt compound (A) are exchanged. In other words, since the onium salt compound (A) typically has a function of capturing an acid generated by the photoacid generator (D), it has basicity with respect to this acid.

Therefore, in the unexposed part of the resist film, the onium salt compound (A) in the unexposed part accepts the acid generated from the photoacid generator (D) and diffused in the unexposed part in the exposed part, and the acid diffusion phenomenon Has the effect of suppressing On the other hand, in the exposed area, the onium salt compound (A) is decomposed to lose basicity with respect to the acid generated from the photoacid generator (D). Therefore, in the exposed area, the acid is not captured by the onium salt compound and is effectively used for the chemical amplification reaction, so that good contrast is obtained in the exposed area and the unexposed area.
Thus, the composition of the present invention can exhibit high resolution (roughness performance, etc.) by containing a so-called “photobase quencher” having the above functions. The acid strength of the salt compound (A) is sufficient to suppress the phenomenon of acid diffusion to the unexposed area by performing the above exchange with the acid generated from the photoacid generator (D). Thus, it is considered that an excellent sensitivity is obtained, an unintended reaction in an unexposed portion is suppressed, and generation of a residue is suppressed. Further, the onium salt compound (A) has a lower degree of polarity than a conventionally known sulfonium salt compound as a photobase quencher and an onium salt compound containing a nitrogen atom in the cation moiety. As a result, compared to the case of using the above-described conventionally known photobase quencher, aggregation of the onium salt compound (A) is suppressed, and the interaction with the compound (B) containing a phenolic hydroxyl group is improved. As a result, it is considered that the onium salt compound (A) is more uniformly distributed in the resist film, and it is possible to capture the acid uniformly in the unexposed area, thereby suppressing the generation of residues.
From the above, according to the composition of the present invention, it can be considered that a pattern extremely excellent in sensitivity and isolated space pattern resolving power can be formed in the pattern forming technique using the crosslinked negative resist composition.

  Hereinafter, each component mentioned above in the composition of this invention is demonstrated in order.

[1] Onium salt compound (A) represented by general formula (1) (hereinafter also referred to as “compound (A)”)
As described above, the composition of the present invention contains an onium salt compound (A) represented by the following general formula (1).

In the general formula (1),
M represents an onium cation, and X represents an organic group.

  The onium cation represented by M is not particularly limited, and examples thereof include a sulfonium cation, an iodonium cation, and a phosphonium cation.

  In the present invention, examples of the onium cation in the preferred onium salt compound include a sulfonium cation represented by the following general formula (ZI) or an iodonium cation represented by the general formula (ZII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, a carbonyl group, or a sulfonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the general formulas (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later. Can be mentioned.
A cation having a plurality of structures represented by the general formula (ZI) may also be used. For example, at least one of R _{201 to} R ₂₀₃ of the cation represented by the general formula (ZI) is a single bond or at least one of R _{201 to} R ₂₀₃ of the other cation represented by the general formula (ZI). It may be a cation having a structure bonded through a linking group.

  More preferable examples of the general formula (ZI) include cations (ZI-1), (ZI-2), (ZI-3), and (ZI-4) described below.

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

The aryl group of the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group that the arylsulfonium cation has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms). , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group and the like may be substituted. The substituent may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, a carbonyl group, or a sulfonyl group.

Next, the cation (ZI-2) will be described.
The cation (ZI-2) is a cation in which R _{201 to} R ₂₀₃ in the general formula (ZI) each independently represent an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group not containing an aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

As the alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ , a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, the cation (ZI-3) will be described.
The cation (ZI-3) is a cation represented by the following general formula (ZI-3), and is a phenacylsulfonium cation.

In general formula (ZI-3),
R _{1c to} R _5c are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. In addition, this ring structure may contain an oxygen atom, a sulfur atom, a ketone group, a sulfonyl group, an ester bond, or an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group, and examples of the alkylene group include a methylene group and an ethylene group. .

Specific examples of the alkoxy group in the alkoxycarbonyl group as R _1c to R _5c are the same as specific examples of the alkoxy group as the _R 1c _{to R 5c.}
Specific examples of the alkyl group in the alkylcarbonyloxy group and alkylthio group as R _1c to R _5c are the same as specific examples of the alkyl group of the _R 1c _{to R 5c.}
Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R _1c to R _5c are the same as specific examples of the cycloalkyl group of the _R 1c _{to R 5c.}
Specific examples of the aryl group in the aryloxy group and arylthio group as R _1c to R _5c are the same as specific examples of the aryl group of the _R 1c _{to R 5c.}

  Examples of the cation (ZI-2) or cation (ZI-3) cation in the present invention include cations described in paragraph [0036] and thereafter of US Patent Application Publication No. 2012/0076996.

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

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
R ₁₄ is independently a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group, when a plurality of R ₁₄ are present. Represents. These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ 's are bonded to each other to form a ring, the ring skeleton may contain a hetero atom such as an oxygen atom or a nitrogen atom. In one embodiment, it is preferred that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure.
l represents an integer of 0-2.
r represents an integer of 0 to 8.

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -A butyl group, a t-butyl group, etc. are preferable.
As the cation (ZI-4) in the present invention, paragraphs [0121], [0123] and [0124] of JP2010-256842A, and paragraphs [0127] and [0129] of JP2011-76056A are disclosed. ], [0130] and the like.

Next, general formula (ZII) will be described.
In formula _{(ZII), R} 204 ~R ₂₀₅ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _205, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₅ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group in R ₂₀₄ to R _205, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₅ may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _205, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

In the general formula (1), X represents an organic group, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic hydrocarbon group, an alkoxycarbonyl group, and a lactone group. Two or more of these groups may be combined, or two or more of these groups may be combined by an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a sulfone bond, or a sulfonamide bond.
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, and a cyano group.

The alkyl group represented by X may be linear or branched. The alkyl group preferably has 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms, and still more preferably 1 to 20 carbon atoms. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadadecyl, isopropyl, isobutyl, sec-butyl, t- A butyl group, 1-ethylpentyl group, 2-ethylhexyl group, etc. are mentioned.
The cycloalkyl group represented by X may be monocyclic or polycyclic. The cycloalkyl group is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group, or a C 6-20 carbon atom such as an adamantyl group or a norbornane group. Examples thereof include a cycloalkyl group of a ring.
The alkenyl group represented by X may be linear or branched. The alkenyl group preferably has 2 to 50 carbon atoms, more preferably 2 to 30 carbon atoms, and still more 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 X, those having 6 to 14 carbon atoms are preferable. Examples of such groups include a phenyl group and a naphthyl group.
The heterocyclic hydrocarbon group represented by X preferably has 5 to 20 carbon atoms, and more preferably has 6 to 15 carbon atoms. The heterocyclic hydrocarbon group may have aromaticity or may not have aromaticity. This heterocyclic hydrocarbon group preferably has aromaticity.
The heterocyclic ring contained in the above heterocyclic hydrocarbon group may be monocyclic or polycyclic. Examples of such heterocyclic rings include imidazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 2H-pyrrole ring, 3H-indole ring, 1H-indazole, purine ring, isoquinoline ring, 4H-quinolidine ring, Quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, phenanthridine ring, acridine ring, phenanthroline ring, phenazine ring, perimidine ring, triazine ring, benzisoquinoline ring, thiazole ring, thiadiazine ring , An azepine ring, an azocine ring, an isothiazole ring, an isoxazole ring, and a benzothiazole ring.

  The alkyl group contained in the alkoxycarbonyl group represented by X may be linear or branched. The alkyl group preferably has 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms, and still more preferably 1 to 20 carbon atoms. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadadecyl, isopropyl, isobutyl, sec-butyl, t- A butyl group, 1-ethylpentyl group, 2-ethylhexyl group, etc. are mentioned.

  The lactone group represented by X is, for example, a 5- to 7-membered lactone group, and other ring structures are condensed to form a bicyclo structure or a spiro structure on the 5- to 7-membered lactone group. It may be. Specifically, a group having the structure shown below is preferable.

  The lactone group may or may not have a substituent (Rb2). Preferred examples of the substituent (Rb2) include the same substituents as those described above as the substituent for X. When n2 is 2 or more, the plurality of substituents (Rb2) may be the same or different. A plurality of substituents (Rb2) may be bonded to form a ring.

  X is preferably a group having an alicyclic structure, and specific examples include groups having specific examples of the monocyclic or polycyclic cycloalkyl groups described above. X is more preferably a group having a polycyclic alicyclic structure, and specific examples include groups having specific examples of the polycyclic cycloalkyl group described above.

  The onium salt compound (A) is preferably an onium salt compound represented by the following general formula (2).

In the general formula (2),
M represents an onium cation, and Y represents a hydrogen atom or an organic group.

In the general formula (2), the onium cation represented by M has the same meaning as the onium cation represented by M in the general formula (2), and the preferred range is also the same.
In the general formula (2), the organic group represented by Y has the same meaning as the organic group represented by X in the general formula (2), and the preferred range is also the same.

  In general formula (2), Y is preferably a group having a polycyclic alicyclic structure. Specific examples of the group having a polycyclic alicyclic structure as Y are the same as the specific examples of the group having a polycyclic alicyclic structure as X in the general formula (1).

  The following are mentioned as an example of the anion structure of the said General formula (1).

The pKa of the acid generated from the onium salt compound (A) represented by the general formula (1) upon irradiation with actinic rays or radiation is preferably −3 or more and 5 or less, and −2 or more and 4 or less. More preferably, it is −1 or more and 3 or less.
In the onium salt compound (A) represented by the general formula (1), the pKa of the acid generated by exposure is preferably higher than the pKa of the acid generated from the photoacid generator (D) described later. . That is, a compound that generates an acid weaker than an acid generated from the photoacid generator (D) by exposure is preferable.

  In this specification, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution. For example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.) The lower the value, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett The values based on the substituent constants and the database of known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

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

In the present invention, the compound (A) has a volume of 130 to ³ or more from the viewpoint of suppressing the diffusion of the acid generated by irradiation with actinic rays or radiation to the non-exposed portion and improving the resolution and pattern shape. it is a compound that generates the size of the acid is preferred, more preferably a compound capable of generating an acid volume of 210 Å ³ or more dimensions, compounds capable of generating an acid volume of 270 Å ³ or more dimensions Is more preferable, and a compound that generates an acid having a volume of 400 ³ or more is particularly preferable. However, from the viewpoints of sensitivity and coating solvent solubility, the volume is preferably 2000 ³ or less, and more preferably 1500 ³ or less. The volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid related to each compound is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.

  Examples of the compound represented by the general formula (1) include the following.

A compound (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the compound (A) is usually in the range of 0.1 to 30% by mass, preferably 0.5 to 20% by mass, more preferably 0.7, based on the total solid content of the composition. It is in the range of ˜15% by mass.

[2] Compound (B) containing phenolic hydroxyl group
In one embodiment, the composition of the present invention preferably contains a compound (B) containing a phenolic hydroxyl group (hereinafter also referred to as compound (B)).
The phenolic hydroxyl group in the present invention is a group formed by substituting a hydrogen atom of an aromatic ring group with a hydroxy group. The aromatic ring of the aromatic ring group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

The compound (B) 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 weight compound such as a molecular resist or a polymer compound. As the molecular resist, for example, low molecular weight cyclic polyphenol compounds described in JP 2009-173623 A and JP 2009-173625 A can be used.
When the composition of the present invention contains the compound (B), a crosslinking reaction proceeds between the compound (B) containing a phenolic hydroxyl group and the compound (C) described later by the action of an acid generated in the exposed area. As a result, a negative pattern is formed.

  In the present invention, the compound (B) preferably has no acid-decomposable group. An acid-decomposable group means a group having a property of causing a decomposition reaction by the action of an acid generated by a photoacid generator.

  When the compound (B) containing a phenolic hydroxyl group of the present invention is a polymer compound, the polymer compound contains a repeating unit having at least one phenolic hydroxyl group. Although it does not specifically limit as a repeating unit which has a phenolic hydroxyl group, It is preferable that it is a repeating unit represented by the following general formula (II).

Where
R ₂ represents a hydrogen atom, an optionally substituted methyl group, 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 for R ₂ include a trifluoromethyl group and a hydroxymethyl group.
R ₂ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom for developability reasons.

As the divalent linking group for B ′, a carbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group (—S (═O) ₂ —), —O -, -NH- or a divalent linking group in combination of these is preferred.
B ′ preferably represents a single bond, a carbonyloxy group (—C (═O) —O—) or —C (═O) —NH—, and 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 may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, or a phenanthrene ring. Good aromatic hydrocarbon ring or, for example, thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc. An aromatic heterocycle including a heterocycle of Among these, a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is most preferable from the viewpoint of sensitivity.

  m is preferably an integer of 1 to 5, and most preferably 1. When m is 1 and Ar ′ is a benzene ring, the substitution position of —OH is a meta position even in the para position relative to the bonding position with the B ′ of the benzene ring (the polymer main chain when B ′ is a single bond). However, from the viewpoint of crosslinking reactivity, the para position and the meta position are preferable, and the para position is more preferable.

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

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

In general formula (2),
R ₁₂ represents a hydrogen atom or a methyl group.
Ar represents an aromatic ring.
R ₁₂ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom for reasons of developability.

Ar in the general formula (2) has the same meaning as Ar ′ in the general formula (II), and the preferred range is also the same. The repeating unit represented by the general formula (2) is a repeating unit derived from hydroxystyrene (that is, a repeating unit in which R ₁₂ is a hydrogen atom and Ar is a benzene ring in the general formula (2)). Is preferable from the viewpoint of sensitivity.

  The compound (B) as the polymer compound may be composed only of a repeating unit having a phenolic hydroxyl group as described above. The compound (B) as the polymer compound may have a repeating unit as described later in addition to the repeating unit having a phenolic hydroxyl group as described above. In that case, it is preferable that the content rate of the repeating unit which has a phenolic hydroxyl group is 10-98 mol% with respect to all the repeating units of the compound (B) as a high molecular compound, and is 30-97 mol%. It is more preferable, and it is still more preferable that it is 40-95 mol%. Thereby, especially when the resist film is a thin film (for example, when the thickness of the resist film is 10 to 150 nm), the alkali development of the exposed portion in the resist film of the present invention formed using the compound (B) is performed. The dissolution rate with respect to the liquid can be more reliably reduced (that is, the dissolution rate of the resist film using the compound (B) can be controlled to an optimum one more reliably). As a result, the sensitivity can be improved more reliably.

  Hereinafter, although the example of the repeating unit which has a phenolic hydroxyl group is described, it is not limited to this.

  Compound (B) is a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure and having a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted, so that a high glass transition temperature (Tg) can be obtained. The dry etching resistance is preferable.

  When the compound (B) has the specific structure described above, the glass transition temperature (Tg) of the compound (B) is increased, and a very hard resist film can be formed. Resistance can be controlled. Therefore, the diffusibility of the acid in the exposed portion of actinic rays or radiation such as an electron beam or extreme ultraviolet rays is greatly suppressed, so that the resolution, pattern shape and LER in a fine pattern are further improved. Further, it is considered that the compound (B) having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure contributes to further improvement in dry etching resistance. Furthermore, although the details are unknown, the polycyclic alicyclic hydrocarbon structure has a high hydrogen radical donating property, and becomes a hydrogen source when the photoacid generator is decomposed, further improving the decomposition efficiency of the photoacid generator and improving the acid generation efficiency. Is estimated to be higher, and this is considered to contribute to better sensitivity.

  The above-mentioned specific structure that the compound (B) according to the present invention may have is an aromatic ring such as a benzene ring and a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure. Are linked via an oxygen atom derived from a functional hydroxyl group. As described above, the structure not only contributes to high dry etching resistance, but also can increase the glass transition temperature (Tg) of the compound (B), and a higher resolution is provided by the effect of these combinations. It is estimated to be.

In the present invention, non-acid-decomposable means a property in which a decomposition reaction does not occur due to an acid generated by a photoacid generator.
More specifically, the group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure is preferably a group stable to acids and alkalis. The group stable to acid and alkali means a group that does not exhibit acid decomposability and alkali decomposability. Here, acid decomposability means the property of causing a decomposition reaction by the action of an acid generated by a photoacid generator.

Alkali decomposability means the property of causing a decomposition reaction by the action of an alkali developer, and the group exhibiting alkali decomposability is contained in a resin suitably used in a positive chemically amplified resist composition. And a group (for example, a group having a lactone structure) that decomposes under the action of a conventionally known alkali developer and increases the dissolution rate in the alkali developer.
The group having a polycyclic alicyclic hydrocarbon structure is not particularly limited as long as it is a monovalent group having a polycyclic alicyclic hydrocarbon structure, but the total number of carbon atoms is preferably 5 to 40, and 7 to 30. It is more preferable that 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. It may be a bridge type. As the monocyclic alicyclic hydrocarbon group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. A structure having a plurality of cyclic alicyclic hydrocarbon groups has a plurality of these groups. The structure having a plurality of monocyclic alicyclic hydrocarbon groups preferably has 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferably has two.

  Examples of the polycyclic alicyclic hydrocarbon structure include bicyclo, tricyclo, and tetracyclo structures having 5 or more carbon atoms, and polycyclic cyclostructures having 6 to 30 carbon atoms are preferable. For example, an adamantane structure and a decalin structure , Norbornane structure, norbornene structure, cedrol structure, isobornane structure, bornane structure, dicyclopentane structure, α-pinene structure, tricyclodecane structure, tetracyclododecane structure, and androstane structure. A part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

  Preferred examples of the polycyclic alicyclic hydrocarbon structure include an adamantane structure, a decalin structure, a norbornane structure, a norbornene structure, a cedrol structure, a structure having a plurality of cyclohexyl groups, a structure having a plurality of cycloheptyl groups, and a plurality of cyclooctyl groups. And a structure having a plurality of cyclodecanyl groups, a structure having a plurality of cyclododecanyl groups, and a tricyclodecane structure, and an adamantane structure is most preferable from the viewpoint of dry etching resistance (that is, the non-acid-decomposable polycyclic fatty acid described above). Most preferably, the group having a ring hydrocarbon structure is a group having a non-acid-decomposable adamantane structure).

These polycyclic alicyclic hydrocarbon structures (for structures having a plurality of monocyclic alicyclic hydrocarbon groups, the monocyclic alicyclic hydrocarbon structure corresponding to the monocyclic alicyclic hydrocarbon group (specifically Specifically, chemical formulas of the following formulas (47) to (50))) are shown below.

  Furthermore, the polycyclic alicyclic hydrocarbon structure may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), Aryl group (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 (preferably having 2 to 7 carbon atoms) And a group formed by combining these groups (preferably having a total carbon number of 1 to 30, more preferably a total carbon number of 1 to 15).

Examples of the polycyclic alicyclic hydrocarbon structure include a structure represented by any one of the above formulas (7), (23), (40), (41) and (51), and an arbitrary structure in the structure of the above formula (48). A structure having two monovalent groups each having one hydrogen atom as a bond is preferable, a structure represented by any one of the above formulas (23), (40) and (51), A structure having two monovalent groups each having an arbitrary hydrogen atom in the structure as a bond is more preferable, and a structure represented by the above formula (40) is most preferable.
The group having a polycyclic alicyclic hydrocarbon structure is preferably a monovalent group having any one hydrogen atom in the polycyclic alicyclic hydrocarbon structure as a bond.

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

In General Formula (3), R ₁₃ represents a hydrogen atom or a methyl group.
X represents a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure.
Ar ₁ represents an aromatic ring.
m2 is an integer of 1 or more.

R ₁₃ in the general formula (3) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.
As the aromatic ring of Ar _{1 in} the general formula (3), for example, an aromatic group optionally having a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring, or the like. Hydrocarbon ring or heterocycle such as thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring Aromatic heterocycles containing can be mentioned. Among these, a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is most preferable.

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

X represents a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure. Specific examples and 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 —Y—X ₂ in the general formula (4) described later.
m2 is preferably an integer of 1 to 5, and most preferably 1. When m2 is 1 and Ar ₁ is a benzene ring, the substitution position of —OX may be in the para position, the meta position, or the ortho position with respect to the bonding position of the benzene ring with the polymer main chain. The para position is preferred.

In the present invention, the repeating unit represented by the general formula (3) is preferably a repeating unit represented by the following general formula (4).
When a polymer compound having a repeating unit represented by the general formula (4) is used, the polymer compound (B) has a high Tg and forms a very hard resist film. Can be controlled more reliably.

In the general formula (4), R ₁₃ represents a hydrogen atom or a methyl group.
Y represents a single bond or a divalent linking group.
X ₂ represents a non-acid-decomposable polycyclic alicyclic hydrocarbon group.

Preferred examples of the repeating unit represented by the general formula (4) used in the present invention are described below.
R ₁₃ in the general formula (4) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.

In general formula (4), Y is preferably a divalent linking group. Preferred groups as the divalent linking group for 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, —COCH ₂ —, —NH—. Or a divalent linking group (preferably having a total carbon number of 1 to 20, more preferably a total carbon number of 1 to 10), or more preferably a carbonyl group, —COCH ₂ —, a sulfonyl group, —CONH— , —CSNH—, more preferably a carbonyl group, —COCH ₂ —, and particularly preferably a carbonyl group.

X ₂ represents a polycyclic alicyclic hydrocarbon group and is non-acid-decomposable. The total number of carbon atoms of the polycyclic alicyclic hydrocarbon group is preferably 5 to 40, and more preferably 7 to 30. The polycyclic alicyclic hydrocarbon group may have an unsaturated bond in the ring.
Such a polycyclic alicyclic hydrocarbon group is a group having a plurality of monocyclic alicyclic hydrocarbon groups or a polycyclic alicyclic hydrocarbon group, and may be a bridged type. The monocyclic alicyclic hydrocarbon group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Having a plurality of groups. The group having a plurality of monocyclic alicyclic hydrocarbon groups preferably has 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferably has two.

  Examples of the polycyclic alicyclic hydrocarbon group include a group having a bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms, and a group having a polycyclic cyclo structure having 6 to 30 carbon atoms is preferable. And adamantyl group, norbornyl group, norbornenyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclododecyl group, and androstanyl group. A part of carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

The polycyclic alicyclic hydrocarbon groups described above X _2, preferably an adamantyl group, a decalin group, a norbornyl group, a norbornenyl group, a cedrol group, a group having a plurality of cyclohexyl groups, having plural groups cycloheptyl group, a cyclooctyl group A group having a plurality, a group having a plurality of cyclodecanyl groups, a group having a plurality of cyclododecanyl groups, and a tricyclodecanyl group, and an adamantyl group is most preferable from the viewpoint of dry etching resistance. The chemical formula of the polycyclic alicyclic hydrocarbon structure in the polycyclic alicyclic hydrocarbon group of X ₂ is the same as the chemical formula of the polycyclic alicyclic hydrocarbon structure in the group having the polycyclic alicyclic hydrocarbon structure described above. The preferable range is also the same. Examples of the polycyclic alicyclic hydrocarbon group represented by X ₂ include a monovalent group having any one hydrogen atom in the above-described polycyclic alicyclic hydrocarbon structure as a bond.

Further, the alicyclic hydrocarbon group may have a substituent, and examples of the substituent include the same as those described above as the substituent that the polycyclic alicyclic hydrocarbon structure may have.
The substitution position of —O—Y—X ₂ in the general formula (4) may be the para position, the meta position, or the ortho position with respect to the bonding position of the benzene ring to the polymer main chain, but the para position is preferred.

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

In General Formula (4 ′), R ₁₃ represents a hydrogen atom or a methyl group.
R ₁₃ in formula (4 ′) represents a hydrogen atom or a methyl group, and a hydrogen atom is particularly preferable.
The substitution position of the adamantyl ester group in the general formula (4 ′) may be in the para position, the meta position, or the ortho position with respect to the bonding position with the polymer main chain of the benzene ring, but the para position is preferred.

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

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

The compound (B) as the polymer compound used in the present invention preferably further has the following repeating units (hereinafter, also referred to as “other repeating units”) as repeating units other than the above repeating units.
Examples of polymerizable monomers for forming these other repeating units include styrene, alkyl-substituted styrene, alkoxy-substituted styrene, halogen-substituted styrene, O-alkylated styrene, O-acylated styrene, hydrogenated hydroxystyrene, and anhydrous maleic acid. Acid, acrylic acid derivative (acrylic acid, acrylic ester, etc.), methacrylic acid derivative (methacrylic acid, methacrylic ester, etc.), N-substituted maleimide, acrylonitrile, methacrylonitrile, vinyl naphthalene, vinyl anthracene Inden etc. which may be sufficient can be mentioned.

  The compound (B) as the polymer compound may or may not contain these other repeating units, but when it is contained, the content in the compound (B) as the polymer compound of these other repeating units. Is generally 1 to 30 mol%, preferably 1 to 20 mol%, more preferably 2 to 10 mol%, based on all repeating units constituting the compound (B) as the polymer compound.

  The compound (B) as the polymer compound can be synthesized by a known radical polymerization method, anion polymerization method or living radical polymerization method (such as an iniferter method). For example, in an anionic polymerization method, a vinyl monomer can be dissolved in a suitable organic solvent, and a polymer can be obtained by usually reacting under a cooling condition using a metal compound (such as butyl lithium) as an initiator.

  As the compound (B) as the polymer compound, a polyphenol compound produced by a condensation reaction of an aromatic ketone or aromatic aldehyde and a compound containing 1 to 3 phenolic hydroxyl groups (for example, JP 2008-145539 A). ), Calixarene derivatives (for example, Japanese Patent Application Laid-Open No. 2004-18421), Noria derivatives (for example, Japanese Patent Application Laid-Open No. 2009-222920), and polyphenol derivatives (for example, Japanese Patent Application Laid-Open No. 2008-94782) can also be applied. good.

Further, the compound (B) as the polymer compound is preferably synthesized by modifying a polymer synthesized by a radical polymerization method or an anion polymerization method by a polymer reaction.
The weight average molecular weight of the compound (B) as the polymer compound is preferably 1000 to 200000, more preferably 2000 to 50000, and still more preferably 2000 to 15000.

The dispersity (molecular weight distribution) (Mw / Mn) of the compound (B) as the polymer compound is preferably 2.0 or less, and preferably from 1.0 to 1. from the viewpoint of improving sensitivity and resolution. 80, more preferably 1.0 to 1.60, and most preferably 1.0 to 1.20. Use of living polymerization such as living anionic polymerization is preferable because the degree of dispersion (molecular weight distribution) of the resulting polymer compound becomes uniform. The weight average molecular weight and dispersity of the compound (B) as the polymer compound are defined as polystyrene converted values by GPC measurement.
The amount of compound (B) added to the composition of the present invention is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, particularly preferably 50 to 85% by mass, based on the total solid content of the composition. Used.

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

[3] Crosslinking agent (C)
The composition of the present invention contains a crosslinking agent (C) (hereinafter also referred to as “compound (C)” or “crosslinking agent”). The compound (C) is preferably a compound having an acid crosslinkable group, and is preferably a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in the molecule. Moreover, it is preferable that a compound (C) contains the methylol group from a viewpoint of LER improvement.
Moreover, the compound (B) demonstrated above and a crosslinking agent (C) may be the same components.

First, the case where the compound (C) is a low molecular compound will be described (hereinafter referred to as the compound (C ′)). The compound (C ′) is preferably a hydroxymethylated or alkoxymethylated phenol compound, an alkoxymethylated melamine compound, an alkoxymethylglycoluril compound, and an alkoxymethylated urea compound. Particularly preferred compounds (C ′) include phenol derivatives and alkoxymethyl glycols containing 3 to 5 benzene rings in the molecule, and further having two or more hydroxymethyl groups or alkoxymethyl groups, and a molecular weight of 1200 or less. Examples include uril derivatives.
As the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable.

  Among the examples of the 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. A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst.

  Examples of another preferable compound (C ′) further have an N-hydroxymethyl group or an N-alkoxymethyl group such as alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds, and alkoxymethylated urea compounds. A compound can be mentioned.

Examples of such compounds include hexamethoxymethyl melamine, hexaethoxymethyl melamine, tetramethoxymethyl glycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethylene urea, bismethoxymethyl urea, and the like. 133, 216A, West German Patent 3,634,671, 3,711,264, EP 0,212,482A.
Of the specific examples of the compound (C ′), those particularly preferred are listed below.

Wherein, L ₁ ~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 the present invention, the content of the compound (C ′) is preferably 3 to 65% by mass, more preferably 5 to 50% by mass in the total solid content of the composition. By making the content rate of a compound (C ') into the range of 3-65 mass%, while maintaining that the remaining film rate and resolving power fall, the stability at the time of the preservation | save of the composition of this invention is kept favorable. be able to.

In the present invention, the compound (C ′) may be used alone or in combination of two or more. From the viewpoint of a good pattern shape, it is preferable to use a combination of two or more.
For example, in addition to the above-described phenol derivative, in the case where another compound (C ′), for example, the above-described compound having an N-alkoxymethyl group is used in combination, the ratio of the above-described phenol derivative to the other compound (C ′) is The molar ratio is usually 90/10 to 20/80, preferably 85/15 to 40/60, more preferably 80/20 to 50/50.

  Compound (C) may be in the form of a resin containing a repeating unit having an acid-crosslinkable group (hereinafter also referred to as compound (C ″)). In such an embodiment, the molecular unit of the repeating unit contains Since it contains a cross-linking group, it has higher cross-linking reactivity than a normal resin + cross-linking agent system, so that a hard film can be formed, and acid diffusibility and dry etching resistance can be controlled. As a result, the diffusibility of the acid in the exposed part of actinic rays or radiation such as an electron beam or extreme ultraviolet rays is greatly suppressed, so that the resolution, pattern shape and LER in a fine pattern are excellent. When the reaction point of the resin and the reaction point of the crosslinking group are close to each other as in the repeating unit represented by (1), the composition has an improved sensitivity during pattern formation.

Examples of the compound (C ″) include a resin containing a repeating unit represented by the following general formula (1). The repeating unit represented by the general formula (1) may have a substituent. It is a structure containing at least one good methylol group.
Here, the “methylol group” is a group represented by the following general formula (M), and in one embodiment of the present invention, a hydroxymethyl group or an alkoxymethyl group is preferable.

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

  First, general formula (1) will be described.

In 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 of 0 to 4.
n represents an integer of 1 to 5.
m + n is 5 or less.
When m is 2 or more, the plurality of Y may be the same as or different from each other.
When n is 2 or more, the plurality of R ₂ , R ₃ and Z may be the same as or different from each other.
Two or more of Y, R ₂ , R ₃ and Z may be bonded to each other to form a ring structure.
R ₁ , R ₂ , R ₃ , L and Y may each have a substituent.

When m is 2 or more, a plurality of Y may be bonded to each other through a single bond or a linking group to form a ring structure.
Moreover, the repeating unit represented by the general formula (1) is preferably represented by the following general formula (2) or (3).

In general formulas (2) and (3),
R ₁ , R ₂ , R ₃ , Y, Z, m and n are as defined in the general formula (1).
Ar represents an aromatic ring.
W ₁ and W ₂ represent a divalent linking group or a single bond.

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

R ₁ , Y, Z, m and n in the general formulas (2 ′) and (3 ′) have the same meanings as the groups in the general formula (1). Ar in the general formula (2 ′) has the same meaning as Ar in the general formula (2).
In the general formula (3 ′), W ₃ is a divalent linking group.

In the said general formula (2 ') and (3'), f is an integer of 0-6.
In the general formulas (2 ′) and (3 ′), g is 0 or 1.

  The general formula (2 ′) is particularly preferably represented by any one of the following general formulas (1-a) to (1-c). The compound (C ″) particularly preferably contains a repeating unit represented by any one of the following general formulas (1-a) to (1-c) or a repeating unit represented by the above general formula (3 ′). .

R ₁ , Y and Z in the general formulas (1-a) to (1-c) have the same meanings as the groups in the general formula (1).
In the general formulas (1-b) to (1-c),
Y ″ represents a hydrogen atom or a monovalent substituent. However, Y ″ may be a methylol group.
R ₄ represents a hydrogen atom or a monovalent substituent.
f represents an integer of 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 3 to 40 mol%, more preferably 5 to 30 mol%, based on all the repeating units of the compound (C ″). It is more preferable.
The content of the compound (C ″) is preferably 5 to 50% by mass and more preferably 10 to 40% by mass in the total solid content of the composition.

The compound (C ″) may contain two or more repeating units having an acid crosslinkable group, or two or more compounds (C ″) may be used in combination. Further, the compound (C ′) and the compound (C ″) can be used in combination.
Specific examples of the repeating unit having an acid crosslinkable group contained in the compound (C ″) include the following structures.

[4] Compound (D) that generates acid upon irradiation with actinic rays or radiation
The composition of the present invention differs from the onium salt compound (A) in that it generates an acid upon irradiation with actinic rays or radiation (hereinafter referred to as “compound (D)”, “acid generator” or “photoacid generation”). It is preferable to contain an agent.
Preferred forms of the acid generator include onium salt compounds. Examples of such onium salt compounds include sulfonium salts, iodonium salts, phosphonium salts, and the like.

Another preferred form of the acid generator includes a compound that generates sulfonic acid, imide acid, or methide acid upon irradiation with actinic rays or radiation. Examples of the acid generator in the form include a sulfonium salt, an iodonium salt, a phosphonium salt, an oxime sulfonate, and an imide sulfonate.
As an acid generator that can be used in the present invention, not only a low molecular compound, but also a compound in which a group capable of generating an acid upon irradiation with actinic rays or radiation is introduced into the main chain or side chain of a polymer compound can be used.

The acid generator is preferably a compound that generates an acid upon irradiation with an electron beam or extreme ultraviolet rays.
In the present invention, preferred onium salt compounds include sulfonium compounds represented by the following general formula (7) or iodonium compounds represented by the general formula (8).

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

R _a1 , R _a2 and R _a3 in the general formula (7), and R _a4 and R _a5 in the general formula (8) each independently represent an organic group, preferably R _a1 , At least one of R _a2 and R _a3 and at least one of R _a4 and R _a5 are each an aryl group. As the aryl group, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
Examples of the organic anion of X ^{− in} the general formulas (7) and (8) include a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, and preferably the following general anions An organic anion represented by the formula (9), (10) or (11), more preferably an organic anion represented by the following general formula (9).

In the general formulas (9), (10) and (11), R _c1 , R _c2 , R _c3 and R _c4 each independently represents an organic group.
The X ⁻ organic anion corresponds to sulfonic acid, imide acid, methide acid, and the like, which are acids generated by actinic rays or radiation such as electron beams and extreme ultraviolet rays.
Examples of the organic group of R _c1 , R _c2 , R _c3 and R _c4 include an alkyl group, an aryl group, or a group in which a plurality of these groups are linked. Of these organic groups, the 1-position is more preferably an alkyl group substituted with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity generated by light irradiation is increased and the sensitivity is improved. However, the terminal group preferably does not contain a fluorine atom as a substituent.

  The pKa of the acid generated from the compound (D) upon irradiation with actinic rays or radiation is preferably −10 or more and 2 or less, more preferably −5 or more and 1 or less, and −4 or more, 0 More preferably, it is as follows.

Then, in the present invention, compound (D), to suppress the diffusion of the non-exposed portion of the exposed acid, from the viewpoint of improving the resolution and pattern shape, volume 130 Å ³ or more the size of the acid ( preferably more preferably a compound capable of generating a sulfonic acid), the volume is more preferably 190 Å ³ or more the size of the acid (more preferably a compound capable of generating a sulfonic acid), volume 270 Å ³ or more dimensions More preferably, the compound generates an acid (more preferably sulfonic acid), and particularly preferably a compound that generates an acid having a volume of 400 to ³ or more (more preferably sulfonic acid). However, from the viewpoints of sensitivity and coating solvent solubility, the volume is preferably 2000 ³ or less, and more preferably 1500 ³ or less.
The value of the volume can be measured in the same manner as the volume of the acid generated from the onium salt compound (A) represented by the general formula (1) by irradiation with actinic rays or radiation.

In the present invention, particularly preferred acid generators are shown below. In addition, the calculated value of the volume is appended to a part of the example (unit ^{３ 3} ). In addition, the calculated value calculated | required here is a volume value of the acid which the proton couple | bonded with the anion part.

In addition, as the acid generator (preferably onium compound) used in the present invention, a group in which an acid is generated by irradiation with actinic rays or radiation (photoacid generating group) is introduced into the main chain or side chain of the polymer compound. Molecular acid generators can also be used.
The content of the acid generator in the composition is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, and still more preferably based on the total solid content of the composition. 1 to 18% by mass.
An acid generator can be used individually by 1 type or in combination of 2 or more types.

In one aspect, the composition of the present invention is a composition suitably used for exposure to electron beams or extreme ultraviolet rays.
Additional components that may be included in the composition according to the present invention include [5] basic compound, [6] surfactant, [7] organic carboxylic acid, [8] carboxylic acid onium salt, [9] acid proliferating agent, And [10] solvent. The composition of the present invention can be used for pattern formation, for example, according to a method described later as “pattern formation method”.

[5] Basic 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, the change in performance over time from exposure to post-heating can be reduced. Such basic compounds are preferably organic basic compounds, and more specifically, aliphatic amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, and sulfonyl groups. A nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like. Amine oxide compound (described in JP-A-2008-102383), ammonium salt (preferably hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is LER. Is preferable from the viewpoint).

Furthermore, a compound whose basicity is increased by the action of an acid can also be used as one kind of basic compound.
Specific examples of amines include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, tetradecylamine, pentadecylamine. , Hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N-dihexylaniline, 2,6- Diisopropylaniline, 2,4,6-tri (t-butyl) aniline, triethanolamine, N, N-dihydroxyethylaniline, tris (methoxyethoxyethyl) amine, and columns 3, 60 of US Pat. No. 6,040,112. Beyond And 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and U.S. Patent Application Publication No. 2007 / 0224539A1. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above. Examples of the compound having a nitrogen-containing heterocyclic structure include 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, N-hydroxyethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl ) Sebacate, 4-dimethylaminopyridine, antipyrine, hydroxyantipyrine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] -undec-7-ene And tetrabutylammonium hydroxide.

In addition, a photobasic generator (for example, a compound described in JP 2010-243773 A) is also used as appropriate.
Among these basic compounds, ammonium salts are preferable from the viewpoint of improving resolution.

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

[6] Surfactant The composition of the present invention may further contain a surfactant in order to improve coatability. Examples of surfactants include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Nonionic surfactants such as sorbitan fatty acid ester, Megafac F171 and Megafac F176 (manufactured by DIC Corporation), Florard FC430 (manufactured by Sumitomo 3M), Surfynol E1004 (manufactured by Asahi Glass), PF656 and PF6320 manufactured by OMNOVA And fluorine-based surfactants such as organosiloxane polymers and polysiloxane polymers.

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

[7] Organic carboxylic acid The composition of the present invention preferably contains an organic carboxylic acid in addition to the above components. Examples of such organic carboxylic acid compounds include aliphatic carboxylic acid, alicyclic carboxylic acid, unsaturated aliphatic carboxylic acid, oxycarboxylic acid, alkoxycarboxylic acid, ketocarboxylic acid, benzoic acid derivative, phthalic acid, terephthalic acid, isophthalic acid , 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, and the like, but when performing electron beam exposure under vacuum, it volatilizes from the resist film surface. Since there is a possibility of contaminating the inside of the drawing chamber, preferred examples of the compound are aromatic organic carboxylic acids, among which benzoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid are suitable. is there.

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

  If necessary, the composition of the present invention may further comprise a dye, a plasticizer, an acid proliferating agent (WO95 / 29968, WO98 / 24000, JP-A-8-305262, No. 9-34106, JP-A-8-248561, JP-T 8-503082, U.S. Pat. No. 5,445,917, JP-A-8-503081, JP-A-5-503081 534,393, US Pat. No. 5,395,736, US Pat. No. 5,741,630, US Pat. No. 5,334,489, US Pat. No. 5,582 No. 956, US Pat. No. 5,578,424, US Pat. No. 5,453,345, US Pat. No. 5,445,917, EP 665,960 , European Patent No. 7 No. 7,628, European Patent No. 665,961, US Pat. No. 5,667,943, JP-A-10-1508, JP-A-10-282642, JP-A-9-512498. No. 2000, No. 2000-62337, No. 2005-17730, No. 2008-209889, and the like. As for these compounds, the respective compounds described in JP-A-2008-268935 can be mentioned.

[8] Carboxylic acid onium salt The composition of the present invention may contain a carboxylic acid onium salt. Examples of the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt. In particular, the carboxylic acid onium salt is preferably a carboxylic acid sulfonium salt or a carboxylic acid iodonium salt. Furthermore, in this invention, it is preferable that the carboxylate residue of carboxylic acid onium salt does not contain an aromatic group and a carbon-carbon double bond. As a particularly preferable anion moiety, a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.

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

[9] Acid Proliferating Agent The composition of the present invention may further contain one or more compounds that generate an acid upon decomposition by the action of an acid (hereinafter also referred to as an acid proliferating agent). The acid generated by the acid proliferating agent is preferably sulfonic acid, methide acid or imide acid. The content of the acid proliferating agent is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the total solid content of the composition, and 1.0 to More preferably, it is 20 mass%.

  As a quantitative ratio between the acid proliferator and the acid generator (solid content of the acid proliferator based on the total solid content in the composition / solid content of the acid generator based on the total solid content in the composition) Although not particularly limited, 0.01 to 50 is preferable, 0.1 to 20 is more preferable, and 0.2 to 1.0 is particularly preferable.

  Although the example of the acid growth agent which can be used for this invention below is shown, it is not limited to these.

[10] Solvent The composition of the present invention may contain a solvent, and examples of the solvent include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2- Propanol), propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate , Β-methoxyisobutyrate methyl, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate , Diacetone alcohol, N- methylpyrrolidone, N, N- dimethylformamide, .gamma.-butyrolactone, N, N- dimethylacetamide, propylene carbonate, and ethylene carbonate is preferred. These solvents are used alone or in combination.

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

<Resist film and mask blanks>
The present invention also relates to a resist film formed from the composition of the present invention. Such a film is formed, for example, by applying the composition of the present invention on a support such as a substrate. The thickness of this film is preferably 0.02 to 0.1 μm. As a method for coating on the substrate, spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. are applied on the substrate, but spin coating is preferred, and the number of rotations is 1000 to 3000 rpm is preferable. The coating film is pre-baked at 60 to 150 ° C. for 1 to 20 minutes, preferably 80 to 120 ° C. for 1 to 10 minutes to form a thin film.

For example, in the case of a semiconductor wafer, a silicon wafer can be used as the material constituting the substrate to be processed and its outermost layer. Examples of the material that becomes the outermost layer include Si, SiO ₂ , SiN, SiON, TiN, Examples thereof include WSi, BPSG, SOG, and an organic antireflection film.

  The present invention also relates to a mask blank provided with a resist film obtained as described above. In order to obtain a mask blank having such a resist film, when forming a pattern on a photomask blank for producing a photomask, the transparent substrate used may be a transparent substrate such as quartz or calcium fluoride. be able to. In general, a light-shielding film, an antireflection film, a phase shift film, and additional functional films such as an etching stopper film and an etching mask film are laminated on the substrate. As a material for the functional film, a film containing a transition metal such as silicon or chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium is laminated. In addition, as a material used for the outermost layer, silicon or a material containing oxygen and / or nitrogen in silicon as a main constituent material, and further a silicon compound material containing a transition metal-containing material as a main constituent material Or a transition metal, in particular, one or more selected from chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium, etc., or a material further containing one or more elements selected from oxygen, nitrogen, and carbon The transition metal compound material is exemplified.

  The light shielding film may be a single layer, but more preferably has a multilayer structure in which a plurality of materials are applied. In the case of a multilayer structure, the thickness of the film per layer is not particularly limited, but is preferably 5 to 100 nm, and more preferably 10 to 80 nm. Although it does not restrict | limit especially as thickness of the whole light shielding film, It is preferable that it is 5-200 nm, and it is more preferable that it is 10-150 nm.

  Among these materials, when a pattern is formed using a composition on a photomask blank generally comprising a material containing oxygen or nitrogen in chromium as the outermost layer, a constricted shape is formed in the vicinity of the substrate. Although the so-called undercut shape tends to be obtained, the use of the present invention can improve the undercut problem as compared with the conventional one.

  Next, the resist film is irradiated with actinic rays or radiation (such as an electron beam) (hereinafter also referred to as “exposure”), and preferably baked (usually 80 to 150 ° C., more preferably 90 to 130 ° C.). ,develop. Thereby, a good pattern can be obtained. Then, using this pattern as a mask, etching processing, ion implantation, and the like are performed as appropriate to create a semiconductor microcircuit, an imprint mold structure, and the like.

  In addition, about the process in the case of producing the mold for imprints using the composition of this invention, patent 4109085 gazette, Unexamined-Japanese-Patent No. 2008-162101, and "Nanoimprint basics and technical development. Application Development-Nanoimprint Substrate Technology and Latest Technology Development-Editing: Yoshihiko Hirai (Frontier Publishing) "

<Pattern formation method>
The composition of this invention can be used suitably for the formation process of the negative pattern shown below. That is, a resist film is formed by coating the composition of the present invention on a substrate, the resist film is irradiated with actinic rays or radiation (that is, exposed), and the exposed film is developed using a developer. Thus, it can be preferably used in a process including obtaining a negative pattern. As such a process, for example, the processes described in JP 2008-292975 A, JP 2010-217884 A, and the like can be used.

  The present invention includes exposing the resist film or the mask blank provided with the film, and developing the exposed resist film or the mask blank including the exposed film. It also relates to a pattern forming method. In the present invention, the exposure is preferably performed using an electron beam or extreme ultraviolet rays.

In the production of a precision integrated circuit element or the like, the exposure (pattern formation step) on the resist film is preferably performed by first irradiating the resist film of the present invention with an electron beam or extreme ultraviolet rays (EUV). In the case of an electron beam, the exposure amount is about 0.1 to 20 μC / cm ² , preferably about 3 to 10 μC / cm ² , and in the case of extreme ultraviolet light, about 0.1 to 20 mJ / cm ² , preferably 3 to 15 mJ / the exposure so that the cm ^2. Next, post-exposure baking (post-exposure baking) is performed on a hot plate at 60 to 150 ° C. for 1 to 20 minutes, preferably 80 to 120 ° C. for 1 to 10 minutes, followed by development, rinsing and drying. Form a pattern.
The developer is appropriately selected, but it is preferable to use an alkali developer (typically an alkaline aqueous solution) or a developer containing an organic solvent (also referred to as an organic developer). When the developer is an alkaline aqueous solution, 0.1 to 5% by mass, preferably 2-3% by mass alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), The development is performed for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as a dip method, a paddle method, or a spray method. An appropriate amount of alcohol and / or surfactant may be added to the alkaline developer. Thus, the unexposed portion of the film is dissolved, and the exposed portion is hardly dissolved in the developer, and a target pattern is formed on the substrate.

When the resist pattern forming method of the present invention includes a step of developing using an alkali developer, examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia. Inorganic alkalis such as water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, Alcohol amines such as ethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, teto Hexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, tetraalkylammonium hydroxide, trimethylphenylammonium hydroxide, trimethyl Alkaline aqueous solutions such as quaternary ammonium salts such as benzylammonium hydroxide and triethylbenzylammonium hydroxide, and cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.

As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.
In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

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

In the present invention, the ester solvent is a solvent having an ester group in the molecule, the ketone solvent is a solvent having a ketone group in the molecule, and the alcohol solvent is alcoholic in the molecule. It is a solvent having a hydroxyl group, an amide solvent is a solvent having an amide group in the molecule, and an ether solvent is a solvent having an ether bond in the molecule. Among these, there is a solvent having a plurality of types of the above functional groups in one molecule. In that case, it corresponds to any solvent type including the functional group of the solvent. For example, diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification. Further, the hydrocarbon solvent is a hydrocarbon solvent having no substituent.
In particular, a developer containing at least one kind of solvent selected from ketone solvents, ester solvents, alcohol solvents and ether solvents is preferable.

The developer has 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10), and 2 or less heteroatoms, from the viewpoint that the swelling of the resist film can be suppressed. It is preferable to use the ester solvent.
The hetero atom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms is preferably 2 or less.
Preferred examples of the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, Examples include heptyl propionate and butyl butanoate, and it is particularly preferable to use isoamyl acetate.

Instead of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms, the developer may be a mixed solvent of the ester solvent and the hydrocarbon solvent, or the ketone solvent and the carbonized solvent. A mixed solvent of hydrogen solvent may be used. Even in this case, it is effective in suppressing the swelling of the resist film.
When an ester solvent and a hydrocarbon solvent are used in combination, isoamyl acetate is preferably used as the ester solvent. As the hydrocarbon solvent, it is preferable to use a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of adjusting the solubility of the resist film.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyric acid Examples include butyl and methyl 2-hydroxyisobutyrate.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, 4-methyl-2-pentanol, tert-butyl alcohol, isobutyl alcohol, n -Alcohols such as hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, may be mentioned glycol monoethyl ether and methoxymethyl butanol.
Examples of the ether solvent include anisole, dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyrate formate , Ester solvents such as propyl formate, ethyl lactate, butyl lactate and propyl lactate, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n Alcohol solvents such as heptyl alcohol, n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene Glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl Glycol ether solvents such as butanol, ether solvents such as tetrahydrofuran, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and aromatic hydrocarbons such as toluene and xylene And aliphatic hydrocarbon solvents such as octane and decane.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropio , Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, Alcohol solvents such as alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol, triethylene glycol, etc. Glycol solvents, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol ether solvents such as methoxymethyl butanol, N- Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Amide solvents, aromatic hydrocarbon solvents such as xylene, octane, decane, include aliphatic hydrocarbon solvents undecane.

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

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-334540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and particularly preferably 0.0005 to 1% by mass with respect to the total amount of the developer.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

  Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.

  Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using the developing solution containing an organic solvent.

  After the step of developing with a developer containing an organic solvent, a step of washing with a rinse solution may be included. From the viewpoint of throughput (productivity), the amount of rinse solution used, etc. It is not necessary to include the step of using and washing.

The rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. . As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.
More preferably, after the step of developing using a developer containing an organic solvent, a rinse solution containing at least one organic solvent selected from the group consisting of ester solvents, alcohol solvents, and hydrocarbon solvents is used. It is preferable to perform a cleaning step using a rinsing liquid containing an alcohol solvent or a hydrocarbon solvent.

As the organic solvent contained in the rinsing liquid, it is also preferable to use a hydrocarbon solvent among the organic solvents, and it is more preferable to use an aliphatic hydrocarbon solvent. As the aliphatic hydrocarbon solvent used in the rinsing liquid, an aliphatic hydrocarbon solvent having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, Hexadecane, etc.) are preferred, aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.
In addition, although the upper limit of the carbon atom number of the said aliphatic hydrocarbon solvent is not specifically limited, For example, 16 or less is mentioned, 14 or less is preferable and 12 or less is more preferable.
Among the above fat-side hydrocarbon solvents, decane, undecane, and dodecane are particularly preferable, and undecane is most preferable.
By using a hydrocarbon solvent (especially an aliphatic hydrocarbon solvent) as the organic solvent contained in the rinsing liquid, the developer slightly soaked into the resist film after development is washed away, and swelling is further suppressed. Thus, the effect of suppressing pattern collapse is further exhibited.

  A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.

  The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

  The vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution.

  In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. Moreover, it is also preferable to include a heating process (PostBake) after the rinsing process. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  The composition of the present invention is preferably a resist composition, and is typically a negative resist composition used for the formation of a negative pattern, so that the unexposed film is dissolved and the exposed part is a compound. It is difficult to dissolve in the developer due to the crosslinking of. By utilizing this, a target pattern can be formed on the substrate.

The present invention also relates to a method for manufacturing an electronic device including the pattern forming method of the present invention described above.
The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

<Synthesis Example 1; Synthesis of Compound (A-1)>
20 g of ion exchange resin (QAE Sephadex A-25) manufactured by GE Healthcare Biosciences was swollen with ultrapure water all day and night, and then filled into a column tube. A solution obtained by dissolving 28 g of sodium benzenesulfinic acid salt represented by the following formula (X-1) in methanol was poured into a column tube filled with an ion exchange resin, thereby supporting the sulfin anion on the ion exchange resin. After flashing back with a sufficient amount of methanol, a solution of 5.2 g of triphenylsulfonium chloride dissolved in methanol was poured into the column tube to carry out an anion exchange reaction. The solvent of the obtained solution was distilled off with an evaporator, and then dried overnight at room temperature to obtain a compound represented by the formula (A-1) (hereinafter also referred to as “compound (A-1)”) ( Yield 7.0 g).
In the same manner as in the synthesis of compound (A-1), (A-9) was synthesized from compound (A-2) shown in Table 1. Table 1 also shows the structures of comparative compounds (R1) to (R4) used as comparative examples.

<Examples 1E to 19E and Comparative Examples 1E to 4E: electron beam exposure; negative type; alkali development>
(1) Preparation of Support A 6-inch wafer on which Cr oxide was vapor-deposited (prepared with a shielding film used for ordinary photomask blanks) was prepared.

(2) Preparation of resist coating liquid (coating liquid composition of chemically amplified negative resist composition N1)
Compound (A-1) (the structural formula is the above) 0.04 g
Photoacid generator (z61) (structural formula is below) 0.47 g
Compound (P2) (structural formula is below) 4.68 g
Cross-linking agent CL-1 (structural formula below) 0.59 g
Cross-linking agent CL-4 (the structural formula is shown below) 0.30 g
2-hydroxy-3-naphthoic acid (organic carboxylic acid) 0.11 g
Surfactant PF6320 (manufactured by OMNOVA) 0.005g
75.0 g of propylene glycol monomethyl ether acetate (solvent S2)
Propylene glycol monomethyl ether (solvent S1) 18.8 g

The composition solution was microfiltered with a polytetrafluoroethylene filter having a pore size of 0.04 μm to obtain a resist coating solution.
Chemical amplification negative resist compositions N2 to N19, chemical amplification negative resist comparison, similar to the chemical amplification negative resist composition N1, except that the components listed in Table 2 below were used as the resist liquid formulation Compositions N1-N4 were prepared.

  Abbreviations of components other than those used above in the examples / comparative examples are described below.

  [Compound containing phenolic hydroxyl group (compound (B))]

  [Photoacid generator (compound (D))]

  [Crosslinking agent (compound (C))]

[Organic carboxylic acid]
D1: 2-hydroxy-3-naphthoic acid D2: 2-naphthoic acid D3: benzoic acid

[Surfactant]
W-1: PF6320 (manufactured by OMNOVA)
W-2: Megafuck F176 (manufactured by DIC Corporation; fluorine-based)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)

〔solvent〕
S1: Propylene glycol monomethyl ether (1-methoxy-2-propanol)
S2: Propylene glycol monomethyl ether acetate (1-methoxy-2-acetoxypropane)
S3: 2-Heptanone S4: Propylene carbonate

(3) Preparation of resist film A resist coating solution is applied onto the 6-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron, and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 50 nm. It was. That is, resist-coated mask blanks were obtained.

(4) Production of Negative Resist Pattern Pattern irradiation was performed on this resist film using an electron beam drawing apparatus (manufactured by Elionix Co., Ltd .; ELS-7500, acceleration voltage 50 KeV). After irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried.

(5) Evaluation of resist pattern The obtained pattern was evaluated for sensitivity and isolated space pattern resolving power by the following methods.

〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). The exposure amount when resolving a 1: 1 line and space resist pattern with a line width of 50 nm was defined as sensitivity. The smaller this value, the higher the sensitivity.

[Isolated space pattern resolution]
The critical resolving power (minimum space width at which lines and spaces were separated and resolved) of the isolated space pattern (line: space = 100: 1) at the above sensitivity was determined. This value was defined as “isolated space pattern resolving power (nm)”. The smaller this value, the better the performance.

  The evaluation results are shown in Table 3.

  From the results shown in Table 3, it can be seen that the composition of the present invention is excellent in sensitivity and isolated space pattern resolution in electron beam exposure.

<Examples 1F to 6F and Comparative Examples 1F to 4F: EUV exposure; negative type; alkali development>
The negative resist composition shown in Table 4 below was microfiltered with a polytetrafluoroethylene filter having a pore size of 0.04 μm to obtain a resist coating solution.

(Create resist film)
A resist coating solution was applied onto the 6-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron, and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 50 nm. That is, resist-coated mask blanks were obtained.

(Resist evaluation)
With respect to the obtained resist film, sensitivity and isolated space pattern resolving power were evaluated by the following methods.

  The resulting resist film was exposed using EUV light (wavelength 13 nm) through a reflective mask having a 1: 1 line and space pattern with a line width of 50 nm, and then baked at 110 ° C. for 90 seconds. Then, it developed using the 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution.

〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.). The exposure amount when resolving a 1: 1 line and space resist pattern with a line width of 50 nm was defined as sensitivity. The smaller this value, the higher the sensitivity.

Isolated space pattern resolution (EUV)
Irradiation energy when resolving a 1: 1 line and space pattern with a line width of 50 nm was defined as sensitivity (Eop).
The critical resolving power (minimum space width at which lines and spaces were separated and resolved) of the isolated space pattern (line: space = 5: 1) at the irradiation dose showing the above sensitivity was obtained. This value was defined as “isolated space pattern resolving power (nm)”.

  The evaluation results are shown in Table 4.

  From the results shown in Table 4, it can be seen that the composition according to the present invention is excellent in sensitivity and isolated space pattern resolution in EUV exposure.

<Examples 1C to 6C and Comparative Examples 1C to 4C: EB exposure; negative type; organic solvent development>
(1) Preparation of resist composition and production of resist film The compositions shown in Table 5 below were microfiltered with a membrane filter having a pore size of 0.1 μm to obtain a resist composition.

  This resist composition was applied onto a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and dried on a hot plate at 100 ° C. for 60 seconds to form a film. A resist film having a thickness of 50 nm was obtained.

(2) EB exposure and development The wafer coated with the resist film obtained in (1) above was subjected to pattern irradiation using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). . At this time, drawing was performed so that a 1: 1 line and space was formed. After the electron beam drawing, after heating at 110 ° C. for 60 seconds on a hot plate, paddle the organic developer shown in Table 5 and develop for 30 seconds, and rinse using the rinse solution shown in the same table. Thereafter, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds and then heated at 90 ° C. for 60 seconds to obtain a 1: 1 line and space pattern resist pattern having a line width of 50 nm.

  With respect to the obtained resist film, sensitivity and isolated space pattern resolving power were evaluated in the same manner as in Examples 1E to 19E and Comparative Examples 1E to 4E. The results are shown below.

上記実施例／比較例で用いた前掲以外の成分の略称を以下に記載する。

Abbreviations of components other than those used above in the examples / comparative examples are described below.

[Developer / Rinse solution]
S8: Butyl acetate S9: Pentyl acetate S10: Anisole S11: 1-Hexanol S12: Decane

  From the results shown in Table 5, it can be seen that the composition according to the present invention is excellent in sensitivity and isolated space pattern resolution in EB exposure.

Claims (14)

An actinic ray-sensitive or radiation-sensitive composition containing an onium salt compound (A) represented by the following general formula (1) and a crosslinking agent (C).

In the general formula (1),
M represents an onium cation, and X represents an organic group.   Furthermore, the actinic-ray sensitive or radiation sensitive composition of Claim 1 containing the compound (B) containing a phenolic hydroxyl group.   Furthermore, the actinic-ray sensitive or radiation sensitive composition of Claim 1 or 2 containing the photo-acid generator (D) different from the said onium salt compound (A).   The actinic-ray sensitive or radiation sensitive composition of any one of Claims 1-3 whose X in the said General formula (1) is group which has an alicyclic structure.   The actinic-ray sensitive or radiation sensitive composition of any one of Claims 1-4 whose X in the said General formula (1) is group which has a polycyclic alicyclic structure. The actinic ray-sensitive or radiation-sensitive according to any one of claims 1 to 5, wherein the volume of the acid generated from the onium salt compound (A) upon irradiation with actinic rays or radiation is 210 ³ or more. Sex composition. The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 1 to 6, wherein the onium salt compound (A) is an onium salt compound represented by the following general formula (2).

In the general formula (2),
M represents an onium cation, and Y represents a hydrogen atom or an organic group.   The actinic ray-sensitive or radiation-sensitive composition according to claim 7, wherein Y in the general formula (2) is a group having a polycyclic alicyclic structure.   The actinic ray-sensitive or radiation-sensitive composition according to any one of claims 2 to 8, wherein the compound (B) containing a phenolic hydroxyl group does not have an acid-decomposable group.   The resist film formed with the actinic-ray-sensitive or radiation-sensitive composition of any one of Claims 1-9.   A mask blank comprising the resist film according to claim 10.   A pattern forming method comprising: irradiating the resist film according to claim 10 with actinic rays or radiation; and developing the film irradiated with the actinic rays or radiation.   The manufacturing method of an electronic device containing the pattern formation method of Claim 12.   A resist pattern forming method, comprising: irradiating a mask blank provided with the resist film according to claim 10 with actinic rays or radiation; and developing the mask blanks irradiated with the actinic rays or radiation.