KR102051343B1 - Negative actinic ray-sensitive or radiation-sensitive resin composition, negative actinic ray-sensitive or radiation-sensitive film, pattern formation method, and manufacturing method of electronic device - Google Patents

Abstract

식 중, R₁은 수소 원자, 알킬기, 또는 할로젠 원자를 나타내고, R₂와 R₃은, 각각 독립적으로, 수소 원자, 알킬기, 사이클로알킬기, 아랄킬기, 또는 아릴기를 나타내며, R₄는 수소 원자, 알킬기, 사이클로알킬기, 아릴기, 또는 아실기를 나타내고, L은 단결합 또는 2가의 연결기를 나타내며, Ar은 방향족기를 나타내고, m과 n은, 각각 독립적으로, 1 이상의 정수를 나타낸다.In particular, in the formation of an ultrafine pattern (for example, a line width of 50 nm or less), a negative actinic ray capable of forming a pattern excellent in sensitivity, resolution, PED stability, and line edge roughness (LER) performance The mask blank which has a sex or radiation sensitive resin composition and a negative actinic-ray-sensitive or radiation-sensitive film using it, a negative actinic-ray-sensitive or radiation-sensitive film, the pattern formation method, and the electron containing the said pattern formation method Provided is a method of manufacturing a device. Mask blank is, (A) to by a polymer having a repeating unit represented by the general formula (1) compound and, (B) irradiation of actinic ray or radiation, and the volume is 130Å ³ above comprising a compound capable of generating an 2000Å ³ or less acid And a negative actinic ray-sensitive or radiation-sensitive resin composition, and a negative actinic ray-sensitive or radiation-sensitive film and a negative actinic ray-sensitive or radiation-sensitive film using the same.

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, and m and n each independently represent an integer of 1 or more.

Description

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

The present invention can form a high-definition pattern using electron beams or extreme ultraviolet rays, which are suitably used for ultra-microlithography processes such as the manufacture of ultra-LSI and high-capacity microchips and other photofabrication processes. It relates to a negative actinic ray-sensitive or radiation-sensitive resin composition, a negative actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a manufacturing method of an electronic device.

Conventionally, in the manufacturing process of semiconductor devices, such as IC and LSI, the microprocessing by lithography using a photoresist composition is performed. In recent years, with the high integration of integrated circuits, the formation of ultra-fine patterns in the submicron region or the quarter micron region has been required. As a result, the exposure wavelength also shows a tendency to shorten the wavelength, as in g-line to i-line, and also excimer laser light. Lithography using electron beams or X-rays is also currently under development.

These electron beams, X-rays, or EUV optical 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, what is called a negative chemical amplification type resist composition which consists mainly of alkali-soluble resin, a crosslinking agent, and an acid generator is used effectively (for example, refer patent document 1).

In the formation of a negative resist pattern, even when an unexposed part intended to be removed by a developer and an exposed part not intended to be removed by a developer are provided by exposure, the exposed part of the unexposed part Adjacent regions are usually exposed although the exposure amount is low (hereinafter, this region is referred to as a "weak exposure section"). Therefore, also in the weakly exposed portion, insolubilization or poor solubility of the developer proceeds, which causes a bridge between the patterns formed by the development.

On the other hand, as a negative chemically amplified resist composition containing an acid generator, a polymer having both in the polymer structure a crosslinking group in which a crosslinking reaction proceeds with an acid, and a site capable of crosslinking reaction with the crosslinking group (hereinafter, , "Crosslinked supported polymer") is being developed. In a general negative chemically amplified resist composition which is negatively formed using a low molecular crosslinking agent, volatilization of the low molecular crosslinking agent in the process is often a problem, but in a crosslinking supporting polymer, there is an advantage that there is no such concern. For example, Patent Document 2 describes a polymer having a methylol group as a crosslinkable group in a polymer having a phenolic hydroxyl group.

Patent Document 1: Japanese Unexamined Patent Publication No. 2002-99085 Patent Document 2: Japanese Patent Application Laid-open No. Hei 2-170165

However, in the formation of ultra fine patterns such as 50 nm or less in line width, sufficient resolution was not obtained.

Moreover, although the further improvement of PED stability (coating film stability in the case of leaving it to stand until performing heating operation (PEB) after exposure) is also requested | required, in patent document 2, it is not mentioned about PED stability. At the same time, the actual PED stability is insufficient.

Accordingly, an 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 (e.g., 50 nm or less in line width). The mask blank which has a negative actinic-ray-sensitive or radiation-sensitive resin composition which can be used, and a negative actinic-ray-sensitive or radiation-sensitive film using it, a negative actinic-ray-sensitive or radiation-sensitive film, the pattern formation method, the said pattern It is providing the manufacturing method of an electronic device containing a formation method, and an electronic device.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said objective was achieved by the resist composition which combined the high molecular compound of a specific structure and the specific compound which generate | occur | produces an acid by irradiation of actinic light or a radiation.

That is, this invention is as follows.

〔One〕

(A) to by a polymer having a repeating unit represented by the general formula (1) compound and, (B) irradiation of actinic ray or radiation, that the volume contains a compound capable of generating an 130Å ³ than 2000Å ³ or less acid, a negative-type Actinic ray-sensitive or radiation-sensitive resin composition.

[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 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 each independently represent an integer of 1 or more.

〔2〕

The negative actinic-ray-sensitive or radiation-sensitive resin composition as described in said [1] whose repeating unit represented by the said General formula (1) is a repeating unit represented by the following General formula (2).

[Formula 2]

Wherein, R _1, R _2, R ₃ and R ₄ is an R _1, R _2, R ₃ and R ₄ with the consent of the general formula (1). m 'represents 1 or 2, n' represents the integer of 1-3.

[3]

The negative actinic ray-sensitive or radiation-sensitive resin composition according to the above [2], wherein the repeating unit represented by General Formula (2) is a repeating unit represented by the following General Formula (3).

[Formula 3]

Wherein, R _2, R _3, and R ₄ is an R _2, R _3, and R ₄ and the consent of the general formula (1). n 'represents the integer of 1-3.

〔4〕

The negative actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above [1] to [3], wherein the compound (B) is a sulfonium salt.

[5]

The negative actinic ray-sensitive or radiation-sensitive according to any one of the above [1] to [4], further comprising a basic compound or an ammonium salt compound (C), the basicity of which is lowered by irradiation of actinic rays or radiation. Resin composition.

[6]

The negative actinic ray-sensitive or radiation-sensitive resin composition according to the above [5], wherein the compound (C) is an onium salt compound represented by the following General Formula (4).

[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) valence organic group, X represents a single bond or a linking group, and A _N represents nitrogen A basic site including an atom is shown. When two or more R _<A> , R <_B> , X and A <_N> respectively exist, they may be same or different.

When A is a sulfur atom, q is an integer of 1-3 and o is an integer which 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 o + q = 2.

p represents the integer of 1-10, 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]

Negative actinic-ray-sensitive or radiation-sensitive resin composition in any one of said [1]-[6] whose dispersion degree of the said high molecular compound (A) is 1.0-1.40.

〔8〕

Negative persimmon as described in any one of said [1]-[7] whose said high molecular compound (A) is a high molecular compound manufactured by the manufacturing method which uses the polymer of the repeating unit represented by following General formula (5) as a raw material. Actinic or radiation-sensitive resin composition.

[Formula 5]

R ₁ in the formula is R ₁ and consent of the general formula (1).

[9]

The negative actinic-ray-sensitive or radiation-sensitive resin composition as described in said [8] whose dispersion degree of the polymer of the repeating unit represented by the said General formula (5) is 1.0-1.20.

[10]

Negative actinic-ray-sensitive or radiation-sensitive resin composition as described in said [3] whose R <_2> and R <_3> in the said General formula (3) are both hydrogen atoms.

[11]

The negative actinic ray-sensitive or radiation-sensitive film formed using the negative actinic-ray-sensitive or radiation-sensitive resin composition in any one of said [1]-[10].

[12]

The mask blank provided with the negative actinic-ray-sensitive or radiation-sensitive film as described in said [11].

[13]

Applying the negative actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above [1] to [10] onto a substrate to form a film,

Exposing the film, and

And forming a negative pattern by developing the exposed film.

[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, particularly in the formation of an ultrafine pattern (e.g., 50 nm or less in line width), it is possible to form a negative actinic ray characteristic capable of forming a pattern excellent in sensitivity, resolution, PED stability, and LER performance. Manufacture of an electronic device comprising a mask blank having a radiation sensitive resin composition and a negative actinic ray-sensitive or radiation-sensitive film, a negative actinic ray-sensitive or radiation-sensitive film using the same, a pattern forming method, and the pattern forming method A method, and an electronic device can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

In the description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

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

In addition, unless otherwise indicated, "exposure" in this specification means not only exposure of the bright spectrum of a mercury lamp, the ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, EUV light, etc., but an electron beam, an ion beam, etc. Drawing by particle beam is also included in exposure.

In this specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersion degree (Mw / Mn) of a high molecular compound and resin are GPC measurement (solvent: HLC-8120GPC) by GPC apparatus (solvent: 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) detector) It is defined as a polystyrene conversion value by.

The negative actinic ray-sensitive or radiation-sensitive resin composition of the present invention,

(A) a polymer compound having a repeating unit represented by General Formula (1) (hereinafter also referred to as "polymer compound (A)"),

(B) A compound which generates an acid having a volume of 130 to ³ or more and 2000 to ³ or less by irradiation with actinic light or radiation (hereinafter also referred to as "acid generator (B)" or "compound (B)).

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 having excellent sensitivity, resolution, PED stability, and LER performance, and using the same A mask blank having a negative actinic ray-sensitive or radiation-sensitive film, a negative actinic ray-sensitive or radiation-sensitive film, a pattern forming method, a manufacturing method of an electronic device comprising the pattern forming method, and an electronic device can be provided. have.

As a reason for the above, the volume of the acid in which the compound (B) is generated by irradiation of actinic light or radiation in the present invention is 130 kPa ³ or more, and the diffusivity of the acid generated from the compound (B) is low. . As a result, the diffusion of excess acid into the unexposed portion is suppressed, and thus, the resolution in the ultrafine region is considered to be improved. Moreover, it is thought that PED stability improves as a result by the low diffusivity of the acid after exposure. However, in the present invention, high resolution that cannot be explained only by the above diffusibility has been obtained. The reason is not clear, but the following is estimated.

The crosslinkable group-containing polymer typically has a large (bulky) crosslinkable structural moiety containing a crosslinkable group in the side chain of the polymer (for example, JP 2014-24999 A), but the polymer compound of the present invention Since (A) has a crosslinkable group couple | bonded with respect to the benzene ring which couple | bonds with the principal chain of a high molecular compound directly, it has a very compact structure compared with said typical crosslinkable group containing polymer. In the case of a typical crosslinkable group-containing polymer, due to its size, since it has a certain free volume even after crosslinking, the effect of suppressing diffusion of an acid generated in the exposed portion is limited, but in the case of a compact structure like the present invention, It is assumed that the free volume is very small, and the above-described acid diffusion inhibiting effect is larger than expected, and as a result, the resolution is very high. In addition, it is estimated that LER performance is also excellent by this effect | action.

Hereinafter, the negative actinic-ray-sensitive or radiation-sensitive resin composition which concerns on this invention is demonstrated.

It is preferable that it is for electron beam or extreme ultraviolet exposure, and, as for the negative actinic-ray-sensitive or radiation-sensitive resin composition which concerns on this invention, it is more preferable for electron beam exposure.

The negative actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition for negative pattern formation, and may be a negative resist composition for organic solvent development or a negative resist composition for alkali development. The composition according to the present invention is typically a chemically amplified resist composition.

Hereinafter, each component in the negative actinic-ray-sensitive or radiation-sensitive resin composition of this invention is demonstrated in detail.

[1] (A) polymer compounds

A high molecular compound (A) is a high molecular compound which has a repeating unit represented by following General formula (1).

[Formula 6]

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 is represented, L represents a single bond or a bivalent coupling group, Ar represents an aromatic group, m and n respectively independently represent the integer of 1 or more.

Examples of the halogen atom for R ₁ include fluorine, chlorine, bromine and iodine. It is preferable that it is a hydrogen atom or a methyl group, and, as for R <_1> , it is more preferable that it is a hydrogen atom.

Examples of the divalent linking group represented by L include a monocyclic or polycyclic aromatic ring, -C (= O)-, -OC (= O)-, -CH ₂ -OC (= O)-, thiocarbonyl group, linear or Branched alkylene groups (preferably having 1 to 10 carbon atoms, more preferably 1 to 6), linear or branched alkenylene groups (preferably having 2 to 10 carbon atoms, more preferably 2 to 6), and cycloalkyl A divalent linking group (preferably total carbon number), a benzene group (preferably having 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms), a sulfonyl group, -O-, -NH-, -S-, or a cyclic lactone structure 1-50, More preferably, 1-30 total carbons, More preferably, 1-20 carbons are mentioned.

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 and phenanthrene ring, or for example, thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzo And aromatic hetero rings including hetero rings such as a furan ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring. A benzene ring or a naphthalene ring is more preferable, and a benzene ring is the most preferable.

R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.

As an alkyl group represented by R <_2> and R <_3> , a C1-C10 linear or branched alkyl group etc. are mentioned, As a cycloalkyl group, a C3-C10 cycloalkyl group is mentioned. Specifically, a hydrogen atom, a methyl group, a cyclohexyl group, t-butyl group is mentioned.

When a crosslinking reaction occurs by an acid, -OR ₄ is desorbed to generate a carbo cation and the reaction proceeds. Therefore, R ₂ and R ₃ are substituents that stabilize the carbo cation, that is, an electron donating group, an aromatic group, or a hydrogen atom. desirable. It is preferable that it is an alkyl group, a cycloalkyl group, a phenyl group, or a hydrogen atom specifically, and it is more preferable that it is a hydrogen atom.

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.

Alkyl group as R ₁ in the general formula (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, divalent linking group as L, Ar as The aromatic group may have a substituent, respectively. As this substituent, an alkyl group (any of linear or branched may be sufficient, C1-C12 is preferable), an alkenyl group (C2-C12 is preferable), an alkynyl group (C2-C12 is preferable), and a cyclo Alkyl group (monocyclic, polycyclic, or any one of 3 to 12 carbon atoms), aryl group (preferably 6 to 18 carbon atoms), hydroxy group, alkoxy group, ester group, amide group, urethane group, ureido group And a thioether group, a sulfonamide group, a halogen atom, a haloalkyl group, and a sulfonic acid ester group. Preferred examples include alkyl groups, cycloalkyl groups, halogen atoms, haloalkyl groups, hydroxy groups, alkoxy groups, aryloxy groups, ester groups and aryl groups, and more preferred examples include alkyl groups, halogen atoms, hydroxy groups and alkoxy. The group can be mentioned. Examples of the halogen atom include the same ones as those described above for R ₁ .

The substituent may further have a substituent, and 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, an alkoxycarbonyl group, and an aryl. A group, an alkoxyalkyl group, group which combined these is mentioned, C8 or less is preferable.

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

Moreover, it is more preferable that the repeating unit represented by General formula (1) is a repeating unit represented by following General formula (2).

[Formula 7]

Wherein, R _1, R _2, R ₃ and R ₄ is an R _1, R _2, R ₃ and R ₄ with the consent of the general formula (1). m 'represents 1 or 2, n' represents the integer of 1-3.

R _1, R _2, specific examples and preferable examples of R ₃ and R ₄ are the same as those in described with respect to R _1, R _2, R ₃ and R ₄ in the general formula (1).

It is more preferable that m 'is 1.

n 'represents the integer of 1-3 and it is more preferable that it is 1 or 2.

Moreover, it is more preferable that the repeating unit represented by General formula (2) is a repeating unit represented by following General formula (3).

[Formula 8]

Wherein, R _2, R _3, and R ₄ is an R _2, R _3, and R ₄ and the consent of the general formula (1). n 'represents the integer of 1-3.

R _2, R _3, R ₄ and n 'Specific examples and preferred examples are, R _2, R _3, R ₄ and n in the formula (1) or general formula (2)' is the same as that described for the . Here, it is preferable that both R <_2> and R <_3> are hydrogen atoms.

From the viewpoint of crosslinking efficiency and developability, the content rate of the repeating unit represented by General Formula (1), (2) or (3) is 20-100 mol% with respect to all the repeating units contained in a high molecular compound (A). It is preferable and it is more preferable that it is 40-100 mol%.

In addition, the introduction ratio (hereinafter also referred to as crosslinkable group ratio) of the group represented by-(R ₂ ) (R ₃ ) (OR ₄ ) as a crosslinkable group in General Formula (1), (2) or (3) is From a viewpoint of crosslinking efficiency and developability, it is preferable that it is 20 to 100%, and it is more preferable that it is 40 to 100%. Here, the crosslinkable group ratio is the percentage (%) of the score (number) of the crosslinkable group in a high molecular compound (A) divided by the number (number) of reaction points which can introduce a crosslinkable group. The reaction point which can introduce | transduce a crosslinkable group, for example, when the calculation object has a phenolic hydroxyl group, becomes a point which can introduce a crosslinkable group among the ortho and para position of a phenolic hydroxyl group in consideration of the presence position of a phenolic hydroxyl group. . The detailed description is as mentioned later in the term of an Example.

Although the following structure is mentioned as a specific example of the repeating unit represented by General formula (1), (2) or (3), It is not limited to these.

[Formula 9]

[Formula 10]

[Formula 11]

The high molecular compound (A) may further have a repeating unit which has a phenolic hydroxyl group different from the repeating unit represented by the said General formula (1).

Here, a phenolic hydroxyl group is group which replaces the hydrogen atom of an aromatic ring group with a hydroxyl 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, What has a structural unit represented with the following general formula (II) is preferable.

[Formula 12]

In the formula,

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 General formula (II) represents an organic group, as an organic group, an alkyl group, a cycloalkyl group, and an aryl group are preferable, and a C1-C10 linear or branched alkyl group (for example, a methyl group, an ethyl group, a propyl group, a view) More preferred are a methyl group, a pentyl group), a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, a norbornyl group), and an aryl group having 6 to 10 carbon atoms (e.g., a phenyl group and a naphthyl group). Do.

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

As an organic group in the case of having a substituent, a trifluoromethyl group, a hydroxymethyl group, etc. are mentioned.

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, a divalent linking group is preferably a carbonyl group, an alkylene group, an arylene group, a sulfonyl group, -O-, -NH-, or a combination thereof (for example, an ester bond). Do.

D ₁ is preferably a single bond or a carbonyloxy group, and more preferably a single bond.

As an aromatic ring group which Ar <_2> represents, it is preferable that it is group (n represents the integer of 1 or more) which removed n + 1 hydrogen atom from the monocyclic or polycyclic aromatic ring.

As said aromatic ring, the aromatic hydrocarbon ring (preferably C6-C18) which may have substituents, such as a benzene ring, a naphthalene ring, anthracene ring, a fluorene ring, a phenanthrene ring, and a thiophene ring, Heterocycles such as furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring An aromatic heterocyclic ring is mentioned. Especially, a benzene ring and a naphthalene ring are preferable from a resolution viewpoint, and a benzene ring is the most preferable.

It is preferable that m <_1> is an integer of 1-5, It is more preferable to represent the integer of 1-3, It is more preferable to represent 1 or 2, It is especially preferable to represent 1.

In the case where m ₁ represents 1 and Ar ₂ represents a benzene ring, the substituted position of —OH may be para, meta, or ortho, relative to the position of the bond with the polymer main chain in the benzene ring, but alkali In view of developability, Parawi is preferred.

The aromatic ring in the aromatic ring group of Ar ₂ may have a substituent in addition to the group represented by -OH, and as a substituent, for example, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group , An alkylcarbonyloxy group, an alkylsulfonyloxy group, and an arylcarbonyl group. 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 General Formula (1) as a substituent.

It is preferable that general formula (II) is the following general formula (II-1).

[Formula 13]

In the formula,

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

D ₁ represents a single bond or a divalent linking group.

General formula (II-1) and R _5, and D ₁ and D ₁ and R ₅ of the consent of the general formula (II), a preferred range is also the same.

As for general formula (II), it is more preferable that it is the following general formula (II-2).

[Formula 14]

In formula, R <_5> represents a hydrogen atom, an organic group, or a halogen atom.

R ₅ in the general formula (II-2) are synonymous with R ₅ in the general formula (II), a 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.

[Formula 15]

[Formula 16]

When a high molecular compound (A) has a repeating unit which has a phenolic hydroxyl group different from the repeating unit represented by the said General formula (1), content of the repeating unit is with respect to all the repeating units of a high molecular compound (A). It is preferable that it is 1-80 mol%, It is more preferable that it is 1-70 mol%, It is more preferable that it is 1-60 mol%.

The high molecular compound (A) may further have a repeating unit as mentioned later.

The high molecular compound (A) may have a "structure in which the hydrogen atom of the phenolic hydroxyl group is substituted by the group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure" (hereinafter also referred to as "specific structure"). In this case, it is preferable that a high molecular compound (A) has "the repeating unit which has the" structure which the hydrogen atom of phenolic hydroxyl group substituted by the group which has a non-acid-decomposable polycyclic alicyclic hydrocarbon structure. " Thereby, dry etching resistance becomes favorable at the point where a high glass transition temperature (Tg) is obtained.

By having the above-described specific structure of the polymer compound (A), the glass transition temperature (Tg) of the polymer compound (A) is increased, and a very hard resist film can be formed, and acid diffusion and dry etching resistance can be controlled. have. Therefore, since the diffusivity of the acid in the exposed portion of actinic rays or radiation such as electron beams and extreme ultraviolet rays is very suppressed, the resolution, pattern shape and LER in fine patterns are more excellent. Moreover, it is thought that compound (D) has a non-acid-decomposable polycyclic alicyclic hydrocarbon structure contributes to the further improvement of dry etching resistance. In addition, although the details are unclear, the polycyclic alicyclic hydrocarbon structure has a high donation of hydrogen radicals, and becomes a hydrogen source at the time of decomposition of the photoacid generator, thereby further improving the decomposition efficiency of the photoacid generator, and increasing the acid generation efficiency. It is estimated that. It is thought that this contributes to better sensitivity.

The above-mentioned specific structure which the high molecular compound (A) which concerns on this invention has may have an aromatic ring, such as a benzene ring, and the group which has a non-acid-decomposable polycyclic alicyclic hydrocarbon structure, connected through the oxygen atom derived from a phenolic hydroxyl group. have. As described above, the structure not only contributes to high dry etching resistance, but also can increase the glass transition temperature (Tg) of the polymer compound (A), and it is estimated that higher resolution is provided by the effect of these combinations.

In the present invention, non-acid-decomposable means a property that no decomposition reaction occurs by an acid generated by a photoacid generator.

More specifically, it is preferable that the group which has a non-acid-decomposable polycyclic alicyclic hydrocarbon structure is a group which is stable to an acid and an alkali. A group stable to acid and alkali means a group that does not exhibit acid decomposability and alkali degradability. Here, acid-decomposable means the property which produces a decomposition reaction by the action of the acid which a photo-acid generator produces.

In addition, alkali degradability means the property which produces a decomposition reaction by action of an alkaline developing solution. As a group which shows alkali-decomposability, group which decomposes by the action of the conventionally well-known alkali developing solution contained in resin used suitably in positive chemically amplified resist composition, and the dissolution rate in alkaline developing solution increases (for example, And the like 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 carbon number is preferably 5 to 40, and more preferably 7 to 30. The polycyclic alicyclic hydrocarbon structure may have an unsaturated bond in the ring.

The polycyclic alicyclic hydrocarbon structure in the group having a polycyclic alicyclic hydrocarbon structure means a structure having a plurality of monocyclic alicyclic hydrocarbon groups or a polycyclic alicyclic hydrocarbon structure, and may be bridged. As monocyclic alicyclic hydrocarbon group, a C3-C8 cycloalkyl group is preferable, For example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group, etc. are mentioned, A monocyclic type The structure which has two or more alicyclic hydrocarbon groups of has two or more these groups. It is preferable to have 2-4 monocyclic alicyclic hydrocarbon groups, and, as for the structure which has two or more monocyclic alicyclic hydrocarbon groups, it is especially preferable to have 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, adamantane structure, decalin structure, Norbornene structure, norbornene structure, cedrol structure, isobornane structure, bonane structure, dicyclopentane structure, α-pinene structure, tricyclodecane structure, tetracyclododecane structure, and androstein structure Can be mentioned. In addition, a part of the carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted by hetero atoms, such as an oxygen atom.

Preferred examples of the polycyclic alicyclic hydrocarbon structure include adamantane structure, decalin structure, norbornene structure, norbornene structure, cedrol structure, structure having a plurality of cyclohexyl groups, a structure having a plurality of cycloheptyl groups, and cyclooctyl A structure having a plurality of groups, a structure having a plurality of cyclodecaneyl groups, a structure having a plurality of cyclododecaneyl groups, a tricyclodecane structure, and the adamantane structure are most preferred in view of dry etching resistance (that is, the It is most preferable that the group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure is a group having a non-acid-decomposable adamantane structure).

These polycyclic alicyclic hydrocarbon structures (About the structure which has two or more monocyclic alicyclic hydrocarbon groups, the monocyclic alicyclic hydrocarbon structure corresponding to the said monocyclic alicyclic hydrocarbon group (specifically, following formula (47)-(50) The chemical formula of structure))) is shown below.

[Formula 17]

The polycyclic alicyclic hydrocarbon structure may further have a substituent, and 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), and an aryl group (preferably having carbon atoms). 6-15), halogen atoms, hydroxyl groups, alkoxy groups (preferably having 1 to 6 carbon atoms), carboxyl groups, carbonyl groups, thiocarbonyl groups, alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), and these groups The group formed by combination (preferably total 1-30 carbon atoms, More preferably, 1-15 total carbon atoms) is mentioned.

As said polycyclic alicyclic hydrocarbon structure, the structure represented by any one of said Formula (7), (23), (40), (41) and (51), and any one hydrogen in the structure of said Formula (48) The structure which has two monovalent groups which used the atom as a bond is preferable, The structure represented by any one of said Formula (23), (40), and (51), and any one in the structure of said Formula (48) The structure which has two monovalent groups which made a hydrogen atom the bond is more preferable, and the structure represented by said Formula (40) is the most preferable.

As group which has a polycyclic alicyclic hydrocarbon structure, it is preferable that the monovalent group which made arbitrary one hydrogen atom of the said polycyclic alicyclic hydrocarbon structure a bond.

A high molecular compound (A) may contain the repeating unit represented by the following general formula (IV) or the following general formula (V).

[Formula 18]

In the formula,

R ₆ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group, 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 or fluorinated alkyl group having 1 to 6 carbon atoms, or a carboxyl group.

n <_3> represents the integer of 0-6.

[Formula 19]

In the formula,

R ₇ represents a hydrogen atom, a hydroxy group, a linear, branched or cyclic alkyl group, 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 or fluorinated alkyl group having 1 to 6 carbon atoms, or a carboxyl group.

n ₄ represents an integer of 0-4.

X ₄ is a methylene group, an oxygen atom or a sulfur atom.

Although the specific example of the repeating unit represented by general formula (IV) or the following general formula (V) is shown below, it is not limited to these.

[Formula 20]

Although the specific example (combination of each repeating unit) of a high molecular compound (A) is shown below, this invention is not limited to these.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

The weight average molecular weight of a high molecular compound (A) becomes like this. Preferably it is 1000-200000, More preferably, it is 2000-50000, More preferably, it is 3000-10000, Especially preferably, it is 3000-7000.

Dispersion degree (molecular weight distribution) (Mw / Mn) of a high molecular compound (A) becomes like this. Preferably it is 1.7 or less, More preferably, it is 1.0-1.50 from a viewpoint of the sensitivity and the resolution improvement, Especially preferably, it is 1.0-1.40. to be.

In order to obtain the high molecular compound (A) which has said preferable dispersion degree, it is preferable to manufacture by the manufacturing method which uses the polymer of the repeating unit represented by following General formula (5) with a small dispersion degree as a raw material.

[Formula 21]

R ₁ in the formula is R ₁ and consent of the general formula (1).

As for the dispersion degree of the polymer of the raw material used for the said manufacturing method, in consideration of the possibility of oligomerization by side reaction, 1.0-1.30 are preferable and 1.0-1.20 are more preferable. As for the polymer of the raw material used for the said manufacturing method, the dispersion degree of the high molecular compound obtained becomes uniform by using living polymerization, such as living anion polymerization, and is preferable.

The synthesis of the polymer compound (A) using the above-described raw material can be carried out by referring to the method described in, for example, "Reaction II of Experimental Chemistry Vol. 18 Organic Compound (bottom), page 94" and the like.

You may use a high molecular compound (A) individually by 1 type or in mixture of 2 or more types.

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

[2] (B) A compound which generates an acid having a volume of 130 to ³ or more and 2000 to ³ by irradiation of actinic light or radiation;

In the chemically amplified resist composition of the present invention, a compound (B) which generates an acid having a volume of 130 to ³ or more and 2000 to ³ or less by irradiation of actinic light or radiation (hereinafter, these compounds are appropriately abbreviated as "acid generator"). ).

An onium compound is mentioned as a preferable form of an acid generator. As such an onium compound, a sulfonium salt, an iodonium salt, a phosphonium salt, etc. are mentioned, for example, It is more preferable that it is a sulfonium salt.

Moreover, as another preferable aspect of an acid generator, the compound which generate | occur | produces sulfonic acid, an imid acid, or a metaic acid by irradiation of actinic light or a radiation is mentioned. Examples of the acid generator in the form include a sulfonium salt, an iodonium salt, a phosphonium salt, an oxime sulfonate, an imido sulfonate, and the like.

The acid generator used in the present invention is not limited to a low molecular weight compound, and a group which generates an acid by irradiation with actinic radiation or radiation within the range of 130 to ³ to 2000 Å ^{3 in} the volume of the generated acid, may be a main chain or side chain of the polymer compound. The compound introduced into can also be used. In addition, as mentioned above, when the group which generate | occur | produces an acid by irradiation of actinic light or a radiation exists in the repeating unit which becomes a copolymerization component of the high molecular compound (A) used for this invention, with the high molecular compound of this invention, There may be no acid generator of a separate molecule.

When the compound (B) which generates an acid by irradiation of actinic light or radiation is a form of a low molecular weight compound, it is preferable that molecular weight is 3000 or less, It is more preferable that it is 2000 or less, It is more preferable that it is 1000 or less.

It is preferable that an acid generator is a compound which generate | occur | produces an acid by irradiation of an electron beam or an extreme ultraviolet ray.

In this invention, the sulfonium compound represented by following General formula (7) or the iodonium compound represented by General formula (8) is mentioned as a preferable onium compound.

[Formula 22]

In general formula (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 General formula (7) and the iodonium compound represented by General formula (8) are demonstrated in more detail.

Although R _a1 to R _a3 in the general formula (7) and R _a4 and R _a5 in the general formula (8) each independently represent an organic group, preferably at least one of R _a1 to R _a3 and R At least one of _a4 and R _a5 is each an aryl group. As an aryl group, a phenyl group and a naphthyl group are preferable, More preferably, it is a phenyl group.

The organic anion of X ⁻ in the general formulas (7) and (8) includes, for example, a sulfonic acid anion, a carboxylic acid anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, and the like. These are mentioned, Preferably it is an organic anion represented by following General formula (9), (10) or (11), More preferably, it is an organic anion represented by following General formula (9).

[Formula 23]

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

The organic anion of X ⁻ corresponds to sulfonic acid, imide acid, metaid acid, or the like, which is an acid generated by irradiation of active light or radiation such as electron beam or extreme ultraviolet ray.

Examples of the organic group of Rc ₁ ~ Rc _4, for example there may be mentioned an alkyl group, a cycloalkyl group, an aryl group, or a group of a plurality thereof connected. More preferably among these organic groups is an alkyl group substituted with a fluorine atom or a fluoroalkyl group, a phenyl group substituted with a cycloalkyl group substituted with a fluorine atom or a fluoroalkyl group, a fluorine atom or a fluoroalkyl group. The plurality of organic groups of Rc ₂ to Rc ₄ may be linked to each other to form a ring, and as the group to which the plurality of organic groups are connected, an alkylene group substituted with a fluorine atom or a fluoroalkyl group is preferable. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid produced | generated by light irradiation becomes high and a sensitivity improves. However, it is preferable that a terminal group does not contain a fluorine atom as a substituent.

And, in the present invention, compound (B) which generates the acid is a compound capable of generating a volumetric 130Å (preferably acid than) an acid of more than ^three sizes.

As mentioned above, excellent results are obtained regarding resolution, PED stability and LER performance from the generation of an acid having a volume of 130 kPa ³ or more.

Compound (B) is preferably a compound that generates an acid (more preferably sulfonic acid) having a volume of 190 kPa ³ or more by irradiation of actinic light or radiation, and more preferably an acid having a volume of 270 kPa ³ or more (more preferably Is more preferably a compound generating sulfonic acid), and particularly preferably a compound generating an acid (more preferably sulfonic acid) having a volume of 400 kPa ³ or more. However, in view of the sensitivity and the solubility in coating solvent, wherein the volume is 2000Å ³ or less, more preferably not more than 1500Å ^3.

Here, 1 Hz corresponds to 0.1 nm.

The value of the said volume was calculated | required using "WinMOPAC" by Fujitsu Corporation. That is, first, the chemical structure of the acid according to each example is input. Next, the most stable steric coordinate 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 calculations using the PM3 method on stable steric coordinates, the "accessible volume" of each acid can be calculated.

In the present invention, particularly preferred acid generators are exemplified below. In addition, a part of the example adds the calculated value of a volume (unit # ³ ). In addition, the calculated value calculated here is the volume value of the acid which the proton couple | bonded with the anion part.

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

An acid generator can be used individually by 1 type or in combination of 2 or more type.

The content in the composition of the acid generator is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, based on the total solids of the negative actinic ray-sensitive or radiation-sensitive resin composition. More preferably, it is 1-18 mass%.

[3] (E) basic compounds

It is preferable that the composition of this invention contains a basic compound further as an acid trapping agent. By using a basic compound, the performance change with time from exposure to post-heating can be made small. As such a basic compound, it is preferable that it is an organic basic compound, More specifically, aliphatic amines, aromatic amines, heterocyclic amines, the nitrogen-containing compound which has a carboxyl group, the nitrogen-containing compound which has a sulfonyl group, the nitrogen-containing which has a hydroxyl group And a compound, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative and the like. Amine oxide compounds (described in JP-A-2008-102383) and ammonium salts (preferably hydroxides or carboxylates). More specifically, tetraalkylammonium hydroxides represented by tetrabutylammonium hydroxide are LER. Is preferable in view of the above).

Moreover, the compound which basicity increases by the action of an acid can also be used as one type of basic compound.

Specific examples of the amines include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, tetradecylamine and pentadecyl Amine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexyl aniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline, triethanolamine, N, N-dihydroxyethylaniline, tris (methoxyethoxy Ethyl) amine, or the compound exemplified after column 3, column 60 of US Patent Publication No. 6060112, 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and the compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of US Patent Application Publication No. 2007 / 0224539A1. The. Examples of the compound having a nitrogen-containing heterocyclic structure include 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, N-hydroxyethyl piperidine, and 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] Undes-7-ene, tetrabutylammonium hydroxide, etc. are mentioned.

Photodegradable basic compounds (In the beginning, basic nitrogen atoms act as bases to show basicity, but are decomposed by irradiation with actinic rays or radiation to generate zwitterionic compounds having basic nitrogen atoms and organic acid sites. Compounds whose basicity is reduced or lost by neutralizing in the molecule, for example, Japanese Patent No. 3577743, Japanese Patent Laid-Open No. 2001-215689, Japanese Patent Laid-Open No. 2001-166476, Japanese Patent Laid-Open No. 2008-102383 Onium salt described in the above, and a photobasic generator (for example, the compound described in JP 2010-243773 A).

Among these basic compounds, an ammonium salt is preferable from the viewpoint of resolution improvement.

0.01-10 mass% is preferable with respect to the total solid of a composition, as for the content rate of the basic compound in this invention, 0.03-5 mass% is more preferable, 0.05-3 mass% is especially preferable.

It is preferable that it is said "photodegradable basic compound", and, as for the basic compound in this invention, it is more preferable that it is "a basic compound or an ammonium salt compound (C) whose basicity falls by irradiation of actinic light or a radiation".

A basic compound or an ammonium salt compound (C) whose basicity is lowered by irradiation of such actinic rays or radiation is also referred to as an onium salt compound (hereinafter referred to as "compound (E)") containing a nitrogen atom in a cation portion described below. Is preferred.

As an onium salt compound, a diazonium salt compound, a phosphonium salt compound, a sulfonium salt compound, an iodonium salt compound, etc. are mentioned, for example. 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 has a basic site | part containing a nitrogen atom in the cation part. A "basic site" means the site | part in which pKa of the conjugate acid of the cation site of a compound (E) becomes -3 or more here. It is preferable to exist in the range of -3-15, and, as for this pKa, it is more preferable to exist in the range of 0-15. In addition, this pKa means the calculated value calculated 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 in which one hydrogen atom is removed from an ammonia, a primary amine or a secondary amine; the same below) and a nitrogen-containing heterocyclic group. It is preferable that the said amino group is an aliphatic amino group. Here, an aliphatic amino group means group which removed one hydrogen atom from aliphatic amine.

In these structures, it is preferable from a viewpoint of basic improvement that all of the atoms adjacent to the nitrogen atom contained in a structure are a carbon atom or a hydrogen atom. Moreover, it is preferable that an electron withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom etc.) is not directly connected with respect to a nitrogen atom from a viewpoint of basic improvement.

The onium salt compound may be provided with two or more of the above basic sites.

When the cation part of a compound (E) contains an amino group, it is preferable that this cation part has the partial structure represented by the following general formula (N-I).

[Formula 32]

In the formula,

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

X represents a single bond or a linking group.

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

As an organic group represented by R _<A> or R <_B> , an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic hydrocarbon group, an alkoxycarbonyl group, a lactone group, a sultone group, etc. are mentioned, for example.

These groups may have a substituent and an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group etc. are mentioned as a substituent.

The alkyl group represented by R _A or R _B may be linear or branched. It is preferable that carbon number of this alkyl group is 1-50, It is more preferable that it is 1-30, It is more preferable that it is 1-20. As such an alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-view And a ethyl 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. As this cycloalkyl group, Preferably, C3-C8 monocyclic cycloalkyl groups, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, etc. are mentioned.

The alkenyl group represented by R _A or R _B may be linear or branched. It is preferable that carbon number of this alkenyl group is 2-50, It is more preferable that it is 2-30, It is more preferable that it is 3-20. As such an alkenyl group, a vinyl group, an allyl group, a styryl group, etc. are mentioned, for example.

As an aryl group represented by R _<A> or R <_B> , a C6-C14 thing is preferable. As such a group, a phenyl group, a naphthyl group, etc. are mentioned, for example.

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

The heterocyclic ring contained in said group may be monocyclic, or polycyclic may be sufficient as it. As such a heterocyclic ring, for example, imidazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 2H-pyrrole ring, 3H-indole ring, 1H-indazole ring, purine ring, isoquinoline ring, 4H -Quinoline 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, azepine ring, azosin ring, isothiazole ring, isoxazole ring, and benzothiazole ring.

Examples of R _A or a lactone group represented by R _B, for example, a lactone group of 5 to 7-membered ring, groups 5 to 7-membered ring lactone is that bicyclo structure, the other ring structure in the form of forming the structure of a spy-axis bright You can do it.

As the sulfonic tongi represented by R _A or R _B, for example, a sulfonic tongi a 5-7 membered ring, groups 5 to 7-membered sultone is that bicyclo structure, the other ring structure in the form of forming the structure of a spy-axis bright You can do it.

Specifically, it is preferable that it is group which has a structure shown below.

[Formula 33]

[Formula 34]

The lactone group and the sultone group may or may not have a substituent (Rb ₂ ). As a preferable substituent (Rb _2), there may be mentioned the same substituents as those described as the substituent of R _A and R _B in the above. n ₂ represents an integer of 0-4. substituents (Rb ₂₎ to n ₂ is present, when a plurality is two or more, be the same or different. In addition, a plurality of substituents (Rb ₂ ) may be bonded to each other 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 a group formed by combining two or more thereof. Can be mentioned. X more preferably represents a group formed by combining a single bond, an alkylene group, an alkylene group and an ether bond, or a group formed by combining an alkylene group and an ester bond. 20 or less are preferable and, as for the atom number of the coupling group represented by X, 15 or less are more preferable. 8 or less carbon atoms are preferable and said linear or branched alkylene group and cycloalkylene group may have a substituent. As said substituent, a C8 or less thing is preferable, For example, an alkyl group (C1-C4), a halogen atom, a hydroxyl group, an alkoxy group (C1-C4), a carboxyl group, an alkoxycarbonyl group (C2-C6) Etc. can be mentioned.

At least two of R _A , R _B and X may be bonded to each other to form a ring. 4-20 are preferable, as for carbon number which forms a ring, monocyclic or polycyclic may be sufficient, and the ring may contain an oxygen atom, a sulfur atom, a nitrogen atom, an ester bond, an amide bond, or a carbonyl group.

When the cation part of a compound (E) contains the nitrogen-containing heterocyclic group, this nitrogen-containing heterocyclic group may have aromaticity and does not need to have aromaticity. Moreover, this nitrogen-containing heterocyclic group may be monocyclic or polycyclic. As a nitrogen-containing heterocyclic group, Preferably, group containing a piperidine ring, a morpholine ring, a pyridine ring, an imidazole ring, a pyrazine ring, a pyrrole ring, or a pyrimidine ring is mentioned.

It is preferable that an onium salt compound (E) is a compound represented by following General formula (4).

[Formula 35]

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) valence organic group, X represents a single bond or a linking group, and A _N represents nitrogen A basic site including an atom is shown. When two or more R _<A> , R <_B> , X and A <_N> respectively exist, they may be same or different.

When A is a sulfur atom, q is an integer of 1-3 and o is an integer which 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 o + q = 2.

p represents the integer of 1-10, and Y <^-> represents an anion (as is mentioned later as an anion part of a 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 a chain (linear, branched) or cyclic aliphatic hydrocarbon group, a heterocyclic hydrocarbon group, and an aromatic hydrocarbon group. Preferably, an aromatic hydrocarbon group is mentioned. When R _B is an aromatic hydrocarbon group, it is preferably coupled to the top p- (1,4 above), an aromatic hydrocarbon group.

The linking group represented by X is synonymous with the linking group represented by X in General Formula (N-I) described above, and examples thereof are the same.

The basic moiety represented by A _N is synonymous with the "basic moiety" contained in the cationic moiety of the compound (E) described above, and may include, for example, an amino group or a nitrogen-containing heterocyclic group. If the basic region comprises an amino group, examples of the amino group, there may be mentioned for example, the general formula (NI) of the _{-N (R A) (R B} ) a group described in the above.

As the organic group represented by R _A, for example, there may be mentioned an alkyl group, an alkenyl group, cycloaliphatic group, aromatic hydrocarbon group and heterocyclic hydrocarbon group. In the case of o = 2, two R _{A 's} 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. It is preferable that carbon number of this alkyl group is 1-50, It is more preferable that it is 1-30, It is more preferable that it is 1-20. As such an alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-view And a ethyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group.

The alkenyl group represented by R _A may be linear or branched. It is preferable that carbon number of this alkenyl group is 2-50, It is more preferable that it is 2-30, It is more preferable that it is 3-20. As such an alkenyl group, a vinyl group, an allyl group, and a styryl group are mentioned, for example.

The alicyclic group represented by R _A is a cycloalkyl group, for example. The cycloalkyl group may be monocyclic or polycyclic. As this aliphatic cyclic group, Preferably, C3-C8 monocyclic cycloalkyl groups, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, are mentioned.

The aromatic hydrocarbon groups represented by R _A, it is preferable that a carbon number of 6-14. As such a group, aryl groups, such as a phenyl group and a naphthyl group, are mentioned, for example. The aromatic hydrocarbon group represented by R _A is preferably a phenyl group.

The heterocyclic hydrocarbon group represented by R _A may or may not have aromaticity. It is preferable that this heterocyclic hydrocarbon group has aromaticity.

The heterocyclic ring contained in said group may be monocyclic, or polycyclic may be sufficient as it. As such a heterocyclic ring, for example, imidazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 2H-pyrrole ring, 3H-indole ring, 1H-indazole ring, purine ring, isoquinoline ring, 4H -Quinoline 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, azepine ring, azosin ring, isothiazole ring, isoxazole ring, and benzothiazole ring.

R _A is an aromatic hydrocarbon group or two R _{A 's} are preferably bonded to each other to form a ring.

_A R, X, R, A _N of the at least two are each preferably a 4 to 7-membered ring which may be formed by combining each other, more preferably 5 or 6-membered ring, and that the five-membered ring is particularly preferred. Moreover, you may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom, in a ring skeleton.

If that group, or two R _A represented by R _A is provided with a ring substituent formed by combining each other more, as the substituent, for example, it includes the following. That is, as this substituent, 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 is given, for example. , Acyloxy group, carbamoyloxy group, alkyl sulfoxy group, aryl sulfoxy 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, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO ₃ H) and its conjugated base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, phosphono Group (-PO ₃ H ₂ ) and its conjugated base group (referred to as phosphonate group), phosphonooxy group (-OPO ₃ H ₂ ) and its Conjugated base groups (referred to as phosphonateoxy groups), cyano groups, nitro groups, aryl groups, alkenyl groups, alkynyl groups, heterocyclic groups, silyl groups, and alkyl groups.

Among 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 General formula (4), it is preferable that p is an integer of 1-4, It is more preferable that it is 1 or 2, It is more preferable that it is 1.

In one aspect of the compound (E) represented by General Formula (4), at least one of q R _B in the formula is preferably an aromatic hydrocarbon group. And it is preferable that X in at least one of p-(XA _N ) groups couple | bonded with at least one of this aromatic hydrocarbon group is a coupling group whose coupling | bonding part with the said aromatic hydrocarbon group is a carbon atom.

That is, in the compound (E) in this embodiment, the basic moiety represented by A _N is bonded to the aromatic hydrocarbon group via a carbon atom directly connected to the aromatic hydrocarbon group represented by R _B.

The aromatic hydrocarbon group represented by R _B may contain a heterocycle as an aromatic ring in the aromatic hydrocarbon group. In addition, the aromatic ring may be monocyclic or may be polycyclic.

The aromatic ring group preferably has 6 to 14 carbon atoms. As such a group, aryl groups, such as a phenyl group, a naphthyl group, and an anthryl group, are mentioned, for example. When the aromatic ring contains a heterocyclic ring, for example, as a heterocyclic ring, a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benz An imidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring are mentioned.

Aromatic hydrocarbon group represented by R _B, preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

The aromatic hydrocarbon group represented by R _B may further include a substituent in addition to the group represented by-(XA _N ) described below. As the substituent, for example, it may be used that listed above as substituents in R _A.

In this embodiment, the linking group as X in at least one — (XA _N ) group substituted with the aromatic ring R _B described above is particularly limited as long as the bonding portion with the aromatic hydrocarbon group represented by R _B is a carbon atom. It doesn't work. The linking group contains, for example, an alkylene group, a cycloalkylene group, an arylene group, -COO-, -CO-, or a combination thereof. The linking group is each of these groups, -O-, -S-, -OCO-, -S (= O)-, -S (= O) _2- , -OS (= O) _2- , and -NR'- It may also include at least one combination selected from the group consisting of: Here, R 'represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, for example.

The alkylene group which the linking group represented by X may contain may be linear or branched. It is preferable that it is 1-20, and, as for carbon number of this alkylene group, it is more preferable that it is 1-10. As such an alkylene group, a methylene group, an ethylene group, a propylene group, and a butylene group is mentioned, for example.

The cycloalkylene group which the linking group represented by X may contain may be monocyclic or polycyclic. It is preferable that it is 3-20, and, as for carbon number of this cycloalkylene group, it is more preferable that it is 3-10. As such a cycloalkylene group, a 1, 4- cyclohexylene group is mentioned, for example.

It is preferable that it is 6-20, and, as for carbon number of the arylene group which the coupling group represented by X may contain, it is more preferable that it is 6-10. As such arylene group, a phenylene group and a naphthylene group are mentioned, for example.

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

[Formula 36]

In the formula,

R <_2> and R <_3> represents 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.

[Formula 37]

In the formula,

J represents an oxygen atom or a sulfur atom.

E represents a linking group or a single bond.

As each group represented by R <_2> and R <_3> and the substituent which these can further include, the same thing as what was demonstrated previously about R _<A> is mentioned, for example. It is preferable that the ring which R <_2> and R <_3> couple | bonds and can form, and the ring which at least one of R <_2> and R <_3> can combine with E are 4-7 membered rings, It is more preferable that they are 5 or 6 membered rings desirable. R ₂ and R ₃ are each independently preferably a hydrogen atom or an alkyl group.

The linking group represented by E is, for example, an alkylene group, a cycloalkylene group, an arylene group, -COO-, -CO-, -O-, -S-, -OCO-, -S (= O)-, -S (= O) _2- , -OS (= O) _2- , -NR-, or a combination thereof. 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, an ester bond, an ether bond, a thioether bond, a urethane bond

[Formula 38]

Urea bonding

[Formula 39]

, At least one selected from the group consisting of amide bonds, and sulfonamide bonds. The linking group represented by E is more preferably an alkylene bond, an ester bond or an ether bond.

In addition, the compound (E) may be a compound having a plurality of sites containing a nitrogen atom. For example, the compound (E) may be a compound having a structure in which at least one of R _A in General Formula (4) is represented by General Formula (NI).

In one aspect, the compound (E) represented by General Formula (4) is represented by the following General Formula (N-V).

[Formula 40]

In formula, X, _AN, and Y <^-> are synonymous with each group in General formula (4), and a specific example and a preferable example are also the same.

R <_14> , R <_15> , r and l are synonymous with each group and the index in general formula (ZI-4) which show one aspect of a photo-acid generator, and a specific example and a preferable example are also the same.

In addition, the compound (E) represented by General Formula (4) is represented by the following General Formula (N-VI) in one embodiment.

[Formula 41]

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 alicyclic group, an aromatic hydrocarbon group, or a heterocyclic hydrocarbon group. In the case of m = 2, two R _{11 's} may be bonded to each other to form a ring.

Ar represents an aromatic hydrocarbon group each independently.

Each X ₁ 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 of 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 of m + n = 2.

Y <^-> represents an anion (The detail is as mentioned later as an anion part of a 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 the} alkyl group, alkenyl group and aliphatic ring as R _A in the general formula (4). It is the same as the specific example and preferable example of a tableware, an aromatic hydrocarbon group, and a heterocyclic hydrocarbon group.

Specific examples and preferred examples of the aromatic hydrocarbon groups as Ar is the same as the specific examples of the aromatic hydrocarbon group as R _B in the general formula (4) Examples and preferable examples.

Specific examples and preferable examples of the divalent linking group as X _{1 are the same} as the specific examples and preferable examples of the linking group as X in General Formula (4).

The specific example and preferable example of the organic group as R <_{12> are the same} as the specific example and preferable example of the organic _group as R _<A> and R <_{B> in the} said general formula (NI).

The aspect in which X is an alkylene group (for example, methylene group) and two R <_12> couple | bonds with each other and forms a ring is especially preferable from a viewpoint of post-exposure heating (PEB) temperature dependency and post-exposure line width (PED) stability. Do.

There is no restriction | limiting in particular in the anion part of a compound (E). It is preferable that the anion contained in the compound (E) is a non-nucleophilic anion. Here, a non-nucleophilic anion is an anion which is remarkably low in the ability to produce a nucleophilic reaction, and is an anion which can suppress degradation | decomposition over time by the intramolecular nucleophilic reaction. Thereby, stability with time of the composition concerning this invention improves.

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

As a sulfonic acid anion, an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphorsulfonic acid anion, etc. are mentioned, for example.

As a carboxylic acid anion, an aliphatic carboxylic acid anion, an aromatic carboxylic acid anion, an aralkyl carboxylic acid anion, etc. are mentioned, for example.

The aliphatic moiety in the aliphatic sulfonic acid 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, for example, a methyl group, an ethyl group, a propyl group, and an 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, carbonyl group, etc. may be mentioned. .

As an aromatic group in an aromatic sulfonic acid anion, Preferably, a C6-C14 aryl group, for example, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned.

The alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonic acid anion and aromatic sulfonic acid anion may have a substituent. As a substituent of an alkyl group, a cycloalkyl group, and an aryl group in an aliphatic sulfonic acid anion and an aromatic sulfonic acid anion, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy Group, hydroxyl group, amino group, cyano group, alkoxy group (preferably C1-C15), cycloalkyl group (preferably C3-C15), aryl group (preferably C6-C14), 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 (preferably 1 to 15 carbon atoms), alkyl sulfone Diary (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), aryloxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloctasulfonyl group (preferably Is C7-C20, cycloalkylaryl octasulfonyl group (preferably Crab is C10-20), an alkyloxyalkyloxy group (preferably C5-C20), a cycloalkylalkyloxyalkyloxy group (preferably C8-20), etc. are mentioned. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) is mentioned further as a substituent.

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

As an aromatic group in an aromatic carboxylic acid anion, the same aryl group as in an aromatic sulfonic acid anion is mentioned.

As an aralkyl group in an aralkyl carboxylic acid anion, Preferably, a C6-C12 aralkyl group, for example, a benzyl group, a phenethyl group, a naphthyl methyl group, a naphthyl ethyl group, a naphthyl butyl group, etc. are mentioned.

The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylic acid anion, aromatic carboxylic acid anion and aralkyl carboxylic acid anion may have a substituent. As a substituent of the alkyl group, cycloalkyl group, aryl group, and aralkyl group in aliphatic carboxylic acid anion, aromatic carboxylic acid anion, and aralkyl carboxylic acid anion, for example, the same halogen atom, alkyl group, cycloalkyl group, alkoxy as in aromatic sulfonic acid anion Group, alkylthio group, etc. are mentioned.

As a sulfonyl imide anion, saccharin anion is mentioned, for example.

The alkyl group in the bis (alkylsulfonyl) imide anion and the tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n- Butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group and the like. Substituents for these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxafonyl group, an aryloxafonyl group, a cycloalkylaryloxafonyl group, and the like. Substituted alkyl groups are preferred. Moreover, the aspect which two alkyl groups in a bis (alkylsulfonyl) imide anion couple | bond with each other and forms cyclic structure is also preferable. In this case, it is preferable that the cyclic structure formed is a 5-7 membered ring.

As other non-nucleophilic anion, phosphorus fluoride, a boron fluoride, fluorination antimony etc. are mentioned, for example.

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

Moreover, it is preferable that a non-nucleophilic anion is represented by following General formula (LD1), for example.

[Formula 42]

In the formula,

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

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

L each independently represents a divalent linking group.

Cy represents a cyclic organic group.

x represents the integer of 1-20.

y represents the integer of 0-10.

z represents the integer of 0-10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. It is preferable that it is 1-10, and, as for carbon number of this alkyl group, it is more preferable that it is 1-4. Moreover, it is preferable that the alkyl group substituted by the at least 1 fluorine atom is a perfluoroalkyl group.

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

R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. This alkyl group may have a substituent (preferably a fluorine atom), and the C1-C4 thing is preferable. More preferably, it is a C1-C4 perfluoroalkyl group. R Specific examples of the alkyl group examples having a substituent as ₁ and R _2, 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 F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ are mentioned, among which CF ₃ is preferred.

L represents a bivalent coupling group. Examples of the divalent linking group include -COO-, -OCO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO _2- , an alkylene group, a cycloalkylene group, and Alkenylene group is mentioned. Of these, -CONH-, -CO-, or -SO ₂ - more preferably - are preferred, -CONH- or -SO _2.

Cy represents a cyclic organic group. As a cyclic organic group, an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example.

The alicyclic group may be monocyclic or may be polycyclic. As monocyclic alicyclic group, monocyclic cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, are mentioned, for example. As a polycyclic alicyclic group, polycyclic cycloalkyl groups, such as a norbornyl group, a tricyclodecaneyl group, a tetracyclodecaneyl group, a tetracyclo dodecaneyl group, and an adamantyl group, are mentioned, for example. Among these, alicyclic groups having a bulky structure having a carbon number of 7 or more, such as a norbornyl group, tricyclodecaneyl group, tetracyclodecaneyl group, tetracyclododecaneyl group, and adamantyl group, are diffusive in the film in the PEB (post-exposure heating) process. It is preferable from the viewpoint of suppression and improvement of Mask Error Enhancement Factor (MEEF).

The aryl group may be monocyclic or polycyclic. As this aryl group, a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group are mentioned, for example. Among them, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.

Although a heterocyclic group may be monocyclic or polycyclic, a polycyclic ring can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity and does not need to have aromaticity. As a heterocyclic ring which has aromaticity, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring are mentioned, for example. As a heterocyclic ring which does not have aromaticity, a tetrahydropyran ring, a lactone ring, and a decahydroisoquinoline ring are mentioned, for example. As a heterocyclic ring in a heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is especially preferable. In addition, examples of the lactone ring, there may be mentioned the lactone ring exemplified with respect to R _A and R _B in the general formula (N-1).

The said cyclic organic group may have a substituent. As this substituent, an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group are mentioned, for example. have. The alkyl group may be linear or branched. In addition, the alkyl group preferably has 1 to 12 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic. In addition, the cycloalkyl group preferably has 3 to 12 carbon atoms. The aryl group preferably has 6 to 14 carbon atoms.

1-8 are preferable, as for x, 1-4 are especially preferable, and 1 is especially preferable. 0-4 are preferable and, as for y, 0 is more preferable. As for z, 0-8 are preferable, and 0-4 are especially preferable.

Moreover, it is also preferable that a non-nucleophilic anion is represented by following General formula (LD2), for example.

[Formula 43]

In the general formula (LD2), Xf, R _1, R _2, L, Cy, x, y and z, respectively, and copper in the formula (LD1). Rf is a group containing a fluorine atom.

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

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

Moreover, these alkyl groups, cycloalkyl groups, and aryl groups may further be substituted by the substituent which does not contain a fluorine atom. As this substituent, the thing which does not contain a fluorine atom among the thing demonstrated about Cy before, for example is mentioned.

Examples of the alkyl group having at least one fluorine atom represented by Rf include the same alkyl groups as those described above as the alkyl group substituted with at least one fluorine atom represented by Xf. As a cycloalkyl group which has at least 1 fluorine atom represented by Rf, a perfluoro cyclopentyl group and a perfluorocyclohexyl group are mentioned, for example. As an aryl group which has at least 1 fluorine atom represented by Rf, a perfluorophenyl group is mentioned, for example.

As a preferable aspect of the anion part of a compound (E), the structure illustrated as a preferable anion structure of a photo-acid generator other than the structure represented by general formula (LD1) and (LD2) mentioned above is mentioned.

In addition, the compound (E) preferably has a fluorine content of 0.30 or less, more preferably 0.25 or less, which is represented by (sum of mass of all fluorine atoms included in the compound) / (sum of mass of all atoms contained in the compound). It is preferable, It is more preferable that it is 0.20 or less, It is especially preferable that it is 0.15 or less, It is most preferable that it is 0.10 or less.

Although the specific example of a compound (E) is given to the following, it is not limited to these.

[Formula 44]

[Formula 45]

[Formula 46]

[Formula 47]

[Formula 48]

[Formula 49]

[Formula 50]

[Formula 51]

[Formula 52]

[Formula 53]

A compound (E) may be used individually by 1 type, and may be used in combination of 2 or more type.

Content of a compound (E) is in the range of 0.001-10 mass% normally on the basis of the total solid of a composition, Preferably it is 0.1-10 mass%, More preferably, it is in the range of 1-10 mass%. have.

In addition, it is preferable that the volume of the generated acid from a compound (E) is larger from a viewpoint of resolution improvement.

[4] (C) A compound having an acid crosslinkable group different from the high molecular compound (A)

The composition of this invention can contain the compound (C) (henceforth "a compound (C)" or an "acid crosslinking agent (C)") which has an acid crosslinkable group different from the said high molecular compound (A). As a compound (C), it is preferable that it is a compound containing 2 or more of a hydroxymethyl group or an alkoxymethyl group in a molecule | numerator. Moreover, it is preferable that a compound (C) contains the methylol group from a viewpoint of LER improvement.

First, the case where compound (C) is a low molecular compound (henceforth a "compound (C ')") is demonstrated. As compound (C '), Preferably, a hydroxymethylated or alkoxy methylated phenolic compound, the alkoxy methylated melamine type | system | group compound, the alkoxy methyl glycoluril type compound, and the alkoxy methylation urea type compound are mentioned. As a particularly preferable compound (C '), a phenol derivative or an alkoxymethyl glycoluril derivative having 3 to 5 benzene rings in the molecule, 2 or more in combination with a hydroxymethyl group or an alkoxymethyl group, and having a molecular weight of 1200 or less Can be mentioned.

As an alkoxy methyl group, a methoxymethyl group and an ethoxymethyl group are preferable.

In the example of the said compound (C '), the phenol derivative which has a hydroxymethyl group can be obtained by making a phenol compound which does not have a corresponding hydroxymethyl group, and formaldehyde react with a base catalyst. In addition, the phenol derivative having an alkoxymethyl group can be obtained by reacting a phenol derivative having a corresponding hydroxymethyl group with an alcohol under an acid catalyst.

Examples of other preferred compounds (C ′) further include compounds having N-hydroxymethyl groups or N-alkoxymethyl groups, such as alkoxymethylated melamine compounds, alkoxymethylglycoluril compounds and alkoxymethylated urea compounds. Can be mentioned.

As such a compound, hexamethoxymethylmelamine, hexaethoxymethylmelamine, tetramethoxymethylglycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethyleneurea, bismethoxymethylurea And the like, and are disclosed in EP0,133,216A, West German Patent Nos. 3,634,671, 3,711,264, and EP0,212,482A.

Among the specific examples of the compound (C ′), particularly preferred are listed below.

[Formula 54]

Wherein, L ₁ ~ L ₈ each independently represent a hydrogen atom, hydroxy group, methoxy group, ethoxy 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).

[Formula 55]

In general formula (I),

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

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

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

In one 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, or a propyl group. And isopropyl group.

As an alkyl group represented by R <_2> and R <_5> , a C1-C6 or less alkyl group is preferable, for example, as a cycloalkyl group, a C3-C12 cycloalkyl group is preferable, for example, as an aryl group, A C6-C12 aryl group is preferable, and as an acyl group, it is preferable that carbon number of an alkyl site is 1-6, for example.

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

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

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

These rings may have a substituent and as such a substituent, for example, an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an aryl group, an alkoxymethyl group, an acyl group, an alkoxycarbonyl group, a nitro group, a halogen atom, or a hydroxy group The record time etc. can be mentioned.

Below, the specific example of the ring which R <_3> and R <_4> combines with each other and forms is given. * In a formula represents a connection site with a phenol nucleus.

[Formula 56]

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

It is preferable that compound (C ') couple | bonds R <_3> and R <_4> in general formula (I), for example, and forms the fluorene structure represented by the following general formula (Ia).

[Formula 57]

In the formula,

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

n1 and n2 respectively independently represent the integer of 0-4, Preferably 0 or 1 is represented.

* Represents a linkage site with a phenol nucleus.

Moreover, in 1 aspect of this invention, it is preferable that a compound (C ') is represented with the following general formula (I-b).

[Formula 58]

In the formula,

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

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

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

About the ring which Z forms with the carbon atom in a formula, it is the same as that of the ring which R <_3> and R <_4> combine and form in description of General formula (I) mentioned above.

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

Next, the manufacturing method of the compound (C ') represented by general formula (I) is demonstrated.

Generally, the bisphenol compound which becomes the mother nucleus of the compound (C ') represented by General formula (I) is synthesize | combined by dehydrating condensation reaction of the corresponding 2 molecule phenolic compound, and the corresponding 1 molecule ketone in presence of an acidic catalyst. .

The obtained bisphenol is treated with paraformaldehyde and dimethylamine and aminomethylated to obtain an intermediate represented by the following General Formula (I-c). Then, the target acid crosslinking agent is obtained through acetylation, deacetylation, and alkylation.

[Formula 59]

In formula, R <_1> , R <_3> , R <_4> and R <_6> are synonymous with each group in general formula (I).

Since this synthesis method is less likely to produce oligomers than the synthesis method (for example, JP 2008-273844) via the hydroxymethyl body under conventional basic conditions, there is an effect of suppressing particle formation.

Below, the specific example of compound (C ') represented by general formula (I) is shown.

[Formula 60]

In this invention, a compound (C ') may be used independently and may be used in combination of 2 or more type. It is preferable to use in combination of 2 or more type from a viewpoint of a favorable pattern shape.

The compound (C) containing an acid crosslinkable group is a resin (compound (C ") containing a repeating unit having an acid crosslinkable group, which is different from the repeating unit represented by General Formula (1) in the polymer compound (A). ) May be an aspect.

The negative actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may or may not contain the compound (C). When it contains, the content of the compound (C) is negative actinic ray-sensitive or In the total solid of a radiation sensitive resin composition, Preferably it is 0.5-30 mass%, More preferably, it is 1-15 mass%.

[5] (D) hydrophobic resins

Negative actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, especially when applied to immersion exposure, hydrophobic resin (hereinafter also referred to as "hydrophobic resin (D)" or simply "resin (D)") You may contain it. Moreover, it is preferable that hydrophobic resin (D) differs from the said high molecular compound (A).

As a result, when the hydrophobic resin (D) is localized in the film surface layer and the immersion medium is water, the static / dynamic contact angle of the surface of the resist film with respect to water can be improved, and the immersion liquid followability can be improved.

The hydrophobic resin (D) is preferably designed to be ubiquitous at the interface as described above. Unlike the surfactant, the hydrophobic resin (D) does not necessarily have a hydrophilic group in the molecule and does not necessarily contribute to uniformly mixing the polar / nonpolar material.

The hydrophobic resin (D) preferably has any one or more of "fluorine atom", "silicon atom", and "CH ₃ partial structure contained in the side chain portion of the resin" from the viewpoint of localization to the film surface layer. And it is more preferable to have 2 or more types.

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

When hydrophobic resin (D) contains a fluorine atom, it is preferable that it is resin which has the alkyl group which has a fluorine atom, the cycloalkyl group which has a fluorine atom, or the aryl group which has a fluorine atom as a partial structure which has a fluorine atom.

The alkyl group (preferably C1-C10, more preferably C1-C4) which has a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom was substituted by the fluorine atom, and may further have a substituent other than a fluorine atom. .

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 the 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 the fluorine atom.

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), but the present invention is not limited thereto. .

[Formula 61]

In general formula (F2)-(F4),

R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight chain 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 each independently represent an alkyl group having a fluorine atom or at least one hydrogen atom substituted with a fluorine atom (preferably Preferably it represents C1-C4).

R ₅₇ ~ R ₆₁ and R ₆₅ ~ R ₆₇ are preferably both 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 more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

As a specific example of group represented by general formula (F2), a p-fluorophenyl group, a pentafluorophenyl group, a 3, 5- di (trifluoromethyl) phenyl group, etc. are mentioned, for example.

As a specific example of group represented by general formula (F3), a trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluoro butyl group, hexafluoro isopropyl group, heptafluoro isopropyl group, hexafluoro Low (2-methyl) isopropyl group, nonafluorobutyl group, octafluoro isobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoro isopentyl group, perfluorooctyl group And a perfluoro (trimethyl) hexyl group, a 2,2,3,3-tetrafluorocyclobutyl group, a perfluorocyclohexyl group, and the like. Hexafluoro isopropyl group, heptafluoro isopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoro isobutyl group, nonafluoro-t-butyl group, and perfluoro isopentyl group are preferable. , Hexafluoroisopropyl group, and heptafluoroisopropyl group are more preferable.

Specific examples of the group represented by the general formula (F4), 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, -C (CF ₃ ) ₂ OH is preferred.

The partial structure containing a fluorine atom may be bonded directly to a main chain, and also consists 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 an urylene bond. You may bond with a main chain through the group chosen from the group, or the group which combined two or more of these.

Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.

In the specific examples, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ . X ₂ represents -F or -CF ₃ .

[Formula 62]

[Formula 63]

Hydrophobic resin (D) may contain a silicon atom. It is preferable that it is resin which has an alkylsilyl structure (preferably trialkylsilyl group) or cyclic siloxane structure as a partial structure which has a silicon atom.

Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by general formulas (CS-1) to (CS-3) shown below.

[Formula 64]

In general formula (CS-1)-(CS-3),

R ₁₂ to R ₂₆ each independently represent 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 represent 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 combination of two or more selected from the group consisting of urea bonds (preferably For example, the total carbon number is 12 or less).

n represents the integer of 1-5. n becomes like this. Preferably it is an integer of 2-4.

Hereinafter, although the specific example of the repeating unit which has group represented by General Formula (CS-1)-(CS-3) is given, this invention is not limited to this. In addition, in specific examples, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ .

[Formula 65]

As described above, the hydrophobic resin (D) also preferably includes a CH ₃ partial structure in the side chain portion.

Here, the resin (D) CH ₃ (hereinafter, simply also referred to as "side chain CH ₃ partial structure"), the partial structure having a side chain part of, the include CH ₃ a partial structure having the ethyl group, a propyl group or the like.

On the other hand, the methyl group (for example, (alpha) -methyl group of the repeating unit which has a methacrylic acid structure) couple | bonded with the main chain of resin (D) directly contributes to surface localization of resin (D) by influence of a main chain. it is assumed that because of the small, which is not included in the partial structure CH _3.

More specifically, it is a case where resin (D) contains the repeating unit derived from the monomer which has a polymeric site which has a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M), for example. When R ₁₁ to R ₁₄ are CH ₃ "self", the CH ₃ is not included in the CH ₃ partial structure.

On the other hand, CH ₃ partial structure exists through any atom from the CC main chain, it is assumed for the CH ₃ a partial structure of the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed to have "one" CH ₃ partial structure.

[Formula 66]

In said general formula (M),

R ₁₁ to R ₁₄ each independently represent a side chain moiety.

As R <_11> -R <_14> of a side chain part, a hydrogen atom, monovalent organic group, etc. are mentioned.

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, a cycloalkylaminocarbonyl group, and arylamino Carbonyl group etc. are mentioned, These groups may further have a substituent.

Hydrophobic resin (D) is preferably a resin having a repeating unit having a CH ₃ a partial structure in a side chain part, and, on the other to a same repeating unit, repeating represented by the general formula (II) units, and the general formula (III) It is more preferable to have at least 1 sort (s) of repeating unit (x) among the repeating units represented by these.

Hereinafter, the repeating unit represented by general formula (II) is demonstrated in detail.

[Formula 67]

In General Formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₂ represents an organic group that is stable with respect to an acid having one or more CH ₃ partial structures. Here, the organic group which is stable with respect to an acid is a non-acid-decomposable organic group, and non-acid-decomposable means the property which a decomposition reaction does not generate | occur | produce by the acid which a photo-acid generator generate | occur | produced, as demonstrated in the term of high molecular compound (A). do.

The alkyl group of X _b1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group, and the like.

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. Said 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.

Groups in the acid having at least one partial structure as R ₂ CH ₃ stable organic, it is more preferable to have preferred, and 2 or more than 8 having two or less than 10 CH ₃ a partial structure.

As the alkyl group having at least 1 CH ₃ a partial structure of the R _2, a branched alkyl group having 3 to 20 carbon atoms are preferred. Specific examples of the preferred alkyl group 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 group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-di Methyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, and the like. More preferably, isobutyl group, t-butyl group, 2-methyl-3-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-tetra Methyl-4-heptyl group.

The cycloalkyl group having one or more CH ₃ partial structures in R ₂ may be monocyclic or polycyclic. Specifically, group which has a C5 or more monocyclo, bicyclo, tricyclo, tetracyclo structure, etc. are mentioned. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable. As a preferable cycloalkyl group, an adamantyl group, a noadamantyl group, a decalin residue, a tricyclodecaneyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclo Decanyl group and cyclododecaneyl group are mentioned. More preferably, an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclo dodecaneyl group, and a tricyclodecaneyl group are mentioned. More preferably, they are a norbornyl group, a cyclopentyl group, and a cyclohexyl group.

According to R _2, as the alkenyl group having at least one CH ₃ a partial structure, an alkenyl group of a straight-chain or branched having 1 to 20 carbon atoms are preferred, and more preferably an alkenyl group of branches.

Examples of the aryl group having, at least one CH ₃ a partial structure of the R _2, can be mentioned preferably an aryl group having from 6 to 20 carbon atoms, and examples thereof include a phenyl group, an naphthyl, preferably a phenyl group.

In R _2, As the aralkyl group having at least one CH ₃ partial structure, preferably an aralkyl group having a carbon number of 7-12, and for example, a benzyl group, a phenethyl group, a naphthylmethyl group and the like.

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 and 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, isoocta Methyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-dimethylheptyl, 1,5-dimethyl-3-heptyl, 2,3,5,7-tetramethyl A 4-heptyl group, a 3, 5- dimethyl cyclohexyl group, 4-isopropyl cyclohexyl group, 4-t- butylcyclohexyl group, an isobornyl group, etc. are mentioned. More preferably, 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-di tert-butylcyclohexyl group, 4-isopropylcyclohexyl group, 4 -t-butylcyclohexyl group and isobornyl group.

Preferable specific examples of the repeating unit represented by General Formula (II) are shown below. In addition, this invention is not limited to this.

[Formula 68]

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

Hereinafter, the repeating unit represented by General formula (III) is demonstrated in detail.

[Formula 69]

In General Formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an organic group stable to an acid having one or more CH ₃ partial structures, and n is 1 Represents an integer of 5.

Alkyl group X _b2 is, there is a 1 to 4 carbon atoms include preferably a methyl group, an ethyl group, a propyl group, such as a methyl group to the hydroxy methyl group or trifluoromethyl, is preferably a hydrogen atom.

It is preferable that X _b2 is a hydrogen atom.

Since R <_3> is an organic group which is stable with respect to an acid, it is more preferable that it is an organic group which does not have "the group which decomposes by the action of an acid and produces a polar group" demonstrated in the said resin (A).

Examples of R ₃ include an alkyl group having one or more CH ₃ partial structures.

Groups in the acid having at least one CH ₃ partial structure as R ₃ stable organic, CH ₃ and the partial structure is more preferable to have preferred, and one or more than 8 having 10 or less at least one, at least one 4 It is more preferable to have up to.

As the alkyl group having at least one CH ₃ a partial structure of the R _3, a branched alkyl group having 3 to 20 carbon atoms are preferred. Specific examples of the preferred alkyl group 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 group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-di Methyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, and the like. More preferably, isobutyl group, t-butyl group, 2-methyl-3-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-tetra Methyl-4-heptyl group.

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. can be mentioned. More preferably, it is more preferable that it is C5-C20, and isopropyl group, t-butyl group, 2-methyl-3- 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 And 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 more preferably 1 or 2.

Preferable specific examples of the repeating unit represented by General Formula (III) are shown below. In addition, this invention is not limited to this.

[Formula 70]

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

The resin (D), a case comprising a CH ₃ a partial structure in a side chain part, and repeat that appears as a repeating unit, and the general formula (III) appearing in particular, does not have a fluorine atom and a silicon atom, the general formula (II) It is preferable that it is 90 mol% or more with respect to all the repeating units of resin (D), and, as for content of at least 1 sort (s) of repeating unit (x) among units, it is more preferable that it is 95 mol% or more. The said content is 100 mol% or less normally with respect to all the repeating units of resin (D).

Resin (D) is a repeating unit represented by General Formula (II), and at least 1 type of repeating unit (x) among the repeating units represented by General Formula (III) is 90 to all the repeating units of Resin (D). By containing in mol% or more, the surface free energy of resin (D) increases. As a result, the resin (D) becomes difficult to be ubiquitous on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be surely improved, and the immersion liquid followability can be improved.

Moreover, even when the hydrophobic resin (D) contains (i) a fluorine atom and / or a silicon atom, and (ii) also when the CH ₃ partial structure is included in the side chain portion, the following (x) to (z) You may have at least 1 group chosen from the group of).

(x) diffuse,

(y) a group having a lactone structure, an acid anhydride group, or an acid imide group,

(z) groups decomposed by the action of acids

As the acid group (x), a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, (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 And a tris (alkylsulfonyl) methylene group.

Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

As a repeating unit which has an acidic radical (x), the repeating unit which the acidic radical couple | bonded with the main chain of resin directly through the main chain of resin like the repeating unit by acrylic acid or methacrylic acid, or the linking unit through the coupling group These etc. are mentioned, Furthermore, the polymerization initiator and chain transfer agent which have an acidic radical can be used at the time of superposition | polymerization, and can be introduce | transduced into the terminal of a polymer chain, and any case is preferable. The repeating unit having an acid group (x) may have either a fluorine atom or a silicon atom.

As for content of the repeating unit which has an acidic radical (x), 1-50 mol% is preferable with respect to all the repeating units in hydrophobic resin (D), More preferably, it is 3-35 mol%, More preferably, it is 5-20 Molar%.

Although the specific example of the repeating unit which has an acidic radical (x) is shown below, this invention is not limited to this. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

[Formula 71]

[Formula 72]

As the "group having an lactone structure, an acid anhydride group, or an acid imide group (y)", a group having a lactone structure is particularly preferable.

The repeating unit containing these groups is a repeating unit to which the group is directly bonded to the main chain of the resin, such as, for example, a repeating unit by acrylic acid ester or methacrylic acid ester. Alternatively, the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin through 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.

As a repeating unit which has group which has a lactone structure, the same thing as the repeating unit which has a lactone structure demonstrated in the term of acid-decomposable resin (A) previously, for example is mentioned.

It is preferable that content of the repeating unit which has "a group which has a lactone structure, an acid anhydride group, or an acid imide group (y)" is 1-100 mol% based on all the repeating units in hydrophobic resin (D), It is more preferable that it is 3-98 mol%, and it is still more preferable that it is 5-95 mol%.

In the hydrophobic resin (D), the repeating unit having a group (z) decomposed by the action of an acid is used as it is as a repeating unit having an acid-decomposable group possessed by an acid-decomposable resin widely known as contained in the resist composition. can do. The repeating unit having a group (z) decomposed by the action of an acid may have either a fluorine atom or a silicon atom. 1-80 mol% is preferable with respect to all the repeating units in resin (D), and, as for content of the repeating unit which has group (z) decomposed by the action of an acid in hydrophobic resin (D), it is more preferable. Preferably it is 10-80 mol%, More preferably, it is 20-60 mol%.

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

[Formula 73]

In general formula (III),

R _c31 represents a hydrogen atom, an alkyl group (may be substituted with a fluorine atom, etc.), 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, and 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 the group containing a fluorine atom and a silicon atom.

L _c3 represents a single bond or a divalent linking group.

In General Formula (III), the alkyl group of 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 for L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenylene group, or an ester bond (group represented by -COO-).

The content of the repeating unit represented by General Formula (III) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, more preferably 30 to 70 mol based on all the repeating units in the hydrophobic resin. More preferably%.

It is also preferable that hydrophobic resin (D) further has a repeating unit represented with the following general formula (CII-AB).

[Formula 74]

In formula (CII-AB),

R _c11 ′ and R _c12 ′ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group.

Zc 'includes the two carbon atoms (C-C) bonded to each other and represents an atomic group for forming an alicyclic structure.

The content of the repeating unit represented by General Formula (CII-AB) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, based on all the repeating units in the hydrophobic resin, and 30 to It is more preferable that it is 70 mol%.

Although the specific example of the repeating unit represented by General formula (III) and (CII-AB) below is given, this invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

[Formula 75]

When hydrophobic resin (D) has a fluorine atom, it is preferable that it is 5-80 mass% with respect to the weight average molecular weight of hydrophobic resin (D), and it is more preferable that it is 10-80 mass%. . Moreover, it is preferable that it is 10-100 mol% in all the repeating units contained in hydrophobic resin (D), and, as for the repeating unit containing a fluorine atom, it is more preferable that it is 30-100 mol%.

When hydrophobic resin (D) has a silicon atom, it is preferable that it is 2-50 mass% with respect to the weight average molecular weight of hydrophobic resin (D), and, as for content of a silicon atom, it is more preferable that it is 2-30 mass%. . Moreover, it is preferable that it is 10-100 mol% among all the repeating units contained in hydrophobic resin (D), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-100 mol%.

On the other hand, in particular the resin (D) is in a case comprising a CH ₃ a partial structure in a side chain part, the resin (D) is, the form is also preferably do not contain fluorine atom and a silicon atom in a substantially, and in this case, specifically, It is preferable that content of the repeating unit which has a fluorine atom or a silicon atom is 5 mol% or less with respect to all the repeating units in resin (D), It is more preferable that it is 3 mol% or less, It is further more preferable that it is 1 mol% or less, Ideally, it does not contain 0 mol%, that is, a fluorine atom and a silicon atom. Moreover, it is preferable that resin (D) is comprised substantially 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, it is preferable that 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 is 95 mol% or more in all the repeating units of resin (D), and it is 97 mol% It is more preferable that it is the above, It is more preferable that it is 99 mol% or more, Ideally, it is 100 mol%.

The weight average molecular weight of standard polystyrene conversion of hydrophobic resin (D) becomes like this. Preferably it is 1,000-100,000, More preferably, it is 1,000-50,000, More preferably, it is 2,000-15,000.

Moreover, hydrophobic resin (D) may be used by 1 type, and may be used together in multiple numbers.

0.01-10 mass% is preferable with respect to the total solid in the composition of this invention, as for content in the composition of hydrophobic resin (D), 0.05-8 mass% is more preferable, 0.1-7 mass% is more preferable.

It is preferable that hydrophobic resin (D) contains 0.01-5 mass% of residual monomers and an oligomer component, as well as few impurities, such as a metal, More preferably, 0.01-3 mass% and 0.05-1 mass% are more desirable. Thereby, the actinic-ray-sensitive or radiation-sensitive resin composition which does not change with time, such as a foreign material and sensitivity in a liquid, is obtained. In terms of resolution, resist shape, sidewall of resist pattern, roughness, etc., the molecular weight distribution (Mw / Mn, also referred to as dispersion degree) is preferably in the range of 1 to 5, more preferably 1 to 3, More preferably, it is the range of 1-2.

Various commercial items can also be used for hydrophobic resin (D), and it can synthesize | combine according to a conventional method (for example, radical polymerization). For example, as a general synthetic method, the batch polymerization method which melt | dissolves a monomer species and an initiator in a solvent, and superposes | polymerizes by heating, and the dropping polymerization method which adds the solution of a monomer species and an initiator dropwise for 1 to 10 hours, and adds to a heating solvent Although a 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 30 to 50. It is preferable that it is mass%.

The specific example of hydrophobic resin (D) is shown below. In addition, in the following table, the molar ratio (corresponding in order from each left and each repeating unit) of the repeating unit in each resin, a weight average molecular weight, and dispersion degree are shown.

[Formula 76]

[Formula 77]

[Formula 78]

TABLE 5

[Formula 79]

[Formula 80]

[Formula 81]

[Formula 82]

TABLE 6

TABLE 7

[6] surfactants

The negative actinic ray-sensitive or radiation-sensitive composition of the present invention may further contain a surfactant in order to improve applicability. Examples of the surfactant include, but are not particularly limited to, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Nonionic surfactants, fluorine-based surfactants such as Megapak F171 (made by Dainippon Ink Chemical Co., Ltd.), fluoride FC430 (manufactured by Sumitomo 3M), Sufinol E1004 (manufactured by Asahi Glass), PF656 and PF6320 manufactured by OMNOVA And organosiloxane polymers.

Although the negative actinic-ray-sensitive or radiation-sensitive composition of the present invention may or may not contain a surfactant, the content of the surfactant, when containing the surfactant, is based on the total amount of the composition (excluding the solvent), Preferably it is 0.0001-2 mass%, More preferably, it is 0.0005-1 mass%.

[7] organic carboxylic acids

It is preferable that the negative actinic-ray-sensitive or radiation-sensitive composition of this invention contains organic carboxylic acid other than the said component. As such an organic carboxylic acid compound, 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-naph Earth acid, 2-hydroxy-3-naphthoic acid, etc. are mentioned. When performing electron beam exposure under vacuum, since there is a possibility that it may volatilize from the resist film surface and contaminate the inside of a drawing chamber, As a preferable compound, Aromatic organic carboxylic acid, Especially, For example, benzoic acid, 1-hydroxy-2- naphthoic acid, 2-hydroxy-3-naphthoic acid is suitable.

Although the negative actinic-ray-sensitive or radiation-sensitive composition of this invention may contain or may not contain organic carboxylic acid, when it contains, as a compounding ratio of organic carboxylic acid, it is 0.01- with respect to 100 mass parts of high molecular compounds (A). The inside of the range of 10 mass parts is preferable, More preferably, it is 0.01-5 mass parts, More preferably, it is 0.01-3 mass parts.

As for the negative actinic-ray-sensitive or radiation-sensitive composition of this invention, if necessary, dye, a plasticizer, an acid increasing agent (international publication 95/29968, international publication 98/24000, Japanese Unexamined Patent Publication) Japanese Patent Application Laid-Open No. Hei 8-305262, Japanese Patent Application Laid-Open No. 9-34106, Japanese Patent Application Laid-Open No. 8-248561, Japanese Patent Application Laid-Open No. 8-503082, US Patent Publication No. 5,445,917, Japanese Patent Application Laid-Open No. 8- 503081, U.S. Patent 5,534,393, U.S. Patent 5,395,736, U.S. Patent 5,741,630, U.S. Patent 5,334,489, U.S. Patent 5,582,956, U.S. Patent 5,578,424, U.S. Patent 5,453,345 European Patent Publication No. 665,960, European Patent Publication 757,628, European Patent Publication 665,961, US Patent Publication No. 5,667,943, Japanese Patent Application Laid-open No. Hei 10-1508, Japanese Patent Application Laid-open No. Hei 10-282642, Japanese Laid-Open Patent Publication No. Hei 9-512498, Japanese Laid-Open Patent Publication (As described in Japanese Unexamined Patent Publication No. 2000-62337, Japanese Unexamined Patent Publication No. 2005-17730, Japanese Unexamined Patent Publication No. 2008-209889, etc.), and the like may be further contained. As for all these compounds, each compound described in Unexamined-Japanese-Patent No. 2008-268935 is mentioned.

[8] onium salts

The negative actinic ray-sensitive or radiation-sensitive composition of the present invention may contain a carboxylic acid onium salt. Examples of the carboxylic acid onium salt include carboxylic acid sulfonium salts, carboxylic acid iodonium salts, and carboxylic acid ammonium salts. In particular, carboxylic acid sulfonium salt and carboxylic acid iodonium salt are preferable as the carboxylic acid onium salt. In addition, in this invention, it is preferable that the carboxylate residue of an onium salt of a carboxylic acid does not contain an aromatic group and a carbon-carbon double bond. As an especially preferable anion part, a C1-C30 linear, branched, monocyclic or polycyclic cyclic alkylcarboxylic acid anion is preferable. More preferably, anions of carboxylic acids in which some or all of these alkyl groups are fluorine substituted. You may contain the oxygen atom in the alkyl chain. As a result, transparency to light of 220 nm or less is ensured, sensitivity and resolution are improved, and roughness dependency and exposure margin are improved.

Although the negative actinic-ray-sensitive or radiation-sensitive composition of this invention may contain or may not contain a carboxylic acid onium salt, when it contains, the content of a negative actinic-ray-sensitive or radiation-sensitive composition is content Based on solid content, Preferably it is 0.5-20 mass%, More preferably, it is 0.7-15 mass%, More preferably, it is 1.0-10 mass%.

[9] solvents

It is preferable that the negative actinic-ray-sensitive or radiation-sensitive composition of this invention contains a solvent.

As a solvent which can be used when preparing a negative actinic-ray-sensitive or radiation-sensitive composition, For example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkoxypropionic acid Organic solvents, such as alkyl, cyclic lactone (preferably C4-C10), the monoketone compound (preferably C4-C10) which may have a ring, alkylene carbonate, alkyl alkoxyacetic acid, alkyl pyruvate, are mentioned. .

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 containing a hydroxyl group in the structure, and the solvent which does not contain a hydroxyl group as an organic solvent.

As a solvent containing a hydroxyl group and the solvent which does not contain a hydroxyl group, the above-mentioned exemplary compound can be selected suitably, As a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, alkyl butyrate, etc. are preferable, and propylene is preferable. More preferred are glycol monomethyl ether (PGME, alias 1-methoxy-2-propanol), ethyl lactate, and methyl 2-hydroxyisobutyrate. Moreover, as a solvent which does not contain a hydroxyl group, the alkylene glycol monoalkyl ether acetate, the alkyl alkoxy propionate, the monoketone compound which may contain a ring, cyclic lactone, alkyl acetate, etc. are preferable, Among these, propylene glycol is mentioned. Colmonomethyl ether acetate (PGMEA, alias 1-methoxy-2-acetoxypropane), ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferred. Most preferred are propylene glycol monomethyl ether acetate, ethyl ethoxy propionate and 2-heptanone.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99-99/1, Preferably it is 10/90-90/10, More preferably, it is 20/80-60/40. . The mixed solvent which contains 50 mass% or more of solvents which does not contain a hydroxyl group is especially preferable at the point of coating uniformity.

It is preferable that a solvent contains propylene glycol monomethyl ether acetate, and is a propylene glycol monomethyl ether acetate single solvent, or two or more types of mixed solvents containing propylene glycol monomethyl ether acetate. It is preferable.

It is preferable that solid content concentration of the negative actinic-ray-sensitive or radiation-sensitive composition of this invention is 1-40 mass%. More preferably, it is 1-30 mass%, More preferably, it is 3-20 mass%.

<Negative actinic ray-sensitive or radiation-sensitive film>

The present invention also relates to a negative actinic ray-sensitive or radiation-sensitive film formed by the negative actinic ray-sensitive or radiation-sensitive composition of the present invention. Such a film is, for example, the composition of the present invention is a substrate or the like. It is formed by applying on a support. As for the thickness of this film | membrane, 0.02-0.1 micrometer is preferable. As a method of apply | coating on a board | substrate, although it apply | coats on a board | substrate by suitable coating methods, such as a spin coat, a roll coat, a flow coat, a dip coat, a spray coat, a doctor coat, spin coating is preferable and the rotation speed is 1000- 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.

As the material constituting the substrate and the outermost surface layer, for example, in the case of a semiconductor wafer, a silicon wafer can be used. Examples of the material to be the outermost layer include Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, an organic antireflection film, etc. are mentioned.

Before forming a negative actinic ray sensitive or radiation sensitive film, you may coat an antireflection film on a board | substrate beforehand.

As the antireflection film, both an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. As the organic antireflection film, commercially available organic antireflection films such as DUV-30 series manufactured by Brewer Science, DUV-40 series, and AR-2, AR-3, AR-5 manufactured by Shipley can also be used.

<Mask blank>

Moreover, this invention relates also to the mask blank provided with the negative actinic-ray-sensitive or radiation-sensitive film formed from the 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 fabrication, a transparent substrate such as quartz or calcium fluoride is used. Can be mentioned. Generally, on the said board | substrate, what is required among a functional film, such as a light shielding film, an antireflection film, a phase shift film, and also an etching stopper film and an etching mask film is laminated | stacked. Examples of the material of the functional film include silicon or a film containing transition metals such as chromium, molybdenum, zirconium, tantalum, tungsten, titanium, and niobium. Moreover, as a material used for an outermost surface layer, silicon or the material containing oxygen and / or nitrogen in silicon as a main component material, Furthermore, the silicon compound material which uses as a main component material the material containing a transition metal, , Transition metals, in particular, one or more materials selected from chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium, and the like, or materials further comprising one or more elements selected from oxygen, nitrogen, and carbon Examples thereof include transition metal compound materials having as main constituent material.

Although the light shielding film may be a single layer, it is more preferable that it is a multilayer structure which coat | covered the some material. In the case of a multilayer structure, although the thickness of a film per layer is not specifically limited, It is preferable that it is 5-100 nm, and it is more preferable that it is 10-80 nm. Although it does not restrict | limit especially as thickness of the whole light shielding film, It is preferable that it is 5-200 nm, and it is more preferable that it is 10-150 nm.

Generally, among these materials, when a pattern is formed on a photomask blank having a material containing oxygen or nitrogen in chromium in the outermost layer, it is easy to become a so-called undercut shape in which a concave shape is formed in the vicinity of the substrate. When the invention is used, the undercut problem can be improved as compared with the conventional one.

The negative actinic ray-sensitive or radiation-sensitive film is irradiated with actinic rays or radiation (electron beams, etc.), and preferably developed after baking (usually 80-150 ° C, more preferably 90-130 ° C). . As a result, a good pattern can be obtained. And using this pattern as a mask, an etching process, ion implantation, etc. are performed suitably, and a semiconductor microcircuit, an imprint mold structure, etc. are produced.

In addition, about the process at the time of manufacturing the imprint mold using the negative actinic-ray-sensitive or radiation-sensitive composition of this invention, Unexamined-Japanese-Patent No. 4,090,853, Unexamined-Japanese-Patent No. 2008-162101, for example. And "Basics and Technology Development and Application Development of Nanoimprint-Substrate Technology and Latest Technology Deployment of Nanoimprint-Edit: Hirai Yoshihiko (Frontier Shooting Edition)".

The composition of this invention dissolves the said component in the predetermined organic solvent, Preferably the said mixed solvent, filter-filters, and apply | coats on a predetermined board | substrate, and uses. The pore size of the filter used for the filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, even more preferably 0.03 μm or less, made of polytetrafluoroethylene, polyethylene, or nylon. In the filter filtration, for example, as in JP-A-2002-62667, cyclic filtration may be performed, or plural kinds of filters may be connected in series or in parallel to perform filtration. Moreover, you may filter a composition multiple times. In addition, before and after filter filtration, you may perform a degassing process etc. with respect to a composition.

<Pattern forming method using negative actinic ray-sensitive or radiation-sensitive composition>

The present invention includes a step of forming a film by applying the negative actinic ray-sensitive or radiation-sensitive composition on a substrate, exposing the film, and developing the exposed film to form a negative pattern. It also relates to a pattern formation method. The present invention also relates to a resist pattern forming method comprising a step of exposing a mask blank having the negative actinic ray-sensitive or radiation-sensitive film and a step of developing the exposed mask blank. In this invention, it is preferable that the said exposure is performed using an electron beam or an extreme ultraviolet ray.

Exposure to a negative actinic ray-sensitive or radiation-sensitive film (pattern forming step) in the manufacture of a precision integrated circuit device is first performed by electron beams or poles in a pattern shape on the negative actinic ray-sensitive or radiation-sensitive film of the present invention. It is preferable to perform ultraviolet (EUV) irradiation. The exposure dose is about 0.1-20 μC / cm ^{2 in} the case of an electron beam, preferably about 3-10 μC / cm ² , in the case of extreme ultraviolet rays, about 0.1-20 mJ / cm ² , and preferably about 3-15 mJ / cm ² It exposes as much as possible. Subsequently, a post exposure heating (post exposure bake) is performed on the 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 developing, rinsing and drying to form a pattern. do. The developer is appropriately selected, but it is preferable to use an alkali developer (typically an alkali aqueous solution) or a developer (also referred to as an organic developer) containing an organic solvent. When the developing solution is an aqueous alkali solution, 0.1 to 5% by mass, such as tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide (TBAH), preferably 2 to 3% by mass in an aqueous alkali solution is 0.1 to 3 Minutes, Preferably 0.5-2 minutes, it develops according to conventional methods, such as the dipping method, the puddle method, and the spray method. An appropriate amount of alcohols and / or surfactants may be added to the alkaline developer. In this way, the film | membrane of an unexposed part melt | dissolves, and the exposed part is hard to melt | dissolve in a developing solution, and the target pattern is formed on a board | substrate.

When the resist pattern formation method of this invention has the process of developing using alkaline developing solution, As alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, etc. , First amines such as ethylamine and n-propylamine, second amines such as diethylamine and di-n-butylamine, third amines such as triethylamine and methyldiethylamine, dimethylethanolamine and tri Alcoholamines such as ethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexyl ammonium hydroxide, tetra Octyl Ammonium Hydroxide, Ethyl Trimethyl Ammonium Hydroxide, Butyl Trimethyl Ammonium Tetraalkylammonium hydroxides such as nium hydroxide, methyltriamyl ammonium hydroxide and dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide Alkaline aqueous solutions, such as cyclic amines, such as quaternary ammonium salts, such as a lockside, pyrrole, and piperidine, can be used.

Moreover, alcohol and surfactant can be added to the alkaline aqueous solution in an appropriate amount.

The alkali concentration of alkaline developing solution is 0.1-20 mass% normally.

The pH of alkaline developing solution is 10.0-15.0 normally.

In particular, 2.38 mass% aqueous solution of the tetramethylammonium hydroxide is preferable.

As a rinse liquid in the rinse process performed after alkali image development, you may use it, adding a suitable amount of surfactant using pure water.

In addition, after the development treatment or the rinse treatment, a treatment for removing the developer or rinse liquid attached to the pattern by a supercritical fluid can be performed.

When the resist pattern formation method of this invention has the process of developing using the developing solution containing an organic solvent, as the said developing solution (henceforth an organic developing solution) in the process, it is a ketone solvent, an ester solvent, Polar solvents such as alcohol solvents, amide solvents, ether solvents, and hydrocarbon 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, the alcohol solvent is a solvent having an alcoholic hydroxyl group in the molecule, and the amide solvent is an amide group in the molecule. It is a solvent which has, and an ether type solvent is a solvent which has an ether bond in a molecule | numerator. Among these, there exists also a solvent which has two or more types of the said functional groups in 1 molecule, and in that case, it shall correspond to any solvent species containing the functional group which the solvent has. For example, the diethylene glycol monomethyl ether shall correspond to either the alcohol solvent or the ether solvent in the above classification. In addition, a hydrocarbon solvent is a hydrocarbon solvent which does not have a substituent.

It is especially preferable that it is a developing solution containing at least 1 sort (s) of solvent chosen from a ketone solvent, an ester solvent, an alcohol solvent, and an ether solvent.

Since the developing solution can suppress swelling of the negative actinic ray-sensitive or radiation-sensitive film, the number of carbon atoms is 7 or more (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10). In addition, it is preferable to use an ester solvent having a heteroatom number of 2 or less.

The hetero atom of the said ester solvent is an atom other than a carbon atom and a hydrogen atom, For example, an oxygen atom, a nitrogen atom, a sulfur atom, etc. are mentioned. As for the number of hetero atoms, 2 or less are preferable.

Preferred examples of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, and butyl Butyl carbonate etc. are mentioned, It is especially preferable to use isoamyl acetate.

The developing solution is a mixed solvent of the ester solvent and the hydrocarbon solvent, or a mixed solvent of the ketone solvent and the hydrocarbon solvent, instead of the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms. You may use it. Also in this case, it is effective to suppress swelling of the negative actinic ray-sensitive or radiation-sensitive film.

When using in combination an ester solvent and a hydrocarbon solvent, it is preferable to use isoamyl acetate as an ester solvent. Moreover, as a hydrocarbon-type solvent, from a viewpoint of adjusting the solubility of a negative actinic-ray-sensitive or radiation-sensitive film | membrane, saturated hydrocarbon solvents (for example, octane, nonane, decane, dodecane, undecane, Hexadecane or the like).

As a ketone solvent, For example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, Acetophenone, methylnaphthyl ketone, isophorone, a propylene carbonate, etc. are mentioned.

As ester solvent, for example, 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, formic acid propyl, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate and the like.

As the alcohol solvent, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, 4-methyl-2-pentanol, tert-butyl alcohol, isobutyl alcohol alcohols such as n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and ethylene Glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol And glycol ether solvents such as monoethyl ether and methoxymethylbutanol.

As an ether solvent, anisole, dioxane, tetrahydrofuran etc. are mentioned besides the said glycol ether solvent, for example.

As the amide solvent, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl- 2-imidazolidinone etc. can be used.

As a hydrocarbon solvent, aliphatic hydrocarbon solvents, such as aromatic hydrocarbon solvents, such as toluene and xylene, pentane, hexane, octane, decane, and undecane, are mentioned, for example.

Two or more said solvents may be mixed, and you may use it, mixing with a solvent and water of that excepting the above. However, in order to fully show the effect of the present invention, the water content as the whole developer is preferably less than 10% by mass, more preferably substantially no moisture.

That is, it is preferable that it is 90 mass% or more and 100 mass% or less with respect to the whole amount of a developing solution, and, as for the usage-amount of the organic solvent with respect to an organic developing solution, it is more preferable that it is 95 mass% or more and 100 mass% or less.

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 at 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, and as a result, the dimensional uniformity in the wafer surface is good.

Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methylamylketone), 4-heptanone, 2-hexanone, dia Ketone solvents such as isobutyl ketone, 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- Ester solvents such as methyl-3-methoxybutyl acetate, formic acid butyl, formic acid propyl, ethyl lactate, butyl lactic acid, lactic acid propyl, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert- Butyl Alco Alcohol solvents such as isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol, triethylene glycol and the like Colour solvent, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, Glycol ether solvents such as triethylene glycol monoethyl ether and methoxymethylbutanol, ether solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylacet And amide-based solvents of amide, N, N-dimethylformamide, aromatic hydrocarbon-based solvents such as toluene and xylene, and aliphatic hydrocarbon-based solvents such as octane and decane.

Specific examples having a vapor pressure of 2 kPa or less which are particularly preferred ranges include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone and diiso Ketone solvents such as butyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Colonobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, lactic acid Ester solvents such as butyl and lactic acid propyl, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol Alcohol solvent, ethylene glycol, c. Glycol solvents such as ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol mono Glycol ether solvents such as ethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol, N-methyl-2-pyrrolidone, N, And aromatic hydrocarbon solvents such as amide solvents of N-dimethylacetamide, amide solvents of N, N-dimethylformamide and aromatic hydrocarbons such as xylene, and aliphatic hydrocarbon solvents such as octane, decane and undecane.

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

An appropriate amount of surfactant can be added to the organic developer as needed.

Although it does not specifically limit as surfactant, For example, ionic and nonionic fluorine type and / or silicone type surfactant etc. can be used. As these fluorine type and / or silicone type surfactant, For example, Unexamined-Japanese-Patent No. 62-36663, Unexamined-Japanese-Patent No. 61-226746, Unexamined-Japanese-Patent No. 61-226745, and Japan Unexamined-Japanese-Patent No. 62- 170950, Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9- Surfactants described in 5988, U.S. Patent No. 557520, 5360692, 5529881, 5296330, 5436098, 5576143, 5294511, 5824451, and preferably non- It is an ionic surfactant. Although it does not specifically limit as nonionic surfactant, It is more preferable to use a fluorochemical surfactant or silicone type surfactant.

The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, particularly preferably 0.0005 to 1% by mass, based on the total amount of the developing solution.

As a developing method, for example, a method of immersing a substrate in a bath filled with a developer for a certain time (dip method), a method of developing a developer by raising the developer solution on the surface of the substrate by surface tension to stop for a certain time (puddle method), and a developer on the substrate surface. The spraying method (spray method), the method (dynamic dosing method), etc. which continue to discharge a developing solution while scanning a developer discharge nozzle at a fixed speed on the board | substrate which rotates at a fixed speed are applicable.

When the above various developing methods include a step of discharging the developer from the developing nozzle of the developing apparatus toward the negative actinic ray-sensitive or radiation-sensitive film, the discharge pressure (flow rate per unit area of the developer to be discharged) of the discharged developer is Preferably it is 2 mL / sec / mm <^2> or less, More preferably, it is 1.5 mL / sec / mm <^2> or less, More preferably, it is 1 mL / sec / mm <^2> or less. There is no particular lower limit for the flow rate, but considering the throughput, 0.2 mL / sec / mm ² or more is preferable.

By setting the discharge pressure of the developing solution to be discharged within the above range, the defect of the pattern derived from the resist residue after development can be significantly reduced.

Although the detail of this mechanism is not clear, the pressure which the developing solution gives to a negative actinic-ray-sensitive or a radiation-sensitive film becomes small by possibly setting discharge pressure to the said range, and a negative actinic-ray-sensitive or radiation-sensitive film / pattern It is thought that this careless cutting or collapse is suppressed.

In addition, the discharge pressure (mL / sec / mm ² ) of the developing solution is a value at the developing nozzle outlet in the developing apparatus.

As a method of adjusting the discharge pressure of a developing solution, the method of adjusting discharge pressure with a pump etc., the method of changing by adjusting a pressure by supply from a pressurization tank, etc. are mentioned, for example.

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

After the step of developing using a developer containing an organic solvent, the step of washing with a rinse solution may be included, but the step of washing with a rinse solution from the viewpoint of throughput (productivity), the amount of the rinse solution, and the like. It does not have to include.

There is no restriction | limiting in particular as a rinse liquid used for the rinsing process after the process developed using the developing solution containing the organic solvent, if a resist pattern is not melt | dissolved, The solution containing a general organic solvent can be used. As the rinse liquid, it is preferable to use a rinse liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. Do.

As a specific example of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent, the thing similar to what was demonstrated in the developing solution containing an organic solvent is mentioned.

After the step of developing using a developer containing an organic solvent, the step of washing using a rinse solution containing at least one organic solvent selected from the group consisting of an ester solvent, an alcohol solvent, and a hydrocarbon solvent is performed. It is preferable to carry out, and it is more preferable to perform the process of washing using a rinse liquid containing an alcohol solvent or a hydrocarbon solvent.

As an organic solvent contained in a rinse liquid, it is also preferable to use a hydrocarbon solvent among organic solvents, and it is more preferable to use an aliphatic hydrocarbon solvent. As the aliphatic hydrocarbon solvent used in the rinse liquid, an aliphatic hydrocarbon solvent having 5 or more carbon atoms (e.g., pentane, hexane, octane, decane, undecane, dode) Kane, hexadecane etc.) are preferable, The aliphatic hydrocarbon solvent of 8 or more carbon atoms is more preferable, The aliphatic hydrocarbon solvent of 10 or more carbon atoms is more preferable.

In addition, the upper limit of the carbon atom number of the said aliphatic hydrocarbon solvent is not specifically limited, For example, 16 or less are mentioned, 14 or less are preferable and 12 or less are more preferable.

Among the aliphatic hydrocarbon solvents, particularly preferably, it is decane, undecane and dodecane, and most preferably undecane.

Thus, by using a hydrocarbon solvent (especially an aliphatic hydrocarbon solvent) as the organic solvent contained in the rinse liquid, the developer which slightly penetrated into the negative actinic ray-sensitive or radiation-sensitive film after development is washed away, and swelling It is suppressed more, and the effect that a pattern collapse is suppressed is exhibited further.

Two or more said each components may be mixed, and you may use it, mixing with the organic solvent of that excepting the above.

10 mass% or less is preferable, as for the water content in a rinse liquid, More preferably, it is 5 mass% or less, Especially preferably, it is 3 mass% or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

As for the vapor pressure of the rinse liquid used after the process developed using the developing solution containing the organic solvent, 0.05 kPa or more and 5 kPa or less are preferable at 20 degreeC, 0.1 kPa or more and 5 kPa or less are more preferable, 0.12 kPa or more and 3 kPa or less Most preferable is the following. 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 caused by the penetration of the rinse liquid is suppressed, and the dimensional uniformity in the wafer surface is good.

An appropriate amount of surfactant can also be added and used for a rinse liquid.

In the rinsing step, the wafer subjected to the development using the developer containing the organic solvent is washed using the rinse solution containing the organic solvent. Although the method of a washing process is not specifically limited, For example, the method of continuing to discharge a rinse liquid on the board | substrate which rotates by a fixed speed (rotary coating method), and the method of immersing a board | substrate for a predetermined time in the tank filled with the rinse liquid (dip method) ), And a method (spray method) of spraying a rinse liquid onto the substrate surface can be applied. Among these, it is preferable to perform a washing | cleaning process by the rotation coating method, to rotate a board | substrate at the rotation speed of 2000 rpm-4000 rpm, and to remove a rinse liquid from a board | substrate after washing. Moreover, it is also preferable to include a heating process (PostBake) after a rinse process. By baking, the developer and the rinse liquid remaining between and between the patterns are removed. The heating step after the rinsing step is usually performed at 40 to 160 ° C, preferably at 70 to 95 ° C, usually for 10 seconds to 3 minutes, preferably for 30 seconds to 90 seconds.

Moreover, the pattern formation method of this invention may have the image development process using an organic developing solution, and the image development process using an alkaline developing solution. The part with weak exposure intensity is removed by image development using an organic developer, and the part with strong exposure intensity is also removed by image development using an alkaline developer. In this manner, the pattern development can be performed without dissolving only the region of intermediate exposure intensity by the multiple development process in which the development is carried out a plurality of times. Thus, a finer pattern can be formed (see [Patent Publication No. 2008-292975]. 0077).

Moreover, this invention relates also to the photomask obtained by exposing and developing the mask blank which has the said negative radiation sensitive or actinic ray sensitive film. As exposure and development, the process described above is applied. The photomask is suitably 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 may be a light reflecting mask used in reflecting lithography using EUV light as a light source.

Moreover, you may manufacture the mold for imprint using the composition of this invention, and the detail can be referred to Unexamined-Japanese-Patent No.4109085 and Unexamined-Japanese-Patent No. 2008-162101, for example.

The resist pattern formation method of this invention can also be used for guide pattern formation (for example, ACS Nano Vol. 4 No. 8 Page 4815-4823) in DSA (Directed Self-Assembly).

Moreover, the resist pattern formed by the said method can be used as a core material (core) of the spacer process disclosed by Unexamined-Japanese-Patent No. 3-270227 and Unexamined-Japanese-Patent No. 2013-164509, for example.

Moreover, this invention relates also to the manufacturing method of an electronic device containing the pattern formation method of above-mentioned this invention, and the 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 (such as home appliances, OA media related equipment, optical equipment, communication equipment, and the like).

Example

Hereinafter, although an Example demonstrates this invention further in detail, the content of this invention is not limited by this.

Synthesis Example Synthesis of Polymer Compound (A1)

The high molecular compound (A1) shown in Table 8 described below was synthesized as follows.

[Formula 83]

(Synthesis of Polymer (1a))

10 g of poly (p-hydroxystyrene) (VP2500, dispersion degree 1.10) made by Nippon Soda Co., Ltd. and aqueous potassium hydroxide solution (dissolved 5.7 g of potassium hydroxide in 49 g of water) were mixed, and 20 g of methanol was added thereto. It stirred at 40 degreeC for several minutes. 7.5 g of paraformaldehyde was added thereto and stirred at 40 ° C for 5 hours. After completion | finish of reaction, the reaction liquid was returned to room temperature, 80 ml of ethyl acetate and 80 ml of dilute hydrochloric acid (1N) were added, and liquid separation operation was performed. 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, a solution of 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 | finish of reaction, the reaction liquid was returned to room temperature, 200g of ethyl acetate and 200g of distilled water were added, and liquid separation operation was performed. The organic layer was washed three times with distilled water, and then the organic layer was concentrated. The solution which melt | dissolved the obtained powder in 70 g of ethyl acetate was dripped at 700 g of n-hexanes. The powder was filtered and 5.4 g of a high molecular compound (A1) was obtained after vacuum drying.

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 high molecular compounds A2-A8 were synthesize | combined by the substantially the same method as the above. In addition, the high molecular compound A9 was prepared according to the method of Unexamined-Japanese-Patent No. 2-170165.

In the said synthesis example, the high molecular compound synthesize | combined may increase more than a bicomponent system. For example, in the said synthesis example 1, it may consist of a three component system, ie, the repeating unit whose number of crosslinkable groups is 0, the repeating unit whose number of crosslinkable groups is 1, and the repeating unit whose number of crosslinkable groups is two. Since it is complicated to distinguish and calculate the ratio of the repeating unit whose number of crosslinkable groups is 1, and the repeating unit whose number of crosslinkable groups is 2, the number of crosslinkable groups contained in a high molecular compound was evaluated by the crosslinkable group ratio defined below. .

(Crosslinking rate) = (number of crosslinking groups introduced) / (number of reaction points into which crosslinking groups 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 reaction points into which the methylol group as a crosslinkable group is couple | bonded is a maximum of three places of two ortho and one parawi. In the case of the polymer compound A1, since the parawi is blocked by the bond with the polymer main chain, the number of reaction points (methylolated number) into which the methylol group can be introduced is 2. The said crosslinkable group ratio was computed by guessing the change in reaction back and front of the integral value of the hydrogen atom of the point which can introduce | transduce a crosslinkable group from ¹ H-NMR.

The crosslinkable group ratio, weight average molecular weight, and dispersion degree of a high molecular compound are shown in the following table | surfaces. The weight average molecular weight and dispersion degree were calculated by GPC (solvent: THF) measurement. The structures of the high molecular compounds A1 to A8 may be three or more components as described above, but for the sake of simplicity, the structure of the repeating unit having a crosslinkable group number of 0 and the maximum number of crosslinkable groups (meaning that the reaction points are all reactive) Only the two components of the structure of the repeating unit of are described. In addition, the high molecular compound A9 is obtained by superposition | polymerization of the monomer corresponding to the repeating unit shown in the following table, and has only one component of the repeating unit shown in the following table substantially.

TABLE 8

[Examples 1E to 33E, and Comparative Examples 1ER to 5ER]

(1) Preparation of Support

A 6-inch silicon wafer (having been subjected to a shielding film used for a normal photomask blank) prepared by Cr oxide deposition was prepared.

(2) Preparation of resist coating liquid

The component shown in following Table 9 was melt | dissolved in the solvent shown in the table | surface, each was filtered fine with the polytetrafluoroethylene filter which has a pore diameter of 0.04 micrometer, and the resist coating solution was obtained.

(3) Preparation of resist film

A resist coating solution was 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 form a resist having a thickness of 50 nm as a negative actinic ray-sensitive or radiation-sensitive film. A membrane was obtained. That is, the mask blank provided with the negative actinic-ray-sensitive or radiation-sensitive film was obtained.

(4) Preparation of negative resist pattern

The resist film was subjected to pattern irradiation using an electron beam drawing apparatus (ELS-7500, manufactured by ELIONIX Co., Ltd., acceleration voltage of 50 KeV). After irradiation, the mixture was heated on a hot plate at 120 DEG C for 90 seconds, immersed for 60 seconds using an aqueous 2.38% by mass tetramethylammonium hydroxide (TMAH) solution, and then rinsed with water for 30 seconds to dry.

(5) Evaluation of resist pattern

The obtained pattern was evaluated for sensitivity, resolution, PED stability, and line edge roughness (LER) performance by the following method.

〔Sensitivity〕

The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300, manufactured by Hitachi Seisakusho Co., Ltd.). The exposure amount (electron beam irradiation amount) at the time of resolving the resist pattern of the 1: 1 line and space of 50 nm of line width was made into the 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. Thus, a 1: 1 line and space pattern with a line width of 100 nm was used for Comparative Example 1ER and a line width for Comparative Example 2ER. 1: 1 line and space pattern of 80 nm, 1: 1 line and space pattern of 70 nm line width for Comparative Example 3ER, 1: 1 line and space pattern of 60 nm line width for Comparative Example 4ER, The irradiation energy at the time of resolving the 1: 1 line-and-space pattern having a line width of 65 nm was set as sensitivity (Eop).

〔definition〕

The limit resolution power (minimum line width which the line and space separate and resolve) in the exposure amount (electron beam irradiation amount) which shows said sensitivity was made into resolution power (nm).

[Line Edge Roughness (LER) Performance]

A 1: 1 line and space pattern having a line width of 50 nm was formed with an exposure amount (electron beam irradiation amount) indicating the sensitivity. And about the arbitrary 30 points contained in the 10 micrometers of longitudinal directions, the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi Seisakusho Co., Ltd.). And the standard deviation of this distance was calculated | required and 3σ was computed. Smaller values indicate better performance.

However, in Comparative Example 1ER to 5ER, since the 1: 1 line and space pattern having a line width of 50 nm could not be resolved, in Comparative Example 1ER, in Comparative Example 2ER to a 1: 1 line and space pattern having a line width of 100 nm A 1: 1 line and space pattern with a line width of 80 nm is compared with a 1: 1 line and space pattern with a line width of 70 nm in Comparative Example 3ER, and a 1: 1 line and space pattern with a line width of 60 nm in Comparative Example 4ER. In Example 5ER, the standard deviation of the above distances was calculated for the 1: 1 line-and-space pattern having a line width of 65 nm, respectively, and 3σ was calculated.

(Post Exposure Time Delay Stability)

The line width dimension (0h) on the PEB-treated wafer quickly after exposure and the line line-width dimension on the PEB-treated wafer after 5 hours at an exposure amount at which the line width dimension of the 1: 1 line-and-space pattern having a line width of 50 nm becomes 50 nm. (5.0h) was measured and the line width change rate was computed by the following formula | equation.

% Change in line width = | ΔCD (5.0h-0h) | nm / 50nm

The smaller the value, the better the performance, and the index of PED stability was set.

However, in Comparative Examples 1ER to 5ER, since the 1: 1 line and space pattern having a line width of 50 nm could not be resolved, the exposure dose at which the line width dimension of the 1: 1 line and space pattern having a line width of 100 nm was 100 nm in Comparative Example 1ER. In the above, the line width change rate was calculated. In the comparative example 2ER, said line width change rate was computed in the exposure amount whose line width dimension of the 1: 1 line-and-space pattern of 80 nm of line widths becomes 80 nm. In the comparative example 3ER, the said line width change rate was computed in the exposure amount which the line width dimension of the 1: 1 line-and-space pattern of 70 nm of line widths becomes 70 nm. In the comparative example 4ER, said line width change rate was computed in the exposure amount whose line width dimension of the 1: 1 line-and-space pattern of 60 nm of line width becomes 60 nm. In the comparative example 5ER, said line width change rate was computed in the exposure amount which the line width dimension of the 1: 1 line-and-space pattern of the line width 65 nm becomes 65 nm.

TABLE 9

[Mine generator]

The structure of the photoacid generator used in the example 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 that of the acid generated from the compound (B).

[Formula 84]

[Formula 85]

[Formula 86]

[Basic Compound]

B1: tetrabutylammonium hydroxide

B2: tri (n-octyl) amine

B3: 2,4,5-triphenylimidazole

[Formula 87]

[Cross-linking system]

[Formula 88]

[Other high polymer compounds]

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 the dispersion degree (Mw / Mn) in the other polymer compounds P1 and P2 It shows below.

[Formula 89]

[Organic carboxylic acid]

D1: 2-hydroxy-3-naphthoic acid

D2: 2-naphthoic acid

D3: benzoic acid

〔Surfactants〕

W-1: PF6320 (OMNOVA Co., Ltd. product)

W-2: Megapak F176 (made by Dainippon Ink & Chemicals Co., Ltd .; fluorine system)

W-3: polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd .; silicone type)

〔solvent〕

S1: propylene glycol monomethyl ether acetate (1-methoxy-2-acetoxy propane)

S2: propylene glycol monomethyl ether (1-methoxy-2-propanol)

S3: 2-heptanone

S4: ethyl lactate

S5: cyclohexanone

S6: γ-butyrolactone

S7: Propylene Carbonate

TABLE 10

According to Examples 1E-33E using the pattern formation method which concerns on this invention from the said table, compared with Comparative Examples 1ER-5ER which do not use this, sensitivity, resolution, PED stability, and LER performance can be compatible at a high dimension. I knew it was.

[Examples 1F-10F and Comparative Examples 1FR-4FR]

(Production of Resist Film)

Using the spin coater Mark8 made by Tokyo Electron on the 6-inch silicon wafer, a resist coating solution prepared as described above was applied, dried on a hot plate at 110 ° C. for 90 seconds, and a negative actinic ray-sensitive or radiation-sensitive film. As a result, a resist film having a thickness of 50 nm was obtained. That is, the mask blank provided with the negative actinic-ray-sensitive or radiation-sensitive film was obtained.

(Resist evaluation)

The obtained resist film was evaluated for sensitivity, resolution, PED stability, and line edge roughness (LER) performance by the following method.

〔Sensitivity〕

In the obtained resist film, using an EUV exposure apparatus (MicroExposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) manufactured by Exitech, the exposure amount was 0.1 mJ / cm ^{2 in} the range of 0 to 20.0 mJ / cm ^2. While changing, it passed through the reflective mask of the 1: 1 line-and-space pattern of 50 nm of line width, and after exposing, it baked at 110 degreeC for 90 second. Then, it developed using the 2.38 mass% tetramethylammonium hydrooxide (TMAH) aqueous solution.

The exposure amount which reproduces the mask pattern of 1: 1 line and space of 50 nm of line width was made into the 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, so a 1: 1 line and space pattern with a line width of 350 nm was used for Comparative Example 1FR and a line width for Comparative Example 2FR. Investigation when resolving a 100-nm 1: 1 line-and-space pattern, a 1: 1 line-and-space pattern with a line width of 85 nm for Comparative Example 3FR, and a 1: 1 line-and-space pattern with a line width of 60 nm for Comparative Example 4FR, respectively Energy was made into the sensitivity (Eop).

〔definition〕

The limit resolution (the minimum line width at which the line and the space (line: space = 1: 1) separate and resolve) in the exposure amount indicating the sensitivity was set to resolution (nm).

[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 indicating the sensitivity. And the distance from the reference line which should have an edge was measured using the scanning electron microscope (S-9220 by Hitachi Seisakusho Co., Ltd.) about arbitrary 30 points in 50 micrometers of the longitudinal directions. And the standard deviation of this distance was calculated | required and 3σ was computed. Smaller values indicate better performance.

However, in Comparative Example 1FR to 4FR, since the 1: 1 line and space pattern having a line width of 50 nm could not be resolved, in Comparative Example 1FR, in Comparative Example 2FR to a 1: 1 line and space pattern having a line width of 350 nm. For a 1: 1 line and space pattern with a line width of 100 nm, for a 1: 1 line and space pattern with a line width of 85 nm in Comparative Example 3FR, and for a 1: 1 line and space pattern with a line width of 60 nm in Comparative Example 4FR, respectively. 3σ was calculated by determining the standard deviation of the above distance.

(Post Exposure Time Delay Stability)

In the exposure amount at which the line width dimension of the line-and-space 1: 1 pattern of 50 nm becomes 50 nm, the line width dimension (0h) which was PEB-processed immediately after exposure, and the line width dimension (5.0h) on the wafer which were PEB-processed after 5 hours ) And the line width change rate was computed by the following formula | equation.

% Change in line width = | ΔCD (5.0h-0h) | nm / 50nm

The smaller the value, the better the performance, and the index of PED stability was set.

However, in Comparative Examples 1FR to 4FR, since the 1: 1 line and space pattern having a line width of 50 nm could not be resolved, the exposure dose at which the line width dimension of the 1: 1 line and space pattern having a line width of 350 nm became 350 nm in Comparative Example 1FR. In the above, the line width change rate was calculated. In the comparative example 2FR, said line width change rate was computed in the exposure amount which the line width dimension of the 1: 1 line-and-space pattern of line width 100nm becomes 100 nm. In the comparative example 3FR, said line width change rate was computed in the exposure amount which the line width dimension of the 1: 1 line-and-space pattern of 85 nm of line widths becomes 85 nm. In the comparative example 4FR, said line width change rate was computed in the exposure amount which the line width dimension of the 1: 1 line and space pattern of 60 nm of line width becomes 60 nm.

TABLE 11

According to Examples 1F-10F using the pattern formation method which concerns on this invention from the said table, compared with Comparative Examples 1ER-4FR which do not use this, sensitivity, resolution, PED stability, and LER performance can be compatible at a high dimension. I knew it was.

Claims (14)

(A) a polymer compound having a repeating unit represented by the following General Formula (2),
(B) by irradiation of actinic ray or radiation, a compound that generates a volume 130Å 2000Å ³ or more and ³ or less acid,
(C) The negative actinic ray-sensitive or radiation-sensitive resin composition containing the onium salt compound represented by following General formula (4).

In General Formula (2), 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,
m 'represents 1 or 2,
n 'represents the integer of 1-3.

In general formula (4), 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) valence organic group, X represents a single bond or a linking group, A _N represents a basic moiety including a nitrogen atom. When two or more R _<A> , R <_B> , X and A <_N> respectively exist, they may be same or different.
When A is a sulfur atom, q is an integer of 1-3 and o is an integer which 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 o + q = 2.
p represents the integer of 1-10, 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 method according to claim 1,
The negative actinic-ray-sensitive or radiation-sensitive resin composition whose repeating unit represented by the said General formula (2) is a repeating unit represented by the following General formula (3).
[Formula 3]

Wherein, R _2, R _3, and R ₄ is an R _2, R _3, and R ₄ and the consent of the general formula (2). n 'represents the integer of 1-3. The method according to claim 1,
The negative actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound (B) is a sulfonium salt. delete delete The method according to any one of claims 1 to 3,
The negative actinic-ray-sensitive or radiation-sensitive resin composition whose dispersion degree of the said high molecular compound (A) is 1.0-1.40. The method according to any one of claims 1 to 3,
Negative actinic-ray-sensitive or radiation-sensitive resin composition whose said high molecular compound (A) is a high molecular compound manufactured by the manufacturing method which uses the polymer of the repeating unit represented by following General formula (5) as a raw material.
[Formula 5]

R ₁ in the formula is R ₁ and consent of the general formula (2). The method according to claim 7,
The negative actinic-ray-sensitive or radiation-sensitive resin composition whose dispersion degree of the polymer of the repeating unit represented by the said General formula (5) is 1.0-1.20. The method according to claim 2,
The negative actinic ray-sensitive or radiation-sensitive resin composition, wherein R ₂ and R ₃ in General Formula (3) are both hydrogen atoms. The negative actinic ray-sensitive or radiation-sensitive film formed using the negative actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-3. The mask blank provided with the negative actinic-ray-sensitive or radiation-sensitive film of Claim 10. The process of apply | coating the negative actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-3 on a board | substrate, and forming a film,
Exposing the film, and
And forming a negative pattern by developing the exposed film. The manufacturing method of an electronic device containing the pattern formation method of Claim 12. delete