WO2016163187A1

WO2016163187A1 - Negative active light sensitive or radiation sensitive resin composition, negative active light sensitive or radiation sensitive film, pattern forming method and method for manufacturing electronic device

Info

Publication number: WO2016163187A1
Application number: PCT/JP2016/056856
Authority: WO
Inventors: 金子　明弘; 修平山口
Original assignee: 富士フイルム株式会社
Priority date: 2015-04-07
Filing date: 2016-03-04
Publication date: 2016-10-13
Also published as: TW201636732A; KR20170125358A; JP6402245B2; KR102051343B1; TWI697732B; JPWO2016163187A1

Abstract

Provided are: a negative active light sensitive or radiation sensitive resin composition which is capable of forming a pattern having excellent sensitivity, resolution, PED stability and line edge roughness (LER) performance in the formation of an ultra-thin pattern; a negative active light sensitive or radiation sensitive film which uses this negative active light sensitive or radiation sensitive resin composition; a mask blank which uses this negative active light sensitive or radiation sensitive film; a pattern forming method; and a method for manufacturing an electronic device, which uses this pattern forming method. This negative active light sensitive or radiation sensitive resin composition contains (A) a polymer compound having a repeating unit represented by general formula (1), and (B) a compound which generates an acid having a volume of from 130 Å³ to 2,000 Å³ (inclusive) when irradiated with active light or radiation.

Description

Negative-type actinic ray-sensitive or radiation-sensitive resin composition, negative-type actinic ray-sensitive or radiation-sensitive film, pattern formation method, and electronic device manufacturing method

INDUSTRIAL APPLICABILITY The present invention can form highly refined patterns using electron beams and extreme ultraviolet rays, which are preferably used in ultramicrolithography processes such as the manufacture of VLSI and high-capacity microchips and other photofabrication processes. The present invention relates to a negative actinic ray-sensitive or radiation-sensitive resin composition, a negative-type actinic ray-sensitive or radiation-sensitive film, a pattern formation 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.

These electron beams, X-rays, or EUV light lithography are positioned as next-generation or next-generation pattern forming technologies, and high-sensitivity and high-resolution resist compositions are desired. As a resist composition suitable for negative lithography, a so-called negative chemically amplified resist composition mainly composed of an alkali-soluble resin, a crosslinking agent and an acid generator is effectively used (for example, see Patent Document 1). reference).

In the formation of a negative resist pattern, even when an unexposed portion intended to be removed by a developer and an exposed portion not intended to be removed by a developer are provided by exposure on the resist film, Of these, the area adjacent to the exposed portion is usually exposed with a low exposure amount (hereinafter, this region is referred to as “weakly exposed portion”). Therefore, even in the weakly exposed area, insolubilization or insolubilization with respect to the developing solution proceeds, causing a bridge between patterns formed by development.

On the other hand, as a negative chemically amplified resist composition containing an acid generator, a polymer having a crosslinking structure in which a crosslinking reaction proceeds with an acid and a site capable of crosslinking reaction with the crosslinking group, both in the polymer structure ( Hereinafter, "crosslinked support polymer") has been developed. In general negative chemically amplified resist compositions that are negatively processed using a low molecular crosslinker, volatilization of the low molecular crosslinker during the process is often a problem, but in a crosslinked support polymer, there is no such concern. There is an advantage. For example, Patent Document 2 describes a polymer having a methylol group as a crosslinkable group in a polymer having a phenolic hydroxyl group.

JP 2002-99085 A JP-A-2-170165

However, sufficient resolution has not been obtained in forming an ultrafine pattern having a line width of 50 nm or less.
Moreover, although further improvement of PED stability (coating film stability when it is allowed to stand until it performs heating operation (PEB) after exposure) is requested | required, in patent document 2, regarding PED stability, Not mentioned and in fact PED stability is insufficient.
Therefore, the object of the present invention is to form a pattern excellent in sensitivity, resolution, PED stability, and line edge roughness (LER) performance, particularly in the formation of an ultrafine pattern (for example, a line width of 50 nm or less). Negative-type active light-sensitive or radiation-sensitive resin composition, and negative-type active light-sensitive or radiation-sensitive film, negative-type active light-sensitive or radiation-sensitive film using the same An object of the present invention is to provide a mask blank, a pattern forming method, an electronic device manufacturing method including the pattern forming method, and an electronic device.

As a result of intensive studies, the present inventors have found that the above object can be achieved by a resist composition in which a polymer compound having a specific structure and a specific compound that generates an acid upon irradiation with actinic rays or radiation are combined. It was.

That is, the present invention is as follows.

[1]
(A) a polymer compound having a repeating unit represented by the following general formula (1) and (B) a compound that generates an acid having a volume of 130 to ^{3 to} 2000 to ³ by irradiation with actinic rays or radiation. Negative-type actinic ray-sensitive or radiation-sensitive resin composition.

In the formula, R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and R ₄ Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an acyl group, L represents a single bond or a divalent linking group, Ar represents an aromatic group, m and n are each independently, Represents an integer of 1 or more.
[2]
The negative actinic ray-sensitive or radiation-sensitive resin composition according to the above [1], wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (2).

_{_{_{Wherein, R 1, R 2, R}}} 3 and _{R 4} have the same meanings as in formula _{_{(1) R 1, R 2}} , R 3 and _{R 4} in. m ′ represents 1 or 2, and n ′ represents an integer of 1 to 3.
[3]
The negative actinic ray-sensitive or radiation-sensitive resin composition according to the above [2], wherein the repeating unit represented by the general formula (2) is a repeating unit represented by the following general formula (3).

_Wherein, R 2, _{R 3,} and _{R 4} in general formula (1) _R 2, _{R 3,} and is synonymous with _{R 4.} n ′ represents an integer of 1 to 3.
[4]
The negative actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3] above, wherein the compound (B) is a sulfonium salt.
[5]
Furthermore, the negative active light sensitive material according to any one of the above [1] to [4], which comprises a basic compound or an ammonium salt compound (C) whose basicity is lowered by irradiation with active light or radiation. Or a radiation sensitive resin composition.
[6]
The negative actinic ray-sensitive or radiation-sensitive resin composition according to [5] above, wherein the compound (C) is an onium salt compound represented by the following general formula (4).

In the formula, A represents a sulfur atom or an iodine atom, R _A represents a hydrogen atom or an organic group, R _B represents a (p + 1) -valent organic group, X represents a single bond or a linking group, and A _N represents Represents a basic moiety containing a nitrogen atom. When a plurality of R _A , R _B , X and A _N are present, they may be the same or different.
When A is a sulfur atom, q is an integer of 1 to 3, and o is an integer that satisfies the relationship of o + q = 3.
When A is an iodine atom, q is 1 or 2, and o is an integer that satisfies the relationship of o + q = 2.
p represents an integer of 1 to 10, and Y ⁻ represents an anion.
At least two of R _A , X, R _B and A _N may be bonded to each other to form a ring.
[7]
The negative actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6] above, wherein the polymer compound (A) has a dispersity of 1.0 to 1.40. .
[8]
Any of the above [1] to [7], wherein the polymer compound (A) is a polymer compound produced by a production method using a polymer of a repeating unit represented by the following general formula (5) as a raw material The negative actinic ray-sensitive or radiation-sensitive resin composition according to item 1.

_{R 1} in the formula has the same meaning as _{R 1} in the general formula (1).
[9]
The negative actinic ray-sensitive or radiation-sensitive resin composition as described in [8] above, wherein the polymer having a repeating unit represented by the general formula (5) has a dispersity of 1.0 to 1.20.
[10]
The negative actinic ray-sensitive or radiation-sensitive resin composition according to the above [3], wherein R ₂ and R ₃ in the general formula (3) are both hydrogen atoms.
[11]
A negative actinic ray-sensitive or radiation-sensitive film formed using the negative actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to [10] above.
[12]
Mask blanks comprising the negative actinic ray-sensitive or radiation-sensitive film as described in [11] above.
[13]
A step of forming a film by applying the negative actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10] on a substrate;
A pattern forming method comprising: exposing the film; and developing the exposed film to form a negative pattern.
[14]
The manufacturing method of an electronic device containing the pattern formation method as described in said [13].
[15]
The electronic device manufactured by the manufacturing method of the electronic device as described in said [14].

According to the present invention, in particular, in the formation of an ultrafine pattern (for example, a line width of 50 nm or less), a negative type sensitive activity capable of forming a pattern excellent in sensitivity, resolution, PED stability, and LER performance. Photosensitive or radiation sensitive resin composition, and negative actinic ray sensitive or radiation sensitive film using the same, mask blanks having negative actinic ray sensitive or radiation sensitive film, pattern forming method, and the above pattern An electronic device manufacturing method including a forming method and an electronic device can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is not limited to exposure with a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, EUV light, etc. Drawing with particle beams such as ion beams is also included in the exposure.
In the present specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the polymer compound and the resin are measured by GPC (solvent: HSO-8120GPC manufactured by Tosoh Corporation). Tetrahydrofuran, flow rate (sample injection amount): 10 μl, column: TSK gel Multipore HXL-M (× 4) manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refractive index (RI )) As a polystyrene equivalent value by detector).

The negative actinic ray-sensitive or radiation-sensitive resin composition of the present invention is
(A) a polymer compound having a repeating unit represented by the general formula (1) (hereinafter also referred to as “polymer compound (A)”);
(B) A compound that generates an acid having a volume of 130 ³ or more and 2000 ³ or less when irradiated with actinic rays or radiation (hereinafter also referred to as “acid generator (B)” or “compound (B)”).
Including.

Thereby, in the formation of an ultrafine pattern (for example, a region having a line width of 50 nm or less), a negative actinic ray-sensitive or radiation-sensitive resin composition excellent in sensitivity, resolution, PED stability, and LER performance. , Negative-type actinic ray-sensitive or radiation-sensitive film using the same, mask blanks having a negative-type actinic-ray-sensitive or radiation-sensitive film, a pattern formation method, a method for producing an electronic device including the pattern formation method, and An electronic device can be provided.

The reason why the above is achieved is that, in the present invention, the volume of the acid generated from the compound (B) by irradiation with actinic rays or radiation is as large as 130 ³ or more, and the diffusibility of the acid generated from the compound (B) is Low. This suppresses the diffusion of excess acid to the unexposed area, which is considered to improve the resolution in the ultrafine region. Moreover, it is thought that PED stability improves as a result that the diffusibility of the acid after exposure is low. However, in the present invention, high resolution that cannot be explained only by the above diffusivity was obtained. The reason is not clear, but the following is estimated.

The crosslinkable group-containing polymer typically has a large (bulky) crosslinkable structural site including a crosslinkable group in the side chain of the polymer (for example, JP-A-2014-24999), In the polymer compound (A) of the present invention, since the crosslinkable group is bonded to the benzene ring that is directly bonded to the main chain of the polymer compound, Compared with a very compact structure. In the case of a typical crosslinkable group-containing polymer, since it has a certain amount of free volume even after crosslinking, the effect of suppressing the diffusion of the acid generated in the exposed area is limited. In the case of a compact structure, it is presumed that the free volume after crosslinking is very small and the above-mentioned acid diffusion suppressing effect is larger than expected, and as a result, the resolution is very high. Moreover, it is estimated by this effect | action that it was excellent also in LER performance.

Hereinafter, the negative actinic ray-sensitive or radiation-sensitive resin composition according to the present invention will be described.
The negative actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is preferably for electron beam or extreme ultraviolet exposure, and more preferably for electron beam exposure.
The negative-type actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition for forming a negative pattern, and even if it is a negative resist composition for organic solvent development, alkali development A negative resist composition may be used. The composition according to the present invention is typically a chemically amplified resist composition.

Hereinafter, each component in the negative active light sensitive or radiation sensitive resin composition of the present invention will be described in detail.

[1] (A) Polymer Compound The polymer compound (A) is a polymer compound having a repeating unit represented by the following general formula (1).

In the formula, R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and R ₄ represents Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an acyl group, L represents a single bond or a divalent linking group, Ar represents an aromatic group, and m and n are each independently 1 It represents the above integer.

Examples of the halogen atom for R ₁ include fluorine, chlorine, bromine, and iodine. R ₁ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Examples of the divalent linking group represented by L include a monocyclic or polycyclic aromatic ring, —C (═O) —, —O—C (═O) —, —CH ₂ —O—C (═O )-, A thiocarbonyl group, a linear or branched alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6), a linear or branched alkenylene group (preferably having 2 to 10 carbon atoms) More preferably 2 to 6), a cycloalkylene group (preferably having 3 to 10 carbon atoms, more preferably 3 to 6), a sulfonyl group, —O—, —NH—, —S—, a cyclic lactone structure, or these. Examples thereof include a combined divalent linking group (preferably having a total carbon number of 1 to 50, more preferably a total carbon number of 1 to 30, and even more preferably a total carbon number of 1 to 20).

Ar represents an aromatic group. Preferred examples of the aromatic group include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, fluorene ring, phenanthrene ring, or, for example, thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring And aromatic ring heterocycles including heterocycles such as benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring and thiazole ring. A benzene ring or a naphthalene ring is more preferable, and a benzene ring is most preferable.

R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.
Examples of the alkyl group represented by R ₂ and R ₃ include a linear or branched alkyl group having 1 to 10 carbon atoms, and examples of the cycloalkyl group include cycloalkyl having 3 to 10 carbon atoms. The group can be mentioned. Specific examples include a hydrogen atom, a methyl group, a cyclohexyl group, and a t-butyl group.

When a crosslinking reaction is caused by an acid, —OR ₄ is eliminated and a carbocation is generated and the reaction proceeds. Therefore, R ₂ and R ₃ are substituents that stabilize the carbocation, that is, an electron donating group, aromatic It is preferably a group or a hydrogen atom. Specifically, an alkyl group, a cycloalkyl group, a phenyl group, or a hydrogen atom is preferable, and a hydrogen atom is more preferable.

R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an acyl group. From the viewpoint of crosslinking reactivity, R ₄ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and particularly preferably a methyl group.

In general formula (1), alkyl group as R ₁ , alkyl group as R ₂ and R ₃ , cycloalkyl group, aralkyl group and aryl group, cycloalkyl group as R ₄ , aryl group and acyl group, as L Each of the divalent linking group and the aromatic group as Ar may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms), an alkynyl group (2 to 12 carbon atoms). Is preferable), a cycloalkyl group (which may be monocyclic or polycyclic and preferably has 3 to 12 carbon atoms), an aryl group (preferably having 6 to 18 carbon atoms), a hydroxy group, an alkoxy group, an ester group, Examples include an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, a halogen atom, a haloalkyl group, and a sulfonic acid ester group. Preferable examples include an alkyl group, a cycloalkyl group, a halogen atom, a haloalkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an ester group, and an aryl group, and more preferable examples include an alkyl group, a halogen atom, and a hydroxy group. Group and alkoxy group. Examples of the halogen atom are the same as those described for R ₁ above.
The substituent may further have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom), an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, and an alkoxy group. Examples thereof include a carbonyl group, an aryl group, an alkoxyalkyl group, and a group in which these are combined.

M and n each independently represent an integer of 1 or more. m preferably represents an integer of 1 to 3, more preferably 1.

N is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and particularly preferably 1 or 2.

Further, the repeating unit represented by the general formula (1) is more preferably a repeating unit represented by the following general formula (2).

_{_{_{Wherein, R 1, R 2, R}}} 3 and _{R 4} have the same meanings as in formula _{_{(1) R 1, R 2}} , R 3 and _{R 4} in. m ′ represents 1 or 2, and n ′ represents an integer of 1 to 3.

Specific examples and preferred examples of R _1, _R 2, _{R 3} and _{R 4} are the same as those described for _R _1, R 2, _{R 3} and _{R 4} in the general formula (1).

M ′ is more preferably 1.

N ′ represents an integer of 1 to 3, more preferably 1 or 2.

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

In the formula, R ₂ , R ₃ and R ₄ have the same meanings as R ₂ , R ₃ , R ₄ and n ′ in the general formula (1). n ′ represents an integer of 1 to 3.

R _2, _R 3, _{R 4} and n 'Specific examples and preferred examples of the general formula (1) or _R _2, R 3 in the general formula (2), _{R 4} and n' similar to that as described for the . Here, it is preferable that R ₂ and R ₃ are both hydrogen atoms.

The content of the repeating unit represented by the general formula (1), (2) or (3) is 20 with respect to all the repeating units contained in the polymer compound (A) from the viewpoint of crosslinking efficiency and developability. It is preferably from ˜100 mol%, more preferably from 40 to 100 mol%.
Further, the introduction rate of the group represented by — (R ₂ ) (R ₃ ) (OR ₄ ) as the crosslinkable group in the general formula (1), (2) or (3) (hereinafter referred to as the crosslinkable group rate). Is also preferably 20 to 100%, more preferably 40 to 100% from the viewpoint of crosslinking efficiency and developability. Here, the crosslinkable group ratio is a percentage (%) obtained by dividing the number (number) of crosslinkable groups in the polymer compound (A) by the number (number) of reaction points capable of introducing a crosslinkable group. . For example, when the calculation target has a phenolic hydroxyl group, the reactive point at which the crosslinkable group can be introduced introduces a crosslinkable group from the ortho and para positions of the phenolic hydroxyl group in view of the position of the phenolic hydroxyl group. It will be possible. The detailed description is as described later in the section of the embodiment.

Specific examples of the repeating unit represented by the general formula (1), (2) or (3) include the following structures, but are not limited thereto.

The polymer compound (A) may further have a repeating unit having a phenolic hydroxyl group different from the repeating unit represented by the general formula (1).
Here, the phenolic hydroxyl group 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.

Although it does not specifically limit as a repeating unit which has a phenolic hydroxyl group, It is preferable to have a structural unit represented by the following general formula (II).

Where
R ₅ represents a hydrogen atom, an organic group or a halogen atom.
D ₁ represents a single bond or a divalent linking group.
Ar ₂ represents an aromatic ring group.
m ₁ represents an integer of 1 or more.

When R ₅ in the general formula (II) represents an organic group, the organic group is preferably an alkyl group, a cycloalkyl group, or an aryl group, and a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group) Ethyl group, propyl group, butyl group, pentyl group), cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, norbornyl group), aryl group having 6 to 10 carbon atoms (for example, phenyl group, A naphthyl group) is more preferred.
The organic group may further have a substituent. Examples of the substituent include, but are not limited to, a halogen atom (preferably a fluorine atom), a carboxyl group, a hydroxyl group, an amino group, and a cyano group. As the substituent, a fluorine atom and a hydroxyl group are particularly preferable.
Examples of the organic group having a substituent include a trifluoromethyl group and a hydroxymethyl group.
R ₅ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

When D ₁ represents a divalent linking group, examples of the divalent linking group include a carbonyl group, an alkylene group, an arylene group, a sulfonyl group, —O—, —NH—, or a combination thereof (for example, an ester bond Etc.) is preferable.
D ₁ is preferably a single bond or a carbonyloxy group, and more preferably a single bond.

The aromatic ring group represented by Ar ₂ is preferably a group obtained by removing n + 1 hydrogen atoms from a monocyclic or polycyclic aromatic ring (n represents an integer of 1 or more).
Examples of the aromatic ring include an aromatic hydrocarbon ring (preferably having 6 to 18 carbon atoms) which may have a substituent such as a benzene ring, naphthalene ring, anthracene ring, fluorene ring, phenanthrene ring, and the like. Examples include aromatic heterocycles including heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole. be able to. Among these, a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is most preferable.

m ₁ is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.
When m ₁ represents 1 and Ar ₂ represents a benzene ring, the —OH substitution position may be para, meta or ortho relative to the position of the benzene ring bonded to the polymer main chain. From the viewpoint of sex, the para position is preferred.

The aromatic ring in the aromatic ring group of Ar ₂ may have a substituent other than the group represented by —OH. Examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, and a carboxyl group. , An alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, and an arylcarbonyl group. However, the aromatic ring in the aromatic ring group of Ar ₂ does not have a group represented by —C (R ₂ ) (R ₃ ) (OR ₄ ) in the general formula (1) as a substituent.

The general formula (II) is preferably the following general formula (II-1).

Where
R ₅ represents a hydrogen atom, an organic group or a halogen atom.
D ₁ represents a single bond or a divalent linking group.

_{R 5} and _{D 1} in the general formula (II-1) is the general formula (II) in the same meaning as _{R 5} and _{D 1} of the preferred range is also the same.

The general formula (II) is more preferably the following general formula (II-2).

In the formula, R ₅ represents a hydrogen atom, an organic group or a halogen atom.

R _{5 in} formula (II-2) has the same meaning as R ₅ in formula (II), and the preferred range is also the same.

Hereinafter, although the specific example of the repeating unit represented by general formula (II) is shown, it is not limited to this. Me represents a methyl group.

When the polymer compound (A) has a repeating unit having a phenolic hydroxyl group, which is different from the repeating unit represented by the general formula (1), the content of the repeating unit is that of the polymer compound (A). The amount is preferably 1 to 80 mol%, more preferably 1 to 70 mol%, still more preferably 1 to 60 mol%, based on all repeating units.

The polymer compound (A) may further have a repeating unit as described later.

The polymer compound (A) has a “structure in which a hydrogen atom of a phenolic hydroxyl group is substituted by a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure” (hereinafter also referred to as “specific structure”) ”. You may have. In this case, the polymer compound (A) has “a repeating unit having“ a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted by a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure ””. Is preferred. As a result, a high glass transition temperature (Tg) can be obtained, and dry etching resistance can be improved.

Since the polymer compound (A) has the above-mentioned specific structure, the glass transition temperature (Tg) of the polymer compound (A) is increased, so that a very hard resist film can be formed, and acid diffusion And dry etching 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 (D) 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 even higher. This is considered to contribute to better sensitivity.

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

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. As the group exhibiting alkali decomposability, there is a dissolution rate in an alkali developer that is decomposed by the action of a conventionally known alkali developer contained in a resin suitably used in a positive chemically amplified resist composition. And an increasing group (for example, a group having a lactone structure).
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 preferably 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. 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. 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 A norbornane structure, a norbornene structure, a cedrol structure, an isobornane structure, a bornane structure, a dicyclopentane structure, an α-pinene structure, a tricyclodecane structure, a tetracyclododecane structure, and an 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, monocyclic alicyclic hydrocarbon structures corresponding to the above monocyclic alicyclic hydrocarbon groups (specifically Specifically, the chemical formulas of the following formulas (47) to (50) are shown below.

Further, 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 polymer compound (A) may contain a repeating unit represented by the following general formula (IV) or the following general formula (V).

Where
R ₆ represents a hydrogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (—OCOR Or —COOR: R represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
n ₃ represents an integer of 0 to 6.

Where
R ₇ is a hydrogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (—OCOR Or —COOR: R represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
n ₄ represents an integer of 0 to 4.
X ₄ is a methylene group, an oxygen atom or a sulfur atom.

Specific examples of the repeating unit represented by the general formula (IV) or the following general formula (V) are shown below, but are not limited thereto.

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

The weight average molecular weight of the polymer compound (A) is preferably 1000 to 200000, more preferably 2000 to 50000, still more preferably 3000 to 10000, and particularly preferably 3000 to 7000.

The dispersity (molecular weight distribution) (Mw / Mn) of the polymer compound (A) is preferably 1.7 or less, and more preferably 1.0 to 1.50 from the viewpoint of improving sensitivity and resolution. It is particularly preferably 1.0 to 1.40.

In order to obtain the polymer compound (A) having the above preferable degree of dispersion, it is preferably produced by a production method using a polymer of a repeating unit represented by the following general formula (5) having a low degree of dispersion as a raw material. .

_{R 1} in the formula has the same meaning as _{R 1} in the general formula (1).

The dispersity of the raw material polymer used in the above production method is preferably 1.0 to 1.30, more preferably 1.0 to 1.20 in consideration of the possibility of oligomerization by side reaction. The polymer used as a raw material for the above production method is preferably a living polymer such as a living anion polymerization, whereby the degree of dispersion of the resulting polymer compound becomes uniform.

The synthesis of the polymer compound (A) using the above raw materials can be performed with reference to, for example, the method described in “Experimental Chemistry Course Vol. 18, Organic Compound Reaction II (bottom) page 94”.

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

The content of the polymer compound (A) is preferably 50 to 97% by mass, more preferably 60 to 95% by mass, based on the total solid content of the negative actinic ray-sensitive or radiation-sensitive composition. More preferably, it is 70 to 93% by mass.

[2] (B) by irradiation with an actinic ray or radiation, compounds chemically amplified resist composition of the present invention the volume to generate a 130 Å ³ or more 2000 Å ³ The following acid upon irradiation with actinic rays or radiation, volume 130 Å ³ above 2000 Å ³ compound generating the following acid (B) (hereafter, referred to as appropriate, these compounds are referred to as "acid generator").
Preferred forms of the acid generator include onium compounds. Examples of such an onium compound include a sulfonium salt, an iodonium salt, a phosphonium salt, and the like, and a sulfonium salt is more preferable.
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.

The acid generator used in the present invention is not limited to a low molecular compound, and a polymer compound is a group that generates an acid upon irradiation with actinic rays or radiation in a range where the volume of the generated acid is 130 to ^{3 to} 2000 to ³ . A compound introduced into the main chain or side chain can also be used. Further, as described above, when a group capable of generating an acid upon irradiation with actinic rays or radiation is present in the repeating unit which is a copolymerization component of the polymer compound (A) used in the present invention, There may be no acid generator of a different molecule from the polymer compound.
When the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and 1000 or less. Is more preferable.

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 compounds include sulfonium compounds represented by the following general formula (7) or iodonium compounds represented by the general formula (8).

In general formulas (7) and (8),
R _a1 , R _a2 , R _a3 , R _a4 and R _a5 each independently represent an organic group.
X ⁻ represents an organic anion.
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 to R _a3 of the general formula (7) and R _a4 and R _a5 of the general formula (8) each independently represent an organic group, preferably at least one of R _a1 to R _a3 , In addition, at least one of R _a4 and R _{a5 is} 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 X ^{− in} the general formulas (7) and (8) include a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, and a tris (alkylsulfonyl) methide anion. Organic anions represented by general formula (9), (10) or (11), more preferably organic anions represented by the following general formula (9).

In the general formulas (9), (10) and (11), Rc ₁ , Rc ₂ , Rc ₃ and Rc ₄ each represents an organic group.

The organic anion of X ⁻ corresponds to sulfonic acid, imide acid, methide acid, etc., which are acids generated by irradiation with actinic rays or radiation such as electron beams and extreme ultraviolet rays.
Examples of the organic group of R _c1 to R _c4 include an alkyl group, a cycloalkyl group, an aryl group, or a group in which a plurality of these are connected. More preferably among these organic groups, the alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, a cycloalkyl group substituted with a fluorine atom or a fluoroalkyl group, a phenyl group substituted with a fluorine atom or a fluoroalkyl group It is. A plurality of the organic groups represented by R _c2 to R _c4 may be connected to each other to form a ring, and _examples of the group in which the plurality of organic groups are connected include an alkylene group substituted with a fluorine atom or a fluoroalkyl group. Is preferred. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid 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.

In the present invention, the compound (B) that generates an acid is a compound that generates an acid having a volume of 130 to ³ or more (more preferably, a sulfonic acid).
As described above, since the compound (B) generates an acid having a volume of 130 ³ or more, excellent results regarding resolution, PED stability, and LER performance can be obtained.
Compound (B), the activity by irradiation with light or radiation, volume 190 Å ³ or more is preferable that the size of the acid (more preferably sulfonic acid) is a compound capable of generating a volume 270 Å ³ or more the size of the acid ( preferably more than it is more preferably a compound capable of generating a sulfonic acid), it is particularly preferable acid (more preferably a volume 400 Å ³ or more in size is a compound capable of generating a sulfonic acid). However, from the viewpoint of sensitivity, coating solvent solubility, and the like, the volume is 2000 ³ or less, and more preferably 1500 ³ or less.
Here, 1Å corresponds to 0.1 nm.
The volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example 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.
In the present invention, particularly preferred acid generators are exemplified 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.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the composition is preferably 0.1 to 25% by mass, more preferably 0.1 to 25% by mass, based on the total solid content of the negative actinic ray-sensitive or radiation-sensitive resin composition. The content is 5 to 20% by mass, more preferably 1 to 18% by mass.

[3] (E) Basic compound The composition of the present invention preferably further contains a basic compound as an acid scavenger. 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 US Patent Application Publication No. 2007 / 0224539A1. And the compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above. Compounds 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 photodegradable basic compound (initially a basic nitrogen atom acts as a base to show basicity, but is decomposed by irradiation with actinic rays or radiation to have an amphoteric group having a basic nitrogen atom and an organic acid moiety. Compounds in which basicity is reduced or eliminated by generating ionic compounds and neutralizing them in the molecule, such as Japanese Patent No. 3577743, Japanese Patent Application Laid-Open No. 2001-215589, Japanese Patent Application Laid-Open No. 2001-166476, An onium salt described in JP-A-2008-102383) and a photobasic generator (for example, a compound described in JP-A-2010-243773) are 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.

The basic compound in the present invention is preferably the above “photodegradable basic compound”, and is “a basic compound or an ammonium salt compound (C) whose basicity is reduced by irradiation with actinic rays or radiation”. It is more preferable.
The basic compound or ammonium salt compound (C) whose basicity is lowered by irradiation with such actinic rays or radiation is an onium salt compound (hereinafter referred to as “compound (E)”) containing a nitrogen atom in the cation moiety described below. ").
Examples of the onium salt compound include a diazonium salt compound, a phosphonium salt compound, a sulfonium salt compound, and an iodonium salt compound. Among these, a sulfonium salt compound or an iodonium salt compound is preferable, and a sulfonium salt compound is more preferable.
This onium salt compound typically includes a basic site containing a nitrogen atom in the cation moiety. Here, “basic site” means a site where the pKa of the conjugate acid at the cation site of compound (E) is −3 or more. This pKa is preferably in the range of -3 to 15, more preferably in the range of 0 to 15. In addition, this pKa means the calculated value calculated | required by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).
The basic moiety includes, for example, a structure selected from the group consisting of an amino group (a group obtained by removing one hydrogen atom from ammonia, primary amine, or secondary amine; the same applies hereinafter) and a nitrogen-containing heterocyclic group. . The amino group is preferably an aliphatic amino group. Here, the aliphatic amino group means a group obtained by removing one hydrogen atom from an aliphatic amine.
In these structures, it is preferable from the viewpoint of improving basicity that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly connected to the nitrogen atom.
The onium salt compound may have two or more of the above basic sites.
When the cation part of the compound (E) contains an amino group, the cation part preferably has a partial structure represented by the following general formula (NI).

Where
R _A and R _B each independently represent a hydrogen atom or an organic group.
X represents a single bond or a linking group.
At least two of R _A , R _B and X may be bonded to each other to form a ring.
Examples of the organic group represented by R _A or R _B include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic hydrocarbon group, an alkoxycarbonyl group, a lactone group, and a sultone group. .
These groups may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, and a cyano group.
The alkyl group represented by R _A or R _B may be linear or branched. The alkyl group preferably has 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms, and still more preferably 1 to 20 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples thereof include a butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group.
The cycloalkyl group represented by R _A or R _B may be monocyclic or polycyclic. The cycloalkyl group is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group.
The alkenyl group represented by R _A or R _B may be linear or branched. The alkenyl group has preferably 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.
The aryl group represented by R _A or R _B preferably has 6 to 14 carbon atoms. Examples of such groups include a phenyl group and a naphthyl group.
The heterocyclic hydrocarbon group represented by R _A or R _B preferably has 5 to 20 carbon atoms, 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 group may be monocyclic or polycyclic. Examples of such heterocycle 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 lactone group represented by R _A or R _B is, for example, a 5- to 7-membered lactone group, and other ring structures in the form of forming a bicyclo structure or a spiro structure on the 5- to 7-membered lactone group. It may be a condensed ring.
The sultone group represented by R _A or R _B is, for example, a 5- to 7-membered ring sultone group, and other ring structures in the form of forming a bicyclo structure or a spiro structure in the 5- to 7-membered ring sultone group. It may be a condensed ring.
Specifically, a group having the structure shown below is preferable.

The lactone group and sultone group may or may not have a substituent (Rb ₂ ). Preferred examples of the substituent (Rb _2), the same substituents as those described as the substituent of R _A and R _B in the above. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. A plurality of substituents (Rb ₂ ) may be bonded to form a ring.
Examples of the linking group represented by X include a linear or branched alkylene group, a cycloalkylene group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and combinations of two or more thereof. Groups and the like. X is more preferably a single bond, an alkylene group, a group in which an alkylene group and an ether bond are combined, or a group in which an alkylene group and an ester bond are combined. The number of atoms of the linking group represented by X is preferably 20 or less, and more preferably 15 or less. The above linear or branched alkylene group and cycloalkylene group preferably have 8 or less carbon atoms and may have a substituent. The above substituents are preferably those having 8 or less carbon atoms, for example, alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (carbon atoms). 2 to 6).
At least two of R _A , R _B and X may be bonded to each other to form a ring. The number of carbon atoms forming the ring is preferably 4 to 20, which may be monocyclic or polycyclic, and may contain an oxygen atom, sulfur atom, nitrogen atom, ester bond, amide bond or carbonyl group in the ring. Good.
When the cation part of compound (E) contains a nitrogen-containing heterocyclic group, this nitrogen-containing heterocyclic group may have aromaticity or may not have aromaticity. The nitrogen-containing heterocyclic group may be monocyclic or polycyclic. The nitrogen-containing heterocyclic group is preferably a group containing a piperidine ring, morpholine ring, pyridine ring, imidazole ring, pyrazine ring, pyrrole ring, or pyrimidine ring.
The onium salt compound (E) is preferably a compound represented by the following general formula (4).

In the formula, A represents a sulfur atom or an iodine atom, R _A represents a hydrogen atom or an organic group, R _B represents a (p + 1) -valent organic group, X represents a single bond or a linking group, and A _N represents Represents a basic moiety containing a nitrogen atom. When a plurality of R _A , R _B , X and A _N are present, they may be the same or different.
When A is a sulfur atom, q is an integer of 1 to 3, and o is an integer that satisfies the relationship of o + q = 3.
When A is an iodine atom, q is 1 or 2, and o is an integer that satisfies the relationship of o + q = 2.
p represents an integer of 1 to 10, and Y ⁻ represents an anion (the details are as described below as the anion part of the compound (E)).
At least two of R _A , X, R _B and A _N may be bonded to each other to form a ring.

Examples of the (p + 1) -valent organic group represented by R _B include, for example, a chain (linear, branched) or cyclic aliphatic hydrocarbon group, heterocyclic hydrocarbon group, and aromatic hydrocarbon group. Of these, an aromatic hydrocarbon group is preferable. When R _B is an aromatic hydrocarbon group, those bonded at the p-position (1,4-position) of the aromatic hydrocarbon group are preferred.
The linking group represented by X has the same meaning as the linking group represented by X in the general formula (NI) described above, and the same specific examples can be given.
Basic moiety represented by A _N is synonymous with "base site" contained in the cationic portion of the compound described above (E), for example, include an amino group or a nitrogen-containing heterocyclic group. When the basic moiety includes an amino group, examples of the amino group include —N (R _A ) (R _B ) group in the above general formula (NI).

Examples of the organic group represented by R _A include an alkyl group, an alkenyl group, an aliphatic cyclic group, an aromatic hydrocarbon group, and a heterocyclic hydrocarbon group. When o = 2, two R _A may be bonded to each other to form a ring. These groups or rings may further have a substituent.
The alkyl group represented by R _A 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 an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples thereof include a butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group.
The alkenyl group represented by R _A may be linear or branched. The alkenyl group has preferably 2 to 50 carbon atoms, more preferably 2 to 30 carbon atoms, and still more preferably 3 to 20 carbon atoms. Examples of such alkenyl groups include vinyl groups, allyl groups, and styryl groups.
The aliphatic cyclic group represented by R _A is, for example, a cycloalkyl group. The cycloalkyl group may be monocyclic or polycyclic. Preferred examples of the aliphatic cyclic group include monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
The aromatic hydrocarbon group represented by R _A is preferably one having 6 to 14 carbon atoms. Examples of such a group include aryl groups such as a phenyl group and a naphthyl group. The aromatic hydrocarbon group represented by R _A is preferably a phenyl group.
The heterocyclic hydrocarbon group represented by R _A may have aromaticity or may not have aromaticity. This heterocyclic hydrocarbon group preferably has aromaticity.
The heterocyclic ring contained in the above group may be monocyclic or polycyclic. Examples of such heterocycle 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.
R _A is preferably an aromatic hydrocarbon group, or two R _A are bonded to form a ring.
The ring that may be formed by combining at least two of R _A , X, R, and A _N with each other is preferably a 4- to 7-membered ring, more preferably a 5- or 6-membered ring. A ring is particularly preferable. Further, the ring skeleton may contain a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom.
When the group represented by R _A or the ring formed by bonding two R _A to each other further includes a substituent, examples of the substituent include the following. That is, examples of the substituent include a halogen atom (—F, —Br, —Cl, or —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an amino group, and an acyloxy group. Carbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl- N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, carbamoyl group, alkylsulfinyl group, arylsulfinyl group An alkylsulfonyl group, an arylsulfonyl group, (referred to as a sulfonato group) sulfo group (-SO 3 _H) and its conjugated base group, alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, a phosphono group (-PO 3 _H ₂₎ and Its conjugated base group (referred to as phosphonato group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugated base group (referred to as phosphonatoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group , A silyl group, and an alkyl group.
Of these substituents, a hydroxyl group, an alkoxy group, a cyano group, an aryl group, an alkenyl group, an alkynyl group, an alkyl group, and the like are preferable.

In the general formula (4), p is preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 1.
The compound represented by the general formula (4) (E), in one embodiment, it is preferable that at least one of aromatic hydrocarbon groups of q pieces of R _B in the formula. X in at least one of the p — (X—A _N ) groups bonded to at least one of the aromatic hydrocarbon groups is a carbon atom at the bond to the aromatic hydrocarbon group. A linking group is preferred.
That is, the compounds in this embodiment (E), a basic moiety represented by A _N is through a carbon atom directly bonded to the aromatic hydrocarbon groups represented by R _B, bonded to the aromatic hydrocarbon group is doing.

The aromatic hydrocarbon group represented by R _B may include a heterocyclic ring as the aromatic ring in the aromatic hydrocarbon group. The aromatic ring may be monocyclic or polycyclic.
The aromatic ring group preferably has 6 to 14 carbon atoms. Examples of such a group include aryl groups such as a phenyl group, a naphthyl group, and an anthryl group. When the aromatic ring group includes a heterocyclic ring, examples of the heterocyclic ring include thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, and triazole. A ring, a thiadiazole ring, and a thiazole ring.
Aromatic hydrocarbon groups represented by R _B is preferably a phenyl group or a naphthyl group, particularly preferably a phenyl group.
The aromatic hydrocarbon group represented by R _B may further have a substituent other than the group represented by — (X—A _N ) described below. As a substituent, what was previously enumerated as a substituent in _RA can be used, for example.

In this embodiment, the linking group as X in the at least one — (XA _N ) group substituted on the aromatic ring R _B has a bond with the aromatic hydrocarbon group represented by R _B. If it is a carbon atom, it will not specifically limit. The linking group includes, for example, an alkylene group, a cycloalkylene group, an arylene group, —COO—, —CO—, or a combination thereof. The linking group includes these groups, —O—, —S—, —OCO—, —S (═O) —, —S (═O) ₂ —, —OS (═O) ₂ —, and —NR. A combination with at least one selected from the group consisting of “-” may be included. Here, R ′ represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
The alkylene group that can be contained in the linking group represented by X may be linear or branched. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.
The cycloalkylene group that may be contained in the linking group represented by X may be monocyclic or polycyclic. The cycloalkylene group preferably has 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of such a cycloalkylene group include a 1,4-cyclohexylene group.
The number of carbon atoms of the arylene group that can be contained in the linking group represented by X is preferably 6 to 20, and more preferably 6 to 10. Examples of such an arylene group include a phenylene group and a naphthylene group.
At least one X is preferably represented by the following general formula (N-III) or (N-IV).

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

Where
J represents an oxygen atom or a sulfur atom.
E represents a linking group or a single bond.
Examples of the groups represented by R ₂ and R ₃ and the substituents they may further include are the same as those described above for R _A. The ring that can be formed by combining R ₂ and R ₃ and the ring that can be formed by combining at least one of R ₂ and R ₃ with E is preferably a 4- to 7-membered ring. A 6-membered ring is more preferable. R ₂ and R ₃ are preferably each independently a hydrogen atom or an alkyl group.
The linking group represented by E is, for example, an alkylene group, a cycloalkylene group, an arylene group, —COO—, —CO—, —O—, —S—, —OCO—, —S (═O) —, — S (═O) ₂ —, —OS (═O) ₂ —, —NR—, or a combination thereof is included. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, for example.
The linking group represented by E is an alkylene bond, ester bond, ether bond, thioether bond, urethane bond

, Urea bond

And at least one selected from the group consisting of an amide bond and a sulfonamide bond. The linking group represented by E is more preferably an alkylene bond, an ester bond, or an ether bond.
The compound (E) may be a compound having a plurality of sites containing nitrogen atoms. For example, the compound (E) may be a compound in which at least one of R _A in the general formula (4) has a structure represented by the general formula (NI).
In one embodiment, the compound (E) represented by the general formula (4) is represented by the following general formula (NV).

In the formula, X, A _N and Y ^- have the same meaning as each group in formula (4), and specific examples and preferred examples are also the same.
R ₁₄ , R ₁₅ , r and l have the same meanings as the groups and indices in General Formula (ZI-4) representing one embodiment of the photoacid generator, and specific examples and preferred examples are also the same.
In addition, in one embodiment, the compound (E) represented by the general formula (4) is represented by the following general formula (N-VI).

In general formula (N-VI),
A represents a sulfur atom or an iodine atom.
R ₁₁ each independently represents an alkyl group, an alkenyl group, an aliphatic cyclic group, an aromatic hydrocarbon group, or a heterocyclic hydrocarbon group. When m = 2, two R ₁₁ may be bonded to each other to form a ring.
Ar each independently represents an aromatic hydrocarbon group.
X ₁ each independently represents a divalent linking group.
R ₁₂ each independently represents a hydrogen atom or an organic group.
When A is a sulfur atom, m is an integer of 1 to 3, and n is an integer that satisfies the relationship m + n = 3.
When A is an iodine atom, m is an integer of 1 or 2, and n is an integer that satisfies the relationship m + n = 2.
Y ⁻ represents an anion (the details are as described later as the anion part of the compound (E)).
Specific examples and preferred examples of the alkyl group, alkenyl group, aliphatic cyclic group, aromatic hydrocarbon group, and heterocyclic hydrocarbon group as R ₁₁ include alkyl as R _A in the general formula (4). Specific examples and preferred examples of the group, alkenyl group, aliphatic cyclic group, aromatic hydrocarbon group and heterocyclic hydrocarbon group are the same.
Specific examples and preferred examples of the aromatic hydrocarbon group as Ar are the same as the specific examples and preferred examples of the aromatic hydrocarbon group as R _B in the general formula (4).
Specific examples and preferred examples of the divalent linking group as X _{1 are the same} as the specific examples and preferred examples of the linking group as X in the general formula (4).
Specific examples and preferred examples of the organic group as R _{12 are the same} as the specific examples and preferred examples of the organic group as R _A and R _B in the general formula (NI).
The aspect in which X is an alkylene group (for example, a methylene group) and two R ₁₂ are bonded to each other to form a ring is a view point of post-exposure heating (PEB) temperature dependence and post-exposure line width (PED) stability. Is particularly preferable.
There is no restriction | limiting in particular in the anion part of a compound (E). The anion contained in the compound (E) is preferably a non-nucleophilic anion. Here, the non-nucleophilic anion is an anion having an extremely low ability to cause a nucleophilic reaction, and an anion capable of suppressing degradation with time due to intramolecular nucleophilic reaction. Thereby, the temporal stability of the composition according to the present invention is improved.
Examples of the non-nucleophilic anion include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.
Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.
Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.
The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms, such as methyl Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group and the like.
The aromatic group in the aromatic sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.
The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy group A hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), a cycloalkyl group (preferably having a carbon number of 3 to 15), an aryl group (preferably having a carbon number of 6 to 14), an alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (Preferably 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), aryl An oxysulfonyl group (preferably having 6 to 20 carbon atoms), an alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), a cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group ( Preferable examples include 5 to 20 carbon atoms and a cycloalkylalkyloxyalkyloxy group (preferably 8 to 20 carbon atoms). Regarding the aryl group and ring structure of each group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.
Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.
The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like.
The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include, for example, the same halogen atom and alkyl as in the aromatic sulfonate anion Group, cycloalkyl group, alkoxy group, alkylthio group and the like.
Examples of the sulfonylimide anion include saccharin anion.
The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, Examples thereof include an isobutyl group, a sec-butyl group, a pentyl group, and a neopentyl group. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Alkyl groups substituted with fluorine atoms are preferred. Also preferred is an embodiment in which two alkyl groups in the bis (alkylsulfonyl) imide anion are bonded to each other to form a cyclic structure. In this case, the cyclic structure formed is preferably a 5- to 7-membered ring.
Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.
Examples of the non-nucleophilic anion include an aliphatic sulfonate anion in which the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom. A substituted bis (alkylsulfonyl) imide anion and a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms, a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, Pentafluorobenzenesulfonate anion, 3,5-bis (trifluoromethyl) benzenesulfonate anion.
Moreover, it is preferable that a non-nucleophilic anion is represented by the following general formula (LD1), for example.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁ and R ₂ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Cy represents a cyclic organic group.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.
Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Xf is a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , _{_{_{_{CH 2 CF 3, CH 2 CH}}}} 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 Or CH ₂ CH ₂ C ₄ F ₉ is preferred.
R ₁ and R ₂ are each independently a hydrogen atom, a fluorine atom, or an alkyl group. This alkyl group may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent as R ₁ and R ₂ include, for example, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ Examples include F ₇ , CH ₂ C ₄ F ₉ , and CH ₂ CH ₂ C ₄ F ₉ , among which CF ₃ is preferable.
L represents a divalent linking group. Examples of the divalent linking group include —COO—, —OCO—, —CONH—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, and a cycloalkylene group. And alkenylene groups. Among these, —CONH—, —CO—, or —SO ₂ — is preferable, and —CONH— or —SO ₂ — is more preferable.
Cy represents a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, is a PEB (heating after exposure) step. From the viewpoints of suppressing diffusibility in the film and improving MEEF (Mask Error Enhancement Factor).
The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.
The heterocyclic group may be monocyclic or polycyclic, but the polycyclic group can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable. Examples of the lactone ring include the lactone rings exemplified for R _A and R _B in the general formula (N-1).
The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group. It is done. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 12 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 12 carbon atoms. The aryl group preferably has 6 to 14 carbon atoms.
x is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. y is preferably 0 to 4, more preferably 0. z is preferably 0 to 8, more preferably 0 to 4.
Moreover, it is also preferable that a non-nucleophilic anion is represented by the following general formula (LD2), for example.

In General Formula (LD2), Xf, R ₁ , R ₂ , L, Cy, x, y, and z have the same meanings as in General Formula (LD1). Rf is a group containing a fluorine atom.
Examples of the group containing a fluorine atom represented by Rf include an alkyl group having at least one fluorine atom, a cycloalkyl group having at least one fluorine atom, and an aryl group having at least one fluorine atom. .
These alkyl group, cycloalkyl group and aryl group may be substituted with a fluorine atom, or may be substituted with another substituent containing a fluorine atom. When Rf is a cycloalkyl group having at least one fluorine atom or an aryl group having at least one fluorine atom, other substituents containing a fluorine atom include, for example, alkyl substituted with at least one fluorine atom. Groups.
Further, these alkyl group, cycloalkyl group and aryl group may be further substituted with a substituent not containing a fluorine atom. As this substituent, the thing which does not contain a fluorine atom among what was demonstrated about Cy previously can be mentioned, for example.
Examples of the alkyl group having at least one fluorine atom represented by Rf include those described above as the alkyl group substituted with at least one fluorine atom represented by Xf. Examples of the cycloalkyl group having at least one fluorine atom represented by Rf include a perfluorocyclopentyl group and a perfluorocyclohexyl group. Examples of the aryl group having at least one fluorine atom represented by Rf include a perfluorophenyl group.
Preferred embodiments of the anion moiety of compound (E) include the structures exemplified as preferred anion structures of the photoacid generator in addition to the structures represented by the general formulas (LD1) and (LD2) described above. .
The compound (E) has a fluorine content represented by (total mass of all fluorine atoms contained in the compound) / (total mass of all atoms contained in the compound) of 0.30 or less. It is preferably 0.25 or less, more preferably 0.20 or less, particularly preferably 0.15 or less, and most preferably 0.10 or less.
Although the specific example of a compound (E) is given to the following, it is not limited to these.

A compound (E) may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the compound (E) is usually in the range of 0.001 to 10% by mass, preferably 0.1 to 10% by mass, more preferably 1 to 10%, based on the total solid content of the composition. It is in the range of mass%.
In addition, the direction where the volume of the acid generated from the compound (E) is large is preferable from the viewpoint of improving the resolution.

[4] (C) Compound having acid crosslinkable group different from polymer compound (A) The composition of the present invention is different from the above polymer compound (A) in having compound having acid crosslinkable group (C ) (Hereinafter also referred to as “compound (C)” or “acid crosslinking agent (C)”). The compound (C) 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.

First, the case where the compound (C) is a low molecular compound (hereinafter also referred to as “compound (C ′)”) will be described. 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 having 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.

In the formula, L ₁ to L ₈ each independently represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or an alkyl group having 1 to 6 carbon atoms.
In one embodiment of the present invention, the compound (C ′) is preferably a compound represented by the following general formula (I).

In general formula (I),
R ₁ and R ₆ each independently represents a hydrogen atom or a hydrocarbon group having 5 or less carbon atoms.
R ₂ and R ₅ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an acyl group.
R ₃ and R ₄ each independently represent a hydrogen atom or an organic group having 2 or more carbon atoms. R ₃ and R ₄ may combine with each other to form a ring.

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

As the alkyl group represented by R ₂ and R ₅ , for example, an alkyl group having 1 to 6 carbon atoms is preferable, and as a cycloalkyl group, for example, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and as an aryl group, For example, an aryl group having 6 to 12 carbon atoms is preferred, and an acyl group having, for example, an alkyl moiety having 1 to 6 carbon atoms is preferred.
In one embodiment of the present invention, R ₂ and R ₅ are preferably alkyl groups, more preferably alkyl groups having 1 to 6 carbon atoms, and particularly preferably methyl groups.

Examples of the organic group having 2 or more carbon atoms represented by R ₃ and R ₄ include an alkyl group having 2 or more carbon atoms, a cycloalkyl group, and an aryl group, and R ₃ and R ₄ are bonded to each other. It is preferable to form the ring described in detail below.

Examples of the ring formed by combining R ₃ and R ₄ with each other include, for example, an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a combination of two or more of these rings The polycyclic fused ring formed can be mentioned.

These rings may have a substituent. Examples of such a substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an aryl group, an alkoxymethyl group, an acyl group, and an alkoxycarbonyl group. , A nitro group, a halogen, or a hydroxy group.

Specific examples of the ring formed by combining R ₃ and R ₄ with each other are given below. * In a formula represents a connection part with a phenol nucleus.

In one embodiment of the present invention, R ₃ and R ₄ in the general formula (I) are preferably bonded to form a polycyclic fused ring containing a benzene ring, and more preferably a fluorene structure is formed. preferable.
In the compound (C ′), for example, R ₃ and R _{4 in the} general formula (I) are preferably bonded to form a fluorene structure represented by the following general formula (Ia).

Where
R ₇ and R ₈ each independently represents a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an alkoxymethyl group, an acyl group, an alkoxycarbonyl group, a nitro group, a halogen, and a hydroxy group.
n1 and n2 each independently represents an integer of 0 to 4, preferably 0 or 1.
* Represents a linking site with a phenol nucleus.

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

Where
R _1b and R _6b each independently represents an alkyl group having 5 or less carbon atoms.
R _2b and R _5b each independently represents an alkyl group having 6 or less carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.
Z represents an atomic group necessary for forming a ring together with the carbon atom in the formula.
The ring formed by Z together with the carbon atom in the formula is the same as that described for the ring formed by combining R ₃ and R ₄ with each other in the description of the general formula (I).

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

Next, the manufacturing method of compound (C ') represented by general formula (I) is demonstrated.
In general, the bisphenol compound serving as the mother nucleus of the compound (C ′) represented by the general formula (I) is generally a dehydration condensation reaction between two corresponding molecules of a phenol compound and one corresponding molecule of a ketone in the presence of an acid catalyst. To be synthesized.

The obtained bisphenol compound is treated with paraformaldehyde and dimethylamine and aminomethylated to obtain an intermediate represented by the following general formula (IC). Subsequently, the target acid crosslinking agent is obtained through acetylation, deacetylation, and alkylation.

In formula, R < ₁ >, R < ₃ >, R < ₄ > and R < ₆ > are synonymous with each group in general formula (I).

This synthesis method has an effect of inhibiting particle formation because it is difficult to produce an oligomer as compared with a synthesis method via a hydroxymethyl compound under a basic condition (for example, JP 2008-273844 A). .
Specific examples of the compound (C ′) represented by the general formula (I) are shown below.

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.

The compound (C) containing an acid crosslinkable group is different from the repeating unit represented by the general formula (1) in the polymer compound (A) and contains a resin (compound (C ″ )).

The negative actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may or may not contain the compound (C), but when it is contained, the content of the compound (C) is negative. The total solid content of the mold-type actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.5 to 30% by mass, more preferably 1 to 15% by mass.

[5] (D) Hydrophobic Resin The negative-type actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is a hydrophobic resin (hereinafter referred to as “hydrophobic resin (D)”, particularly when applied to immersion exposure. Or simply “resin (D)”. The hydrophobic resin (D) is preferably different from the polymer compound (A).
As a result, the hydrophobic resin (D) is unevenly distributed in the film surface layer, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to.
The hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (D) does not necessarily need to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

The hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.

When the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin. , May be contained in the side chain.

When the hydrophobic resin (D) contains a fluorine atom, it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. Preferably there is.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. It may have a substituent other than.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .

Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R ₅₇ to R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, at least one of R ₅₇ to R _61, at least one of R ₆₂ to R ₆₄ , and at least one of R ₆₅ to R ₆₈ are each independently a fluorine atom or at least one hydrogen atom substituted with a fluorine atom. Represents an alkyl group (preferably having 1 to 4 carbon atoms).
All of R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are preferably fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, —CH (CF ₃ ) OH and the like are mentioned, and —C (CF ₃ ) ₂ OH is preferable.

The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more.

Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents —F or —CF ₃ .

The hydrophobic resin (D) may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R ₁₂ to R ₂₆ each independently represents a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L ₃ to L _{5 each} represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, and a urea bond, or a combination of two or more ( Preferably, the total carbon number is 12 or less).
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

Specific examples of the repeating unit having groups represented by general formulas (CS-1) to (CS-3) will be given below, but the present invention is not limited thereto. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Further, as described above, the hydrophobic resin (D), it is also preferred to include CH ₃ partial structure side chain moiety.
Here, the CH ₃ partial structure of the side chain portion in the resin (D) (hereinafter also simply referred to as “side chain CH ₃ partial structure”) has a CH ₃ partial structure of an ethyl group, a propyl group, or the like. Is included.
On the other hand, a methyl group directly bonded to the main chain of the resin (D) (for example, α-methyl group of a repeating unit having a methacrylic acid structure) causes uneven distribution of the surface of the resin (D) due to the influence of the main chain. Since the contribution is small, it is not included in the CH ₃ partial structure.

More specifically, the resin (D) includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R ₁₁ to R ₁₄ are CH ₃ “as is”, the CH ₃ is not included in the CH ₃ partial structure.
Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it has “one” CH ₃ partial structure.

In the general formula (M),
R ₁₁ to R ₁₄ each independently represents a side chain portion.
Examples of R ₁₁ to R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.
Examples of the monovalent organic group for R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin (D) is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (III).

Hereinafter, the repeating unit represented by the general formula (II) will be described in detail.

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, the acid-stable organic group is a non-acid-decomposable organic group, and non-acid-decomposable means that a photoacid generator is used as described in the section of the polymer compound (A). It means the property that the decomposition reaction does not occur due to the generated acid.

The alkyl group of _Xb1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group may further have an alkyl group as a substituent.
R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

The alkyl group having one or more CH ₃ partial structures in R ₂ is preferably a branched alkyl group having 3 to 20 carbon atoms. Specific examples of preferable alkyl groups include isopropyl group, isobutyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, and 3-methyl-4. -Hexyl, 3,5-dimethyl-4-pentyl, isooctyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-dimethylheptyl, 1,5-dimethyl-3-heptyl Group, 2,3,5,7-tetramethyl-4-heptyl group and the like. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group is there.

The cycloalkyl group having one or more CH ₃ partial structures in R ₂ may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably 6-30, and particularly preferably 7-25. Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, and tricyclodecanyl group. More preferably, they are a norbornyl group, a cyclopentyl group, and a cyclohexyl group.
The alkenyl group having one or more CH ₃ partial structures in R ₂ is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, and more preferably a branched alkenyl group.
The aryl group having one or more CH ₃ partial structures in R ₂ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. is there.
The aralkyl group having one or more CH ₃ partial structures in R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Specific examples of the hydrocarbon group having two or more CH ₃ partial structures in R ₂ include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 2-methyl-3-butyl. Group, 3-hexyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-t-butylcyclohexyl group, isobornyl group and the like can be mentioned. More preferably, an isobutyl group, t-butyl group, 2-methyl-3-butyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5 , 7-tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 3,5-ditert-butylcyclohexyl group, 4-isopropylcyclohexyl group, 4-t-butylcyclohexyl group and isobornyl group.

Preferred specific examples of the repeating unit represented by the general formula (II) are listed below. Note that the present invention is not limited to this.

The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

Hereinafter, the repeating unit represented by the general formula (III) will be described in detail.

In the above general formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an acid-stable organic group having one or more CH ₃ partial structures, n represents an integer of 1 to 5.

The alkyl group of _Xb2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
X _b2 is preferably a hydrogen atom.

Since R ₃ is an organic group that is stable to an acid, more specifically, the organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). It is preferable that

R ₃ includes an alkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.

The alkyl group having one or more CH ₃ partial structures in R ₃ is preferably a branched alkyl group having 3 to 20 carbon atoms. Specific examples of preferable alkyl groups include isopropyl group, isobutyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, and 3-methyl-4. -Hexyl, 3,5-dimethyl-4-pentyl, isooctyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-dimethylheptyl, 1,5-dimethyl-3-heptyl Group, 2,3,5,7-tetramethyl-4-heptyl group and the like. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group is there.

Specific examples of the alkyl group having two or more CH ₃ partial structures in R ₃ include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 2,3-dimethylbutyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4, 4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, etc. . More preferably, it has 5 to 20 carbon atoms, and is an isopropyl group, t-butyl group, 2-methyl-3-butyl group, 2-methyl-3-pentyl group, or 3-methyl-4-hexyl group. 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3, 5,7-tetramethyl-4-heptyl group and 2,6-dimethylheptyl group.

N represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

Preferred specific examples of the repeating unit represented by the general formula (III) are given below. Note that the present invention is not limited to this.

The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the resin (D) contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II) and the general formula The content of at least one repeating unit (x) among the repeating units represented by (III) is preferably 90 mol% or more, and 95 mol% or more with respect to all the repeating units of the resin (D). It is more preferable that The content is usually 100 mol% or less with respect to all repeating units of the resin (D).

Resin (D) is a repeating unit represented by general formula (II), and at least one repeating unit (x) among repeating units represented by general formula (III) By containing 90 mol% or more with respect to the unit, the surface free energy of the resin (D) increases. As a result, the resin (D) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be reliably improved, and the immersion liquid followability can be improved.

In addition, the hydrophobic resin (D) includes the following (x) to (z) regardless of whether (i) a fluorine atom and / or a silicon atom is included or (ii) a CH ₃ partial structure is included in the side chain portion. ) May have at least one group selected from the group of
(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) a group decomposable by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
The content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 5%, based on all repeating units in the hydrophobic resin (D). 20 mol%.

Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

As the “group having a lactone structure, acid anhydride group, or acid imide group (y)”, a group having a lactone structure is particularly preferable.
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the acid-decomposable resin (A).

The content of the repeating unit having “group having lactone structure, acid anhydride group, or acid imide group (y)” is 1 to 100 mol% based on all repeating units in the hydrophobic resin (D). It is preferably 3 to 98 mol%, more preferably 5 to 95 mol%.

In the hydrophobic resin (D), the repeating unit having a group (z) that is decomposed by the action of an acid has an acid-decomposable group that an acid-decomposable resin widely known to be contained in a resist composition has. Repeat units can be used as they are. The repeating unit having a group (z) that is decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (D), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (D). The amount is preferably 10 to 80 mol%, more preferably 20 to 60 mol%.

The hydrophobic resin (D) may further have a repeating unit represented by the following general formula (III).

In general formula (III):
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a fluorine atom or a silicon atom.
L _c3 represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having a carbon number of 1 to 5), an ether bond, a phenylene group, or an ester bond (a group represented by —COO—).
The content of the repeating unit represented by the general formula (III) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. 30 to 70 mol% is more preferable.

The hydrophobic resin (D) preferably further has a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).
The content of the repeating unit represented by the general formula (CII-AB) is preferably 1 to 100 mol%, based on all repeating units in the hydrophobic resin, and preferably 10 to 90 mol%. More preferred is 30 to 70 mol%.

Specific examples of the repeating unit represented by the general formulas (III) and (CII-AB) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

When the hydrophobic resin (D) has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin (D), and is 10 to 80% by mass. More preferably. Further, the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol% in all repeating units contained in the hydrophobic resin (D).
When the hydrophobic resin (D) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass with respect to the weight average molecular weight of the hydrophobic resin (D), and is 2 to 30% by mass. More preferably. Further, the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin (D).

On the other hand, particularly when the resin (D) contains a CH ₃ partial structure in the side chain portion, a form in which the resin (D) does not substantially contain a fluorine atom and a silicon atom is also preferable. In this case, specifically, The content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, more preferably 1 mol based on all repeating units in the resin (D). % Or less, ideally 0 mol%, that is, no fluorine atom and no silicon atom. Moreover, it is preferable that resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is 95 mol% or more in the total repeating units of the resin (D). Preferably, it is 97 mol% or more, more preferably 99 mol% or more, and ideally 100 mol%.

The weight average molecular weight in terms of standard polystyrene of the hydrophobic resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 2,000 to 15,000. is there.
In addition, the hydrophobic resin (D) may be used alone or in combination.
The content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention. More preferably, it is 1 to 7% by mass.

Naturally, the hydrophobic resin (D) has a small amount of impurities such as metals, and the residual monomer or oligomer component is preferably 0.01 to 5% by mass, more preferably 0.01 to 3%. Even more preferred are mass%, 0.05-1 mass%. As a result, an actinic ray-sensitive or radiation-sensitive resin composition that does not change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1-2.

As the hydrophobic resin (D), various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.
The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (A), but in the synthesis of the hydrophobic resin (D), The concentration of the reaction is preferably 30 to 50% by mass.

Specific examples of the hydrophobic resin (D) are shown below. The following table shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

[6] Surfactant The negative actinic ray-sensitive or radiation-sensitive 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 Fluorine such as nonionic surfactants such as sorbitan fatty acid esters, MegaFac F171 (manufactured by Dainippon Ink and Chemicals), Florard FC430 (manufactured by Sumitomo 3M), Surfinol E1004 (manufactured by Asahi Glass), PF656 and PF6320 manufactured by OMNOVA Surfactants and organosiloxane polymers.
The negative actinic ray-sensitive or radiation-sensitive composition of the present invention may or may not contain a surfactant, but when it contains a surfactant, its content is the total amount of the composition (the solvent Is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass.

[7] Organic carboxylic acid The negative actinic ray-sensitive or radiation-sensitive 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. When performing electron beam exposure under vacuum, there is a risk of volatilization from the resist film surface and contamination of the drawing chamber. Therefore, preferred compounds include aromatic organic carboxylic acids, among which, for example, benzoic acid, 1 -Hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid are preferred.
The negative actinic ray-sensitive or radiation-sensitive composition of the present invention may or may not contain an organic carboxylic acid, but when it is contained, the compounding ratio of the organic carboxylic acid is the polymer compound (A). The amount is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.01 to 3 parts by mass.
If necessary, the negative actinic ray-sensitive or radiation-sensitive composition of the present invention may further comprise a dye, a plasticizer, an acid proliferating agent (WO95 / 29968, WO98 / 24000). JP-A-8-305262, JP-A-9-34106, JP-A-8-248561, JP-A-8-503082, JP-A-5,445,917, JP-A-8. No. -503081, US Pat. No. 5,534,393, US Pat. No. 5,395,736, US Pat. No. 5,741,630, US Pat. No. 5,334,489 Specification, US Pat. No. 5,582,956, US Pat. No. 5,578,424, US Pat. No. 5,453,345, US Pat. No. 5,445,917 European Patent 66 No. 960, European Patent No. 757,628, European Patent No. 665,961, US Pat. No. 5,667,943, Japanese Patent Laid-Open No. 10-1508, Japanese Patent Laid-Open No. 10- No. 282642, JP-A-9-512498, JP-A-2000-62337, JP-A-2005-17730, JP-A-2008-209889, and the like. Examples of these compounds include the respective compounds described in JP-A-2008-268935.

[8] Carboxylic acid onium salt The negative active light-sensitive or radiation-sensitive 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 the present invention, it is preferable that the carboxylate residue of the carboxylic acid onium salt does not contain an aromatic group or a carbon-carbon double bond. A particularly preferred anion moiety is a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms. 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 negative actinic ray-sensitive or radiation-sensitive composition of the present invention may or may not contain a carboxylic acid onium salt, but when it is contained, the content of the carboxylic acid onium salt is a negative actinic ray-sensitive composition. Alternatively, it is preferably 0.5 to 20% by mass, more preferably 0.7 to 15% by mass, still more preferably 1.0 to 10% by mass, based on the total solid content of the radiation-sensitive composition. is there.

[9] Solvent The negative-type actinic ray-sensitive or radiation-sensitive composition of the present invention preferably contains a solvent.
Solvents that can be used in preparing a negative actinic ray-sensitive or radiation-sensitive composition include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate And organic solvents such as cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates and alkyl pyruvates. it can.
Specific examples of these solvents include those described in US Patent Application Publication No. 2008/0187860 [0441] to [0455].

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, alkyl butyrate, etc. are preferable, propylene glycol Monomethyl ether (PGME, also known as 1-methoxy-2-propanol), ethyl lactate, and methyl 2-hydroxyisobutyrate are more preferable. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2 -Heptanone is most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.
The solid concentration of the negative actinic ray-sensitive or radiation-sensitive composition of the present invention is preferably 1 to 40% by mass. More preferably, it is 1 to 30% by mass, and further preferably 3 to 20% by mass.

<Negative actinic ray-sensitive or radiation-sensitive film>
The present invention also relates to a negative-type actinic ray-sensitive or radiation-sensitive film formed from the negative-type actinic ray-sensitive or radiation-sensitive composition of the present invention. Such a film is, for example, a composition of the present invention. It is formed by applying an object 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 preferred. The coating film is prebaked at 60 to 150 ° C. for 1 to 20 minutes, preferably at 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.

Before forming the negative actinic ray-sensitive or radiation-sensitive film, an antireflection film may be coated on the substrate in advance.
As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as Brewer Science DUV30 series, DUV-40 series, Shipley AR-2, AR-3 and AR-5 may be used. it can.

<Mask blanks>
The present invention also relates to a mask blank provided with a negative actinic ray-sensitive or radiation-sensitive film formed from a negative actinic ray-sensitive or radiation-sensitive composition. In order to obtain a mask blank having such a negative actinic ray-sensitive or radiation-sensitive film, when forming a pattern on a photomask blank for photomask production, the transparent substrate used is quartz, A transparent substrate such as calcium fluoride can be used. 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. Examples of the material of the functional film include silicon or a film containing a transition metal such as chromium, molybdenum, zirconium, tantalum, tungsten, titanium, or niobium. 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. The thickness of the entire light shielding film is not particularly limited, but is preferably 5 to 200 nm, and more preferably 10 to 150 nm.

Generally, among these materials, when pattern formation is performed on a photomask blank having a chromium-containing material containing oxygen or nitrogen in the outermost layer, a constricted shape is formed in the vicinity of the substrate, which is a so-called undercut shape. Although it is easy, when the present invention is used, the undercut problem can be improved as compared with the conventional one.
This negative actinic ray-sensitive or radiation-sensitive film is irradiated with actinic rays or radiation (such as an electron beam) 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.
For the process for producing an imprint mold using the negative active light sensitive or radiation sensitive composition of the present invention, for example, Japanese Patent No. 4109085, Japanese Patent Application Laid-Open No. 2008-162101, And “Basics of Nanoimprint and Technology Development / Application Development-Nanoimprint Substrate Technology and Latest Technology Development-Editing: Yoshihiko Hirai (Frontier Publishing)”.

In the composition of the present invention, the above components are dissolved in a predetermined organic solvent, preferably the above mixed solvent, filtered, and then applied onto a predetermined substrate. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

<Pattern formation method using negative type actinic ray-sensitive or radiation-sensitive composition>
The present invention includes a step of coating the negative actinic ray-sensitive or radiation-sensitive composition on a substrate to form a film, a step of exposing the film, and developing the exposed film to form a negative pattern And a pattern forming method including the step of forming the pattern. The present invention also relates to a resist pattern forming method including a step of exposing a mask blank having the negative type actinic ray-sensitive or radiation-sensitive film and a step of developing the exposed mask blank. . In the present invention, the exposure is preferably performed using an electron beam or extreme ultraviolet rays.

In the manufacture of precision integrated circuit elements, exposure (pattern formation process) on the negative actinic ray-sensitive or radiation-sensitive film is first patterned in the negative actinic ray-sensitive or radiation-sensitive film of the present invention. It is preferable to perform electron beam or extreme ultraviolet (EUV) irradiation. Exposure in the case of electron beam, 0.1 ~ 20μC / cm ^2, preferably about 3 ~ 10μC / cm ² or so, if the extreme ultraviolet, 0.1 ~ 20mJ / cm ^2, preferably about 3 ~ 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 at 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, it is 0.1 to 5% by mass, preferably 2 to 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) from the viewpoint that the negative actinic ray-sensitive or radiation-sensitive film can be prevented from swelling. It is preferable to use an ester solvent having 2 or less heteroatoms.
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 ester solvents 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 negative actinic ray-sensitive or radiation-sensitive film.
When an ester solvent and a hydrocarbon solvent are used in combination, isoamyl acetate is preferably used as the ester solvent. In addition, as a hydrocarbon solvent, from the viewpoint of adjusting the solubility of a negative actinic ray-sensitive or radiation-sensitive film, a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) Is preferably used.
Examples of ketone solvents 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 alcohol solvents 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 amide solvents 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, 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, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, 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, n-butyl 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, methoxymethyl butanol and other glycol ether solvents, 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-63-34540, 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 US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. 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 above-described various development methods include a step of discharging the developer from the developing nozzle of the developing device toward the negative actinic ray-sensitive or radiation-sensitive film, the discharge pressure of the discharged developer (the discharged developer) flow rate per unit area of the liquid) is preferably 2mL / sec / mm ² or less, more preferably 1.5mL / sec / mm ² or less, still more preferably 1mL / 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 to the negative actinic ray-sensitive or radiation-sensitive film by the developer decreases, and the negative actinic ray-sensitive or This is considered to be because the radiation-sensitive film / pattern is prevented from being accidentally cut or collapsed.
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.

Further, after the step of developing using a developer containing an organic solvent, a step of stopping development may be performed while substituting with another 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 with 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 step of cleaning using a rinse liquid containing an alcohol solvent or a hydrocarbon solvent, and more preferably.

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.
In this way, a developing solution that has slightly soaked in the negative actinic ray-sensitive or radiation-sensitive film after development by using a hydrocarbon solvent (especially an aliphatic hydrocarbon solvent) as the organic solvent contained in the rinsing solution Is washed away, swelling is further suppressed, and pattern collapse is further suppressed.

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 onto the substrate surface (spray method), and the like can be applied. Among these, it is preferable to perform a cleaning process by a spin coating method, rotate the substrate at a rotational speed of 2000 rpm to 4000 rpm, 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 performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

Further, the pattern forming method of the present invention may have a developing step using an organic developer and a developing step using an alkali developer. A portion with low exposure intensity is removed by development using an organic developer, and a portion with high exposure intensity is also removed by development using an alkali developer. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only an intermediate exposure intensity region, so that a finer pattern than usual can be formed (paragraph of JP 2008-292975 A). [Mechanism similar to [0077]).

The present invention also relates to a photomask obtained by exposing and developing the mask blank having the negative radiation sensitive or actinic ray sensitive film. The steps described above are applied as exposure and development. The photomask is preferably used for semiconductor manufacturing.
The photomask in the present invention may be a light transmissive mask used in an ArF excimer laser or the like, or a light reflective mask used in reflective lithography using EUV light as a light source.

Note that an imprint mold may be produced using the composition of the present invention, and details thereof can be referred to, for example, Japanese Patent No. 4109085 and Japanese Patent Application Laid-Open No. 2008-162101.
The resist pattern forming method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACSano Vol. 4 No. 8 Pages 4815-4823).
Further, the resist pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.

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

Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto.

<Synthesis Example: Synthesis of Polymer Compound (A1)>
The polymer compound (A1) shown in Table 8 below was synthesized as follows.

(Synthesis of Polymer 1a)
10 g of poly (p-hydroxystyrene) (VP 2500, dispersity 1.10) manufactured by Nippon Soda Co., Ltd. and an aqueous potassium hydroxide solution (5.7 g of potassium hydroxide dissolved in 49 g of water) were mixed, and 20 g of methanol was added thereto. In addition, the mixture was stirred at 40 ° C. for several minutes. Thereto, 7.5 g of paraformaldehyde was added and stirred at 40 ° C. for 5 hours. After completion of the reaction, the reaction solution was returned to room temperature, and 80 ml of ethyl acetate and 80 ml of diluted hydrochloric acid (1N) were added to carry out a liquid separation operation. The organic layer was washed with distilled water until the aqueous layer became neutral, and then the organic layer was concentrated. After vacuum drying, 13 g of polymer (1a) was obtained.
¹ H-NMR (DMSO-d6: ppm) δ: 9.04, 8.39, 6.59, 4.11-5.50, 0.92-2.26 (all peaks are broad)

(Synthesis of polymer compound A1)
7 g of the polymer (1a) and 100 g of methanol were mixed, and a solution obtained by mixing 3.4 g of concentrated sulfuric acid and 10 g of methanol was added thereto, followed by stirring at 55 ° C. for 3 hours. After completion of the reaction, the reaction solution was returned to room temperature, 200 g of ethyl acetate and 200 g of distilled water were added, and a liquid separation operation was performed. The organic layer was washed 3 times with distilled water, and then the organic layer was concentrated. A solution obtained by dissolving the obtained powder in 70 g of ethyl acetate was added dropwise to 700 g of n-hexane. The powder was filtered and vacuum dried to obtain 5.4 g of a polymer compound (A1).
¹ H-NMR (DMSO-d6: ppm) δ: 9.02, 8.09, 6.49, 4.27, 3.13, 0.81-2.22 (all peaks are broad)
Other polymer compounds A2 to A8 were synthesized in substantially the same manner as described above. On the other hand, the polymer compound A9 was prepared according to the method described in JP-A-2-170165.

In the above synthesis example, the polymer compound synthesized may be more than the two-component system. For example, in Synthesis Example 1 described above, a three-component system, that is, a repeating unit having 0 crosslinkable groups, a repeating unit having 1 crosslinkable group, and a repeating unit having 2 crosslinkable groups. There may be. Since it is complicated to distinguish and calculate the ratio of the repeating unit having 1 crosslinkable group and the ratio of the repeating unit having 2 crosslinkable groups, the crosslinkable group ratio defined below can be used in the polymer compound. The number of crosslinkable groups contained was evaluated.

(Crosslinkable group ratio) = (Number of points where a crosslinkable group was introduced) / (Number of reaction points where a crosslinkable group can be introduced) × 100 (%)

Here, for example, when the aromatic ring to which the phenolic hydroxyl group is bonded is a benzene ring, the number of reactive sites capable of introducing a methylol group as a crosslinkable group is a maximum of 3 at 2 positions in the ortho position and 1 position in the para position. It is a place. In the case of the polymer compound A1, since the para position is blocked by the bond with the polymer main chain, the number of reaction points at which a methylol group can be introduced (number of methylol groups) is 2. The crosslinkable group ratio was calculated by estimating the change before and after the reaction of the integral value of the hydrogen atom at the point where the crosslinkable group can be introduced, from ¹ H-NMR.

The following table shows the crosslinkable group ratio, weight average molecular weight and dispersity of the polymer compound. The weight average molecular weight and dispersity were calculated by GPC (solvent: THF) measurement. The structure of the polymer compounds A1 to A8 may be a three-component system or more as described above. However, for the sake of simplicity, the structure of the repeating unit having zero crosslinkable groups and the maximum number of crosslinkable groups (reaction points) Only two components of the structure of the repeating unit of (represents the case where all have reacted). On the other hand, the polymer compound A9 is obtained by polymerization of monomers corresponding to the repeating units described in the table below, and substantially has only one component of the repeating units described in the table below.

[Examples 1E to 33E and Comparative Examples 1ER to 5ER]
(1) Preparation of support A 6-inch silicon 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 solution The components shown in Table 9 below were dissolved in the solvents shown in the same table, and each was microfiltered with a polytetrafluoroethylene filter having a pore size of 0.04 µm to obtain a resist coating solution. .

(3) Preparation of resist film A resist coating solution is applied onto the 6-inch silicon 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 negative actinic ray sensitive or A resist film having a thickness of 50 nm was obtained as a radiation sensitive film. That is, a mask blank provided with a negative type actinic ray-sensitive or radiation-sensitive film was 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 120 ° 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, resolving power, PED stability, and line edge roughness (LER) performance 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 (electron beam irradiation amount) when resolving a 1: 1 line and space resist pattern having a line width of 50 nm was defined as sensitivity. The smaller this value, the higher the sensitivity.
However, for Comparative Examples 1ER to 5ER, a 1: 1 line and space pattern with a line width of 50 nm could not be resolved. Therefore, for Comparative Example 1ER, a 1: 1 line and space pattern with a line width of 100 nm was compared. For Example 2ER, a 1: 1 line and space pattern with a line width of 80 nm, for Comparative Example 3ER, a 1: 1 line and space pattern with a line width of 70 nm, and for Comparative Example 4ER, a 1: 1 line and space pattern with a line width of 60 nm. For the comparative example 5ER, the irradiation energy when resolving a 1: 1 line and space pattern with a line width of 65 nm was defined as sensitivity (Eop).

[Resolution]
The resolving power (nm) was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the exposure amount (electron beam irradiation amount) showing the above sensitivity.

[Line edge roughness (LER) performance]
A 1: 1 line and space pattern having a line width of 50 nm was formed with the exposure amount (electron beam irradiation amount) showing the above sensitivity. Then, for any 30 points included in the length direction of 10 μm, the distance from the reference line where the edge should be was measured using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. A smaller value indicates better performance.
However, in Comparative Examples 1ER to 5ER, a 1: 1 line and space pattern having a line width of 50 nm could not be resolved. Therefore, in Comparative Example 1ER, a 1: 1 line and space pattern having a line width of 100 nm was compared. In Example 2ER, a 1: 1 line and space pattern with a line width of 80 nm, in Comparative Example 3ER, a 1: 1 line and space pattern with a line width of 70 nm, and in Comparative Example 4ER, a 1: 1 line and space pattern with a line width of 60 nm. With respect to the pattern, in Comparative Example 5ER, the standard deviation of the above distance was obtained for a 1: 1 line and space pattern with a line width of 65 nm, and 3σ was calculated.

[PED (Post Exposure time Delay) stability]
With an exposure amount at which the line width dimension of a 1: 1 line and space pattern with a line width of 50 nm is 50 nm, the line line width dimension (0 h) on a wafer subjected to PEB treatment immediately after exposure and a wafer subjected to PEB treatment after 5 hours. The upper line line width dimension (5.0 h) was measured, and the line width change rate was calculated by the following equation.
Line width change rate (%) = | ΔCD (5.0h-0h) | nm / 50 nm
A smaller value indicates better performance, and is used as an indicator of PED stability.
However, in Comparative Examples 1ER to 5ER, a 1: 1 line and space pattern with a line width of 50 nm could not be resolved. Therefore, in Comparative Example 1ER, the line width of the 1: 1 line and space pattern with a line width of 100 nm was used. The above-mentioned line width change rate was calculated at an exposure amount with a dimension of 100 nm. In Comparative Example 2ER, the above-described line width change rate was calculated at an exposure amount at which the line width dimension of the 1: 1 line and space pattern having a line width of 80 nm was 80 nm. In Comparative Example 3ER, the above-described line width change rate was calculated at an exposure amount at which the line width dimension of a 1: 1 line and space pattern having a line width of 70 nm was 70 nm. In Comparative Example 4ER, the above-described line width change rate was calculated at an exposure amount at which the line width dimension of the 1: 1 line and space pattern having a line width of 60 nm was 60 nm. In Comparative Example 5ER, the above-described line width change rate was calculated at an exposure amount at which the line width dimension of the 1: 1 line and space pattern having a line width of 65 nm was 65 nm.

[Photoacid generator]
The structure of the photoacid generator used in the examples is shown below together with the volume value of the acid generated by the photoacid generator. Here, the volume value of the acid was obtained by the same calculation method as the volume value of the acid generated from the compound (B).

[Basic compounds]
B1: Tetrabutylammonium hydroxide B2: Tri (n-octyl) amine B3: 2,4,5-triphenylimidazole

[Crosslinking agent]

[Other polymer compounds]
Regarding the composition ratio (molar ratio; corresponding in order from the left) of each repeating unit in the other polymer compound P1, and the weight average molecular weight (Mw) and dispersity (Mw / Mn) in the other polymer compounds P1 and P2 It is shown below.

[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 (Dainippon Ink Chemical Co., Ltd .; Fluorine)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)

〔solvent〕
S1: Propylene glycol monomethyl ether acetate (1-methoxy-2-acetoxypropane)
S2: Propylene glycol monomethyl ether (1-methoxy-2-propanol)
S3: 2-heptanone S4: Ethyl lactate S5: Cyclohexanone S6: γ-butyrolactone S7: Propylene carbonate

From the above table, Examples 1E to 33E using the pattern forming method according to the present invention have higher sensitivity, resolution, PED stability, and LER performance than Comparative Examples 1ER to 5ER that do not use this. It turns out that it is compatible in dimension.

[Examples 1F to 10F and Comparative Examples 1FR to 4FR]
(Create resist film)
On the 6-inch silicon wafer, the resist coating solution prepared as described above was applied using a spin coater Mark8 manufactured by Tokyo Electron, and dried on a hot plate at 110 ° C. for 90 seconds to obtain a negative actinic ray sensitive light Alternatively, a resist film having a thickness of 50 nm was obtained as a radiation sensitive film. That is, a mask blank provided with a negative type actinic ray-sensitive or radiation-sensitive film was obtained.

(Resist evaluation)
With respect to the obtained resist film, sensitivity, resolution, PED stability, and line edge roughness (LER) performance were evaluated by the following methods.

〔sensitivity〕
Using the EUV exposure apparatus (MicroExposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech), the exposure amount of the obtained resist film is 0-20.0 mJ / cm ^2. The film was exposed through a reflective mask having a 1: 1 line-and-space pattern with a line width of 50 nm while changing by 0.1 mJ / cm ^{2 in} the range, and then baked at 110 ° C. for 90 seconds. Then, it developed using the 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution.
The exposure amount for reproducing a 1: 1 line and space mask pattern having a line width of 50 nm was defined as sensitivity. The smaller this value, the higher the sensitivity.
However, for Comparative Examples 1FR to 4FR, a 1: 1 line and space pattern with a line width of 50 nm could not be resolved. Therefore, for Comparative Example 1 FR, a 1: 1 line and space pattern with a line width of 350 nm was compared. For Example 2FR, a 1: 1 line and space pattern with a line width of 100 nm, for Comparative Example 3FR, a 1: 1 line and space pattern with a line width of 85 nm, and for Comparative Example 4FR, a 1: 1 line and space pattern with a line width of 60 nm. Irradiation energy when resolving each pattern was defined as sensitivity (Eop).

[Resolution]
The resolving power (nm) was defined as the limiting resolving power (minimum line width at which a line and a space (line: space = 1: 1) were separated and resolved) at the exposure amount showing the above sensitivity.

[Line edge roughness (LER) performance]
A 1: 1 line and space pattern having a line width of 50 nm was formed with the exposure amount showing the above sensitivity. Then, for any 30 points in the length direction of 50 μm, the distance from the reference line where there should be an edge was measured using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. A smaller value indicates better performance.
However, in Comparative Examples 1FR to 4FR, a 1: 1 line and space pattern having a line width of 50 nm could not be resolved. Therefore, in Comparative Example 1FR, a 1: 1 line and space pattern having a line width of 350 nm was compared. In Example 2FR, a 1: 1 line and space pattern with a line width of 100 nm, in Comparative Example 3FR, a 1: 1 line and space pattern with a line width of 85 nm, and in Comparative Example 4FR, a 1: 1 line and space pattern with a line width of 60 nm. For each of the patterns, the standard deviation of the above distance was obtained, and 3σ was calculated.

[PED (Post Exposure time Delay) stability]
50 nm line-and-space 1: 1 pattern line width dimension is 50 nm, and the line width dimension (0h) of PEB processed immediately after exposure and the line line width on the wafer subjected to PEB processing after 5 hours. The dimension (5.0 h) was measured, and the line width change rate was calculated by the following equation.
Line width change rate (%) = | ΔCD (5.0h-0h) | nm / 50 nm
A smaller value indicates better performance, and is used as an indicator of PED stability.
However, in Comparative Examples 1FR to 4FR, the 1: 1 line and space pattern having a line width of 50 nm could not be resolved. Therefore, in Comparative Example 1FR, the line width of the 1: 1 line and space pattern having a line width of 350 nm was used. The above-mentioned line width change rate was calculated at an exposure amount with a dimension of 350 nm. In Comparative Example 2FR, the line width change rate was calculated at an exposure amount at which the line width dimension of a 1: 1 line and space pattern having a line width of 100 nm was 100 nm. In Comparative Example 3FR, the line width change rate was calculated at an exposure amount at which the line width dimension of the 1: 1 line and space pattern having a line width of 85 nm was 85 nm. In Comparative Example 4FR, the above-described line width change rate was calculated at an exposure amount at which the line width dimension of the 1: 1 line and space pattern having a line width of 60 nm was 60 nm.

From the above table, according to Examples 1F to 10F using the pattern forming method according to the present invention, sensitivity, resolving power, PED stability, and LER performance are higher than those of Comparative Examples 1ER to 4FR that do not use this. It turns out that it is compatible in dimension.

Claims

(A) a polymer compound having a repeating unit represented by the following general formula (1);
(B) by irradiation with actinic rays or radiation, a compound volume to generate a 130 Å 3 or more 2000 Å 3 following acids,
A negative-type actinic ray-sensitive or radiation-sensitive resin composition.

In the formula, R 1 represents a hydrogen atom, an alkyl group, or a halogen atom,
R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group,
R 4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an acyl group,
L represents a single bond or a divalent linking group,
Ar represents an aromatic group,
m and n each independently represents an integer of 1 or more.
The negative actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (2).

Wherein, R 1, R 2, R 3 and R 4 have the same meanings as in formula (1) R 1, R 2 , R 3 and R 4 in. m ′ represents 1 or 2, and n ′ represents an integer of 1 to 3.
The negative actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit represented by the general formula (2) is a repeating unit represented by the following general formula (3).

Wherein, R 2, R 3, and R 4 in general formula (1) R 2, R 3, and is synonymous with R 4. n ′ represents an integer of 1 to 3.
The negative actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the compound (B) is a sulfonium salt.
The negative actinic ray-sensitive or radiation-sensitive compound according to any one of claims 1 to 4, further comprising a basic compound or an ammonium salt compound (C) whose basicity is lowered by irradiation with actinic rays or radiation. Resin composition.
The negative actinic ray-sensitive or radiation-sensitive resin composition according to claim 5, wherein the compound (C) is an onium salt compound represented by the following general formula (4).

In the formula, A represents a sulfur atom or an iodine atom, R A represents a hydrogen atom or an organic group, R B represents a (p + 1) -valent organic group, X represents a single bond or a linking group, and A N represents Represents a basic moiety containing a nitrogen atom. When a plurality of R A , R B , X and A N are present, they may be the same or different.
When A is a sulfur atom, q is an integer of 1 to 3, and o is an integer that satisfies the relationship of o + q = 3.
When A is an iodine atom, q is 1 or 2, and o is an integer that satisfies the relationship of o + q = 2.
p represents an integer of 1 to 10, and Y − represents an anion.
At least two of R A , X, R B and A N may be bonded to each other to form a ring.
The negative actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein the dispersity of the polymer compound (A) is 1.0 to 1.40.
8. The polymer compound according to claim 1, wherein the polymer compound (A) is a polymer compound produced by a production method using a polymer of a repeating unit represented by the following general formula (5) as a raw material. Negative-type actinic ray-sensitive or radiation-sensitive resin composition described in 1.

R 1 in the formula has the same meaning as R 1 in the general formula (1).
The negative actinic ray-sensitive or radiation-sensitive resin composition according to claim 8, wherein the polymer of the repeating unit represented by the general formula (5) has a dispersity of 1.0 to 1.20.
R 2 and R 3 in the general formula (3) are hydrogen atom, a negative actinic ray-sensitive or radiation-sensitive resin composition according to claim 3.
A negative-type actinic ray-sensitive or radiation-sensitive film formed using the negative-type actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10.
Mask blanks comprising the negative actinic ray-sensitive or radiation-sensitive film according to claim 11.
Applying the negative actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10 on a substrate to form a film;
A pattern forming method comprising: a step of exposing the film; and a step of developing the exposed film to form a negative pattern.
An electronic device manufacturing method including the pattern forming method according to claim 13.