TWI697732B - Negative sensitizing radiation or radiation sensitive resin composition, negative sensitizing radiation or radiation sensitive film, pattern forming method, and method of manufacturing electronic component - Google Patents

Abstract

The present invention provides a negative sensitizing radiation or sensitivity that can form patterns with excellent sensitivity, resolution, PED stability, and line edge roughness, that is, LER performance, especially in the formation of ultra-fine patterns with a line width of 50 nm or less. radiation-sensitive resin composition comprising: (A) a polymer compound having repeating units represented by the formula (1) represented by the; (B) by irradiation with actinic rays or radiation to produce a volume of 130Å ³ or more and 2000Å ³ The following acid compounds. 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, Cycloalkyl, aryl, or acyl, 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 photosensitive radiation or radiation-sensitive resin composition, negative photosensitive Chemical radiation or radiation sensitive film, pattern forming method and manufacturing method of electronic component

The present invention relates to a microlithography process suitable for the manufacture of ultra-LSI or high-capacity microchips or other photosensitive etching manufacturing processes, and can use electron beam or extreme ultraviolet to form high-definition patterns The negative-type sensitizing radiation or radiation-sensitive resin composition, the negative-type sensitizing radiation or radiation-sensitive film, the pattern forming method and the manufacturing method of electronic components.

Previously, in the manufacturing process of semiconductor devices such as ICs or LSIs, microfabrication was performed by lithography using photoresist compositions. In recent years, with the increasing integration of integrated circuits, the formation of ultra-fine patterns in the sub-micron area or quarter-micron area has begun to be required. Along with this, it has been discovered that the exposure wavelength has also been shortened by changing from g-rays to i-rays, and then to excimer lasers. Currently, lithography using electron beams or X-rays is also being developed.

These electron beams, X-rays, or EUV photolithography are positioned as the next or next-generation patterning technology, and a high-sensitivity and high-resolution resist composition is desired. As a resist composition suitable for negative lithography, a so-called negative chemically amplified resist composition containing an alkali-soluble resin, a crosslinking agent, and an acid generator as main components is effectively used (for example, refer to Patent Document 1 ).

When forming a negative resist pattern, even if the unexposed part intended to be removed by the developer and the exposed part not intended to be removed by the developer are provided on the resist film by exposure, the unexposed The area adjacent to the exposed area is usually low in exposure, but is also exposed (hereinafter this area is referred to as "weakly exposed area"). As a result, in the weakly exposed portion, it becomes insoluble or poorly soluble in the developer, which becomes a factor that causes a bridge between patterns formed by development.

On the other hand, as a negative chemically amplified resist composition containing an acid generator, a cross-linking group that undergoes a cross-linking reaction by acid, and a site that can undergo a cross-linking reaction with the cross-linking group, have been developed. A polymer containing the two in the polymer structure (hereinafter referred to as "crosslinked supporting polymer"). In general negative chemically amplified resist compositions that use low-molecular-weight cross-linking agents for negative type, the volatilization of low-molecular-weight cross-linking agents in the process often becomes a problem, but the cross-linked supporting polymer does not exist The advantages of this worry. For example, Patent Document 2 describes a polymer containing a phenolic hydroxyl group as a crosslinkable group containing a methylol group. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2002-99085 [Patent Document 2] Japanese Patent Application Publication No. 2-170165

However, when forming ultra-fine patterns with a line width of 50 nm or less, sufficient resolution was not obtained. In addition, it is required to further improve the stability of PED (the stability of the coating film when it is left after exposure to the heating operation (PEB)), but Patent Document 2 does not mention the stability of PED, and in fact PED Insufficient stability. Therefore, the object of the present invention is to provide a method that can form sensitivity, resolution, PED stability, and line edge roughness (LER) performance, especially in ultra-fine pattern formation (for example, line width below 50nm). The pattern of negative sensitizing radiation or radiation sensitive resin composition, and the negative sensitizing radiation or radiation sensitive film using it, the blank mask with negative sensitizing radiation or radiation sensitive film, A pattern forming method, a method of manufacturing an electronic component including the above-mentioned pattern forming method, and an electronic component.

As a result of intensive research, the inventors found that the above object is achieved by a resist composition combining a polymer compound of a specific structure and a compound that generates an acid by irradiating actinic rays or radiation.

That is, the present invention is as follows.

式中，R₁ 表示氫原子、烷基或鹵素原子，R₂ 和R₃ 分別獨立地表示氫原子、烷基、環烷基、芳烷基或芳基，R₄ 表示氫原子、烷基、環烷基、芳基或醯基，L表示單鍵或2價連結基，Ar表示芳香族基，m和n分別獨立地表示1以上的整數。 〔2〕如上述〔1〕所述之負型感光化射線性或感放射線性樹脂組成物，其中，由上述通式（1）所表示之重複單元為由下述通式（2）所表示之重複單元。 【化學式2】

式中，R₁ 、R₂ 、R₃ 及R₄ 與通式（1）中的R₁ 、R₂ 、R₃ 及R₄ 意義相同。m’表示1或2，n’表示1～3的整數。 〔3〕如上述〔2〕所述之負型感光化射線性或感放射線性樹脂組成物，其中，由上述通式（2）所表示之重複單元為由下述通式（3）所表示之重複單元。 【化學式3】

式中，R₂ 、R₃ 、及R₄ 與通式（1）中的R₂ 、R₃ 、及R₄ 意義相同。n’表示1～3的整數。 〔4〕如上述〔1〕至〔3〕中任一個所述之負型感光化射線性或感放射線性樹脂組成物，其中，上述化合物（B）為鋶鹽。 〔5〕如上述〔1〕至〔4〕中任一個所述之負型感光化射線性或感放射線性樹脂組成物，其還包括，由於照射光化射線或放射線而鹼性降低之鹼性化合物或銨鹽化合物（C）。 〔6〕如上述〔5〕所述之負型感光化射線性或感放射線性樹脂組成物，其中，上述化合物（C）為由下述通式（4）所表示之鎓鹽化合物。 【化學式4】

式中，A表示硫原子或碘原子，R_A 表示氫原子或有機基團，R_B 表示（p+1）價的有機基團，X表示單鍵或連結基，A_N 表示含氮原子之鹼性部位。R_A 、R_B 、X及A_N 分別存在多個之情況下，該些可相同亦可不同。 A為硫原子時，q為1～3的整數，o為滿足o+q=3的關係之整數。 A為碘原子時，q為1或2，o為滿足o+q=2的關係之整數。 p表示1～10的整數，Y^- 表示陰離子。 R_A 、X、R_B 、A_N 中的至少2個相互可鍵結而形成環。 〔7〕如上述〔1〕至〔6〕中任一個所述之負型感光化射線性或感放射線性樹脂組成物，其中，上述高分子化合物（A）的分散度為1.0～1.40。 〔8〕如上述〔1〕至〔7〕中任一個所述之負型感光化射線性或感放射線性樹脂組成物，其中，上述高分子化合物（A）為藉由將由下述通式（5）所表示之重複單元的聚合物作為原料之製造方法製造之高分子化合物。 【化學式5】

式中的R₁ 與上述通式（1）中的R₁ 意義相同。 〔9〕如上述〔8〕所述之負型感光化射線性或感放射線性樹脂組成物，其中，由上述通式（5）所表示之重複單元的聚合物的分散度為1.0～1.20。 〔10〕如上述〔3〕所述之負型感光化射線性或感放射線性樹脂組成物，其中，上述通式（3）中的R₂ 及R₃ 同為氫原子。 〔11〕一種負型感光化射線性或感放射線性膜，其藉由使用上述〔1〕至〔10〕中任一個所述之負型感光化射線性或感放射線性樹脂組成物而形成。 〔12〕一種空白遮罩，其具備上述〔11〕所述之負型感光化射線性或感放射線性膜。 〔13〕一種圖案形成方法，其包括： 在基板上塗佈上述〔1〕至〔10〕中任一個所述之負型感光化射線性或感放射線性樹脂組成物而形成膜之步驟； 將上述膜進行曝光之步驟；及 對已曝光之上述膜進行顯影而形成負型圖案之步驟。 〔14〕一種電子元件的製造方法，其包括上述〔13〕所述之圖案形成方法。 〔15〕一種電子元件，其藉由上述〔14〕所述之電子元件的製造方法來製造。[1] A negative-type sensitizing radiation or radiation-sensitive resin composition comprising: (A) a polymer compound having a repeating unit represented by the following general formula (1); (B) by irradiating light ray or radiation to generate 130Å ³ or more and 2000Å ³ or less of a volume of an acid compound. 【Chemical 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, Cycloalkyl, aryl, or acyl, 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 sensitizing radiation or radiation-sensitive resin composition as described in [1] above, wherein the repeating unit represented by the above general formula (1) is represented by the following general formula (2) The repeating unit. 【Chemical formula 2】

_{Wherein, R 1, R 2, R} 3 and R ₄ in the general formula R (1) is _1, R _2, R ₃ and R ₄ the same meaning. m'represents 1 or 2, and n'represents an integer of 1-3. [3] The negative sensitizing radiation or radiation-sensitive resin composition as described in [2] above, wherein the repeating unit represented by the general formula (2) is represented by the following general formula (3) The repeating unit. 【Chemical formula 3】

Wherein, R & lt _2, R _3, and R ₄ in the general formula R (1) _2, the same as R _3, and R ₄ significance. n'represents an integer of 1-3. [4] The negative sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3] above, wherein the compound (B) is a sulfonium salt. [5] The negative-type sensitizing ray-sensitive or radiation-sensitive resin composition as described in any one of [1] to [4] above, which further includes an alkalinity whose alkalinity is reduced due to irradiation with actinic rays or radiation Compound or ammonium salt compound (C). [6] The negative sensitizing radiation-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). 【Chemical formula 4】

Wherein, A represents a sulfur atom or an iodine atom, R _A represents a hydrogen atom or an organic group, R _B represents a (p + 1) valent organic group, X represents a single bond or a linking group, A represents a nitrogen atom of the _N Alkaline site. When there are a plurality of R _A , R _B , X and A _N respectively, these may be the same or different. When A is a sulfur atom, q is an integer of 1 to 3, and o is an integer satisfying the relationship of o+q=3. When A is an iodine atom, q is 1 or 2, and o is an integer satisfying the relationship of o+q=2. p represents an 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] The negative-type sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [6] above, wherein the degree of dispersion of the polymer compound (A) is 1.0 to 1.40. [8] The negative-type sensitizing radiation or radiation-sensitive resin composition according to any one of [1] to [7] above, wherein the polymer compound (A) is formed by the following general formula ( 5) The polymer compound produced by the method of producing the polymer of the repeating unit as the raw material. 【Chemical formula 5】

In the _formula, R ₁ meaning _same as in the general formula R (1) it is. [9] The negative-type sensitizing radiation or radiation-sensitive resin composition according to the above [8], wherein the polymer dispersion of the repeating unit represented by the general formula (5) is 1.0 to 1.20. [10] The negative sensitizing radiation or radiation-sensitive resin composition according to the above [3], wherein R ₂ and R ₃ in the general formula (3) are both hydrogen atoms. [11] A negative-type sensitizing radiation or radiation-sensitive film formed by using the negative-type sensitizing radiation or radiation-sensitive resin composition described in any one of [1] to [10]. [12] A blank mask comprising the negative sensitizing radiation or radiation sensitive film described in [11] above. [13] A pattern forming method, comprising: coating the negative sensitizing radiation or radiation sensitive resin composition of any one of [1] to [10] on a substrate to form a film; The step of exposing the film; and the step of developing the exposed film to form a negative pattern. [14] A method of manufacturing an electronic component, which includes the pattern forming method described in [13] above. [15] An electronic component manufactured by the method of manufacturing the electronic component described in [14] above.

Through the present invention, it is possible to provide a negative sensitizing radiation or a pattern that can form patterns with excellent sensitivity, resolution, PED stability, and LER performance, especially in the formation of ultra-fine patterns (for example, line widths of 50 nm or less). Radiation-sensitive resin composition, negative sensitizing radiation or radiation sensitive film using the same, blank mask with negative sensitizing radiation or radiation sensitive film, pattern forming method, and pattern forming method including the above The manufacturing method of electronic components and electronic components.

Hereinafter, embodiments of the present invention will be described in detail. In the label of the group (atomic group) in this specification, the label not marked with substitution and unsubstituted includes a group without a substituent, and also includes a group with a substituent. For example, the "alkyl" system includes not only an unsubstituted alkyl group (unsubstituted alkyl), but also a substituted alkyl group (substituted alkyl). The "actinic rays" or "radiation rays" in this specification refer to, for example, the bright spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. In addition, in the present invention, light refers to actinic rays or radiation. In addition, unless otherwise specified, the "exposure" in this manual includes not only exposure based on the apparent spectrum of mercury lamps, extreme ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, etc., using electrons The drawing performed by particle beams such as beams and ion beams is also included in the exposure. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (Mw/Mn) of polymer compounds and resins are defined as those performed by a GPC device (HLC-8120GPC manufactured by Tosoh Corporation) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10μl, column: TSK gel Multipore HXL-M (x4) manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL/min, detector : Polystyrene conversion value derived from the differential refractive index (RI) detector.

The negative sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention includes: (A) a polymer compound having a repeating unit represented by the general formula (1) (hereinafter, also referred to as "polymer compound (A)) ");. (B) by irradiation with actinic rays or radiation to generate the volume of 130Å ³ or more and an acid compound of the following size 2000Å ³ (hereinafter also referred to as" acid generator (B) "or" compound (B ).).

Thereby, it is possible to provide a negative-type sensitizing radiation or radiation-sensitive linear resin with excellent sensitivity, resolution, PED stability, and LER performance in the formation of ultra-fine patterns (for example, regions with a line width of 50 nm or less) Composition, negative sensitizing radiation or radiation-sensitive film using the same, blank mask with negative sensitizing radiation or radiation-sensitive film, pattern forming method, and electronic components including the above pattern forming method Manufacturing methods and electronic components.

As the reason for achieving the above, in the present invention, the volume of the acid generated by the compound (B) by irradiation with actinic rays or radiation is greater than 130 Å ³ and the diffusibility of the acid generated by the compound (B) is low. Thereby, since it is possible to suppress the excess acid from diffusing to the unexposed part, it can be considered that the resolution in the ultrafine region is improved. In addition, the diffusibility of the acid after exposure is low, and as a result, it can be considered that the stability of PED is improved. However, in the present invention, high resolution that cannot be explained only by the above-mentioned diffusibility is obtained. Although the reason is not clear, it is estimated as follows.

The crosslinkable group-containing polymer typically has a large (bulk) crosslinkable structure site containing a crosslinkable group on the side chain of the polymer (for example, Japanese Patent Application Laid-Open No. 2014-24999 ), the polymer compound (A) of the present invention is directly bonded to the benzene ring of the main chain of the polymer compound with a crosslinkable group, and therefore has a cross-linkable group-containing The polymer has a very compact structure. In the case of a typical polymer containing crosslinkable groups, due to its size, it also has a certain degree of free volume after crosslinking. Therefore, the effect of inhibiting the diffusion of the acid generated in the exposed part is limited, but As in the case of the compact structure of the present invention, the free volume after crosslinking is very small, and the above-mentioned acid diffusion suppression effect is greater than expected. As a result, it is presumed that the resolution becomes very high. In addition, by this action, it can be estimated that LER performance is also excellent.

Hereinafter, the negative-type sensitizing radiation or radiation-sensitive resin composition of the present invention will be described. The negative-type sensitizing radiation or radiation-sensitive resin composition of the present invention is preferably used for electron beam or extreme ultraviolet exposure, and more preferably used for electron beam exposure. The negative-type sensitizing radiation-sensitive or radiation-sensitive resin composition of the present invention is typically a negative-type patterning resist composition, which may be a negative-type resist composition for organic solvent development, or may be alkaline development Use negative resist composition. In addition, the composition of the present invention is typically a chemically amplified resist composition.

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

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

【Chemical 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, Cycloalkyl, aryl, or acyl, 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.

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

The divalent linking group represented by L includes monocyclic or polycyclic aromatic rings, -C(=O)-, -OC(=O)-, -CH ₂ -OC(=O)-, thiocarbonyl , Straight-chain or branched alkylene (1 to 10 carbon atoms is preferred, 1 to 6 is more preferred), linear or branched alkenylene (2 to 10 carbon atoms is preferred, 2 ～6 is more preferred), cycloalkylene (3～10 is preferred, 3～6 is more preferred), sulfonyl, -O-, -NH-, -S-, cyclic lactone Structure or combination of these divalent linking groups (total carbon atoms are preferably 1-50, total carbon atoms are more preferably 1-30, and total carbon atoms are more preferably 1-20).

Ar represents an aromatic group. Preferable examples of the aromatic group include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, sulphur ring, phenanthrene ring, etc., or containing, for example, thiophene ring, furan ring, pyrrole ring, benzothiophene ring, Aromatic heterocyclic rings such as benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring. A benzene ring or a naphthalene ring is more preferable, and a benzene ring is 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. Examples of the alkyl group represented by R ₂ and R ₃ include linear or branched alkyl groups having 1 to 10 carbon atoms, and examples of the cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms. . Specifically, a hydrogen atom, a methyl group, a cyclohexyl group, and a tertiary butyl group can be mentioned.

When the cross-linking reaction is caused by acid, -OR _{4 is} separated to generate carbocation to proceed the reaction. Therefore, R ₂ and R ₃ are the substituents that stabilize the carbocation, that is, electron releasing group, aromatic group or hydrogen Atoms are preferred. Specifically, an alkyl group, a cycloalkyl group, a phenyl group or a hydrogen atom is preferable, and a hydrogen atom is more preferable.

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

General formula (1) R ₁ is an alkyl group, the alkyl group of R ₂ and R _3, cycloalkyl, aryl and aralkyl group, a cycloalkyl group as R _4, aryl and acyl, as The divalent linking group of L and the aromatic group as Ar may each have a substituent. Examples of the substituent include alkyl (straight-chain or branched, preferably with 1 to 12 carbon atoms), alkenyl (preferably with 2 to 12 carbon atoms), and alkynyl (with 2 carbon atoms). ～12 is preferred), cycloalkyl (monocyclic or polycyclic, preferably with 3 to 12 carbon atoms), aryl (with 6 to 18 carbon atoms is preferred), hydroxyl, alkoxy, Ester group, amide group, urethane group, urea group, thioether group, sulfonamide group, halogen atom, haloalkyl group and sulfonate group. As preferred examples, alkyl groups, cycloalkyl groups, halogen atoms, haloalkyl groups, hydroxyl groups, alkoxy groups, aryloxy groups, ester groups, and aryl groups can be cited. More preferred examples include alkyl groups. , Halogen atom, hydroxyl group, alkoxy group. Examples of the halogen atom include the same as those listed for R ₁ above. The above-mentioned substituent may further have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (such as a fluorine atom), an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an aryl group, The alkoxyalkyl group and a combination of these groups preferably have 8 or less carbon atoms.

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

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

In addition, it is more preferable that the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (2).

【Chemical formula 7】

_{Wherein, R 1, R 2, R} 3 and R ₄ in the general formula R (1) is _1, R _2, R ₃ and R ₄ the same meaning. m'represents 1 or 2, and n'represents an integer of 1-3.

R _1, R _2, R ₃ and R ₄ are specific examples and preferred examples of the general formula R (1) is, R _2, R ₃ and R ₄ are same as those described for _1.

It is more preferable that m'is 1.

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

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

【Chemical formula 8】

Wherein, R & lt _2, R ₃ and R ₄ in the general formula R (1) _2, R ₃ and R ₄ the same meaning. n'represents an integer of 1-3.

R _2, R _3, R ₄ and n 'preferred embodiment and specific examples of the general formula (1) or the general formula R (2) is _2, R _3, R ₄ and n' are those described for the same. Among them, it is preferable that both R ₂ and R ₃ are hydrogen atoms.

From the viewpoint of crosslinking efficiency and developability, the content of the repeating unit represented by the general formula (1), (2) or (3) is relative to all the repeating units contained in the polymer compound (A). 20-100 mol% is preferable, and 40-100 mol% is more preferable. In addition, the introduction rate of the group represented by -(R ₂ )(R ₃ )(OR ₄ ) as a crosslinkable group in the general formula (1), (2) or (3) (hereinafter also referred to as As the ratio of crosslinkable groups), from the viewpoint of crosslinking efficiency and developability, 20-100% is preferable, and 40-100% is more preferable. Here, the ratio of crosslinkable groups is the number of points (number) of crosslinkable groups in the polymer compound (A) divided by the number (number) of reaction points into which crosslinkable groups can be introduced The percentage (%). The reaction point of the crosslinkable group can be introduced. For example, when the calculation object has a phenolic hydroxyl group, considering the position of the phenolic hydroxyl group, the crosslinkable group can be introduced into the ortho and para positions of the phenolic hydroxyl group. The position of the group. The detailed description is described later in the following embodiment items.

As specific examples of the repeating unit represented by the general formula (1), (2), or (3), the following structures can be given, but it is not limited to these.

【Chemical formula 9】

【Chemical formula 10】

【Chemical formula 11】

The polymer compound (A) may further have a repeating unit having a phenolic hydroxyl group that is different from the repeating unit represented by the above general formula (1). Here, the phenolic hydroxyl group is a group obtained by substituting a hydroxyl group for the hydrogen atom of an aromatic ring group. The aromatic ring of the aromatic ring group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

The repeating unit having a phenolic hydroxyl group is not particularly limited, but it is preferable to have a structural unit represented by the following general formula (II).

【Chemical 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 the general formula (II) represents an organic group, the organic group is preferably an alkyl group, a cycloalkyl group, and an aryl group, and a linear or branched alkyl group having 1 to 10 carbon atoms (such as , Methyl, ethyl, propyl, butyl, pentyl), cycloalkyl with 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, norbornyl), aromatic with 6 to 10 carbon atoms Group (for example, phenyl, naphthyl) is more preferred. 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, etc., but it is not limited to these. As the substituent, a fluorine atom and a hydroxyl group are particularly preferred. Examples of the organic group when it has a substituent include trifluoromethyl, hydroxymethyl, and the like. 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, as the divalent linking group, a carbonyl group, an alkylene group, an arylene group, a sulfonyl group, -O-, -NH- or a combination of these groups (for example, ester bond Etc.) is better. D ₁ is preferably a single bond or a carbonyloxy group, more preferably a single bond.

As the aromatic ring group represented by Ar ₂ , a group in which n+1 hydrogen atoms are removed from a monocyclic or polycyclic aromatic ring (n represents an integer of 1 or more) is preferred. Examples of the above-mentioned aromatic ring include an aromatic hydrocarbon ring (preferably having 6 to 18 carbon atoms) which may have substituents such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a thiophene ring. , Furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc. Aromatic heterocycle. Among them, a benzene ring and a naphthalene ring are preferable from the viewpoint of analytical properties, and a benzene ring is the most preferable.

It is preferable that m ₁ is an integer of 1 to 5, an integer of 1 to 3 is more preferable, 1 or 2 is more preferable, and 1 is particularly preferable. When m ₁ represents 1, and Ar ₂ represents a benzene ring, the substitution position of -OH relative to the bonding position of the benzene ring to the polymer backbone can be para, meta, or ortho. It can be developed from alkaline From the viewpoint of sex, it is better to consider the alignment.

The aromatic ring in the aromatic ring group of Ar ₂ may have a substituent in addition to the group represented by -OH. Examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkane group. Oxycarbonyl, alkylcarbonyl, alkylcarbonyloxy, alkylsulfonyloxy, arylcarbonyl. Among them, the aromatic ring in the aromatic ring group of Ar ₂ serves as a substituent and does not have the group represented by -C(R ₂ )(R ₃ )(OR ₄ ) in the general formula (1).

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

【Chemical 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.

₁ the same meaning of the general formula (II-1) in D R ₁ and R ₅ in the general formula (II), and ₅ D, preferred ranges are also the same.

It is more preferable that the general formula (II) is the following general formula (II-2).

【Chemical formula 14】

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

The same meaning of the general formula R ₅ R ₅ in the general formula (II) (II-2) in the, preferred ranges are also the same.

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

【Chemical formula 15】

【Chemical formula 16】

When the polymer compound (A) has a repeating unit having a phenolic hydroxyl group that is different from the repeating unit represented by the above general formula (1), the content of the repeating unit is relative to all repeating units of the polymer compound (A) , Preferably 1 to 80 mol%, more preferably 1 to 70 mol%, and even more preferably 1 to 60 mol%.

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

The polymer compound (A) may have "a structure in which the hydrogen atom of a phenolic hydroxyl group is substituted by a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure (hereinafter, also referred to as a "specific structure")" . In this case, the polymer compound (A) has a "repeating unit with a structure in which the hydrogen atom of a phenolic hydroxyl group is replaced by a group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure". good. Thereby, a higher glass transition temperature (Tg) can be obtained, and the dry etching resistance becomes good.

Since the polymer compound (A) has the aforementioned specific structure, it is possible to form a very hard resist film with a high glass transition temperature (Tg) of the polymer compound (A), and to control the diffusibility and drying of the acid. Etching resistance. Therefore, the diffusibility of acid on the exposed portion of actinic rays such as electron beams and extreme ultraviolet rays or radiation is very well suppressed, so the resolution, pattern shape, and LER in fine patterns are more excellent. In addition, it is considered that the compound (D) has a non-acid-decomposable polycyclic alicyclic hydrocarbon structure and contributes to further improvement of dry etching resistance. In addition, although the detailed mechanism is not clear, it is inferred that the hydrogen radicals of the polycyclic alicyclic hydrocarbon structure have a high supply capacity and become a hydrogen source when the photoacid generator is decomposed. The decomposition efficiency of the photoacid generator is further improved, and the acid generation The efficiency is further increased. It is believed that this will contribute to a more excellent sensitivity.

The polymer compound (A) of the present invention may have the aforementioned specific structure system. Aromatic rings such as a benzene ring and a group of a non-acid-decomposable polycyclic alicyclic hydrocarbon structure are connected via an oxygen atom derived from a phenolic hydroxyl group. . As mentioned above, the above structure not only contributes to higher dry etching resistance, but also can increase the glass transition temperature (Tg) of the polymer compound (A). It is inferred that these combined effects can provide higher resolution.

In the present invention, the so-called non-acid decomposability refers to the property that does not cause decomposition reaction by the acid generated by the photoacid generator. More specifically, the group having a non-acid-decomposable polycyclic alicyclic hydrocarbon structure is preferably a group that is stable in acid and alkali. A group that is stable in acid and alkali refers to a group that does not show acid decomposability and alkali decomposability. Here, the acid decomposability refers to the property of causing a decomposition reaction by the action of the acid generated by the photoacid generator.

In addition, the alkali decomposability refers to the property of causing a decomposition reaction by the action of an alkaline developer. Examples of groups exhibiting alkali-decomposability include those contained in resins suitable for use in positive chemically amplified resist compositions, which are decomposed by the action of a conventionally known alkaline developer and are The group that increases the dissolution rate in the sexual developer (for example, a group with a lactone structure, etc.). 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. The total number of carbon atoms is preferably 5-40, and more preferably 7-30. 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 refers to a structure having multiple monocyclic alicyclic hydrocarbon groups or a polycyclic alicyclic hydrocarbon structure, and may also be a bridged type. As the monocyclic alicyclic hydrocarbon group, a cycloalkyl group having 3 to 8 carbon atoms is preferred. Examples include cyclopropyl, cyclopentyl, cyclohexyl, cyclobutyl, cyclooctyl, etc., which have multiple monomers The structure of the cyclic alicyclic hydrocarbon group has a plurality of these groups. The structure having a plurality of monocyclic alicyclic hydrocarbon groups preferably has 2 to 4 monocyclic alicyclic hydrocarbon groups, and particularly preferably two.

Examples of the polycyclic alicyclic hydrocarbon structure include bicyclic, tricyclic, and tetracyclic structures with 5 or more carbon atoms. Polycyclic structures with 6 to 30 carbon atoms are preferred, for example, adamantane structure , Decahydronaphthalene structure, norbornane structure, norbornene structure, cedarol structure, isobornane structure, camphene structure, dicyclopentane structure, α-pinene structure, tricyclodecane structure, tetracyclic ten Dioxane structure or androstane structure. In addition, part of the carbon atoms in the monocyclic or polycyclic cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

The preferred polycyclic alicyclic hydrocarbon structure includes an adamantane structure, a decahydronaphthalene structure, a norbornane structure, a norbornene structure, a cedarol structure, a structure having multiple cyclohexyl groups, and a structure having multiple cyclohexyl groups. The structure of cycloheptyl, the structure with multiple cyclooctyl groups, the structure with multiple cyclodecyl groups, the structure with multiple cyclododecyl groups, the tricyclodecane structure, from the viewpoint of dry etching resistance, The adamantane structure is optimal (that is, the group having the above-mentioned non-acid-decomposable polycyclic alicyclic hydrocarbon structure is a group having the non-acid-decomposable adamantane structure).

The following shows these polycyclic alicyclic hydrocarbon structures (for structures having multiple monocyclic alicyclic hydrocarbon groups, the monocyclic alicyclic hydrocarbon structures corresponding to the above-mentioned monocyclic alicyclic hydrocarbon groups (specifically, the following Formula (47) ~ (50) structure)) chemical formula.

【Chemical formula 17】

In addition, the above-mentioned polycyclic alicyclic hydrocarbon structure may have a substituent. Examples of the substituent include an alkyl group (preferably with 1 to 6 carbon atoms) and cycloalkyl (preferably with 3 to 10 carbon atoms) , Aryl (preferably with 6 to 15 carbon atoms), halogen atom, hydroxyl, alkoxy (preferably with 1 to 6 carbon atoms), carboxyl, carbonyl, thiocarbonyl, alkoxycarbonyl (with carbon atoms 2-7 is preferred), and a group formed by combining these groups (the total number of carbon atoms is preferably 1-30, and the total number of carbon atoms is more preferably 1-15).

As the above-mentioned polycyclic alicyclic hydrocarbon structure, a structure represented by any one of the above-mentioned formulas (7), (23), (40), (41), and (51), which has two structures that combine the above-mentioned formula (48) The structure in which any hydrogen atom in the structure is used as the univalent group of the bonding bond is preferred. The structure represented by any one of the above formulas (23), (40) and (51) has two The structure in which any hydrogen atom in the structure of formula (48) is used as the univalent group of the bonding bond is more preferable, and the structure represented by the above formula (40) is the most preferable. As the group having a polycyclic alicyclic hydrocarbon structure, it is preferable to use any one of the hydrogen atoms of the above-mentioned polycyclic alicyclic hydrocarbon structure as a univalent group for the bonding.

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

【Chemical formula 18】

In the formula, R ₆ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom , Ester group (-OCOR or -COOR: R is alkyl or fluorinated alkyl with 1 to 6 carbon atoms) or carboxyl group. n ₃ represents an integer of 0-6.

【Chemical formula 19】

In the formula, R ₇ represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom , Ester group (-OCOR or -COOR: R is alkyl or fluorinated alkyl with 1 to 6 carbon atoms) or carboxyl group. n ₄ represents an integer of 0-4. X ₄ is a methylidene 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 this.

【Chemical formula 20】

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

【Table 1】

【Table 2】

【table 3】

【Table 4】

The weight average molecular weight of the polymer compound (A) is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, still more preferably 3,000 to 10,000, and particularly preferably 3,000 to 7,000.

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

In order to obtain the above-mentioned polymer compound (A) with a better degree of dispersion, it is preferably produced by a method of manufacturing a polymer having a smaller degree of dispersion and a repeating unit represented by the following general formula (5) as a raw material .

【Chemical formula 21】

In the _formula, R ₁ meaning _same as in the general formula R (1) it is.

In consideration of the possibility of oligomerization caused by side reactions, the polymer dispersion degree of the raw materials used in the above manufacturing method is preferably 1.0-1.30, and more preferably 1.0-1.20. For the polymer of the raw material used in the above-mentioned production method, the dispersion degree of the obtained polymer compound becomes uniform by living polymerization such as living anionic polymerization, which is preferable.

The synthesis of the polymer compound (A) using the above-mentioned raw materials can be carried out by, for example, the method described in "Experimental Chemistry Lectures Volume 18, Reaction II of Organic Compounds (Part 2), page 94".

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

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

[2] (B) by irradiation with actinic rays or radiation to generate 130Å ³ or more and a volume of chemical amplification resist composition of 2000Å ³ acid compound of the present invention contains the following by irradiation with actinic rays or radiation and an acid generating compound or less of 2000Å ³ (B) and a volume of more than 130Å ³ (hereinafter appropriately abbreviated as the compounds such as "acid generator"). As a preferable form of the acid generator, an onium compound can be mentioned. Examples of such onium compounds include sulfonium salt, iodonium salt, and phosphonium salt, and sulfonium salt is more preferable. In addition, as another preferred form of the acid generator, a compound that generates sulfonic acid, imidic acid, or methylated acid by irradiation with actinic rays or radiation can be cited. Examples of the acid generator in its form include sulfonium salt, phosphonium salt, phosphonium salt, oxime sulfonate, and iminosulfonate.

The acid generator used in the present invention is not limited to low molecular weight compound, the volume of the acid may be used and produced of 2000Å ³ in the range of less than 130Å ^3, and the by irradiation with actinic rays or radiation to generate an acid of A compound in which a group is introduced into the main chain or side chain of a polymer compound. Also, as described above, when a group that generates an acid by irradiating actinic rays or radiation is present in the repeating unit that becomes the copolymer component of the polymer compound (A) used in the present invention, it is higher than that of the present invention. The acid generators of different molecules of the molecular compound may not be present. When the compound (B) that generates acid by irradiating actinic rays or radiation is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and more preferably 1000 or less.

The acid generator is preferably a compound that generates acid by irradiating electron beams or extreme ultraviolet rays.

In the present invention, preferred onium compounds include an alumium compound represented by the following general formula (7) or an iodo compound represented by the general formula (8).

【Chemical formula 22】

In the general formulas (7) and (8), R _a1 , R _a2 , R _a3 , R _a4 and R _a5 each independently represent an organic group. X ^- represents an organic anion. Hereinafter, the alumium compound represented by the general formula (7) and the iodonium compound represented by the general formula (8) will be described in further detail.

_Ra1 to _Ra3 of the above general formula (7) and _Ra4 and _{Ra5 of the} above general formula (8) each independently represent an organic group, preferably at least one of _Ra1 to _Ra3 and _Ra4 At least one of and R _a5 is an aryl group. As the aryl group, phenyl and naphthyl are preferred, and phenyl is more preferred. The organic anions of X ^- in the general formulas (7) and (8) include, for example, sulfonic acid anions, carboxylic acid anions, bis(alkylsulfonyl)amide anions, and tris(alkylsulfonyl) The methide anion or the like is preferably an organic anion represented by the following general formula (9), (10) or (11), and more preferably an organic anion represented by the following general formula (9).

【Chemical formula 23】

In the above 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 the acid generated by irradiating actinic rays or radiation such as electron beam or extreme ultraviolet, that is, sulfonic acid, imine acid, methylated acid, etc. Examples of the organic groups of Rc ₁ to Rc ₄ include an alkyl group, a cycloalkyl group, an aryl group, or a group obtained by connecting a plurality of these groups. Among these organic groups, an alkyl group substituted with a fluorine atom or a fluoroalkyl group at the 1-position, a cycloalkyl group substituted with a fluorine atom or a fluoroalkyl group, and a phenyl group substituted with a fluorine atom or a fluoroalkyl group are preferable. A plurality of the above-mentioned organic groups of Rc ₂ to Rc ₄ may be connected to each other to form a ring. As the group connecting the plurality of organic groups, an alkylene substituted with a fluorine atom or a fluoroalkyl group is preferred. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation increases, and the sensitivity is improved. However, it is preferable that the terminal group does not contain a fluorine atom as a substituent.

Furthermore, in the present invention, the compound (B) that produces the above acid is a compound that produces an acid (more preferably a sulfonic acid) having a volume of 130Å ³ or more. As described above, by generating an acid with a volume of 130 Å ³ or more by the compound (B), excellent results in resolution, PED stability, and LER performance can be obtained. Compound (B) is preferably a compound that generates an acid with a volume of 190 Å ³ or more (more preferably a sulfonic acid) by irradiating actinic rays or radiation, and preferably produces an acid with a volume of 270 Å ³ or more (more preferably Sulfonic acid) compounds are more preferred, and compounds that produce acids (more preferably sulfonic acids) with a volume of 400 Å ³ or more are particularly preferred. However, from the viewpoint of sensitivity, the coating solvent solubility considerations, more preferably above a volume of 2000Å ³ or less, more preferably 1500Å ³ or less. Among them, 1Å is equivalent to 0.1nm. The value of the above-mentioned volume was obtained using "WinMOPAC" manufactured by Fujitsu Limited. That is, firstly, input the chemical structure of the acid in each example. Secondly, use the structure as the initial structure and determine the most stable three-dimensional configuration of each acid by the molecular force field calculation of the MM3 method. The stable three-dimensional configuration is calculated using the molecular orbital calculation of the PM3 method, so that the "accessible volume" of each acid can be calculated. Hereinafter, in the present invention, particularly preferred acid generators are shown below. In addition, in some examples, the calculated value of the volume (unit Å ³ ) is noted. In addition, the calculated value obtained here is the volume value of the acid with protons bonded to the anion part.

【Chemical formula 24】

【Chemical formula 25】

【Chemical formula 26】

【Chemical formula 27】

【Chemical formula 28】

【Chemical formula 29】

【Chemical formula 30】

【Chemical formula 31】

An acid generator can be used individually by 1 type or in combination of 2 or more types. The content of the acid generator in the composition is based on the total solid content of the negative sensitizing radiation or radiation-sensitive resin composition, and is preferably 0.1-25% by mass, more preferably 0.5-20% by mass, and more preferably It is 1-18% by mass.

[3] (E) Basic compound The composition of the present invention preferably further contains a basic compound as an acid scavenger. By using a basic compound, it is possible to reduce the change in performance caused by time from exposure to post-heating. The basic compound is preferably an organic basic compound. More specifically, it can include aliphatic amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having carboxyl groups, and sulfonyl groups. Nitrogen-containing compounds, nitrogen-containing compounds with hydroxyl groups, nitrogen-containing compounds with hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amide derivatives, amide derivatives, etc. Amine oxide compounds (described in JP 2008-102383 A), ammonium salts (hydroxides or carboxylates are preferred. More specifically, from the viewpoint of LER, tetrahydroxide Tetraalkylammonium hydroxide represented by butylammonium is preferred.). In addition, a compound whose basicity is increased by the action of an acid can also be used as one type of basic compound. Specific examples of amines include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, tetradecylamine, and pentadecane. Amine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N,N-dimethyldodecylamine, methyldioctadecylamine , N,N-Dibutylaniline, N,N-Dihexylaniline, 2,6-Diisopropylaniline, 2,4,6-Tris(tert-butyl)aniline, Triethanolamine, N,N- Dihydroxyethylaniline, tris(methoxyethoxyethyl)amine; the compounds exemplified after the third column and 60th line of the specification of US Patent No. 6040112, 2-[2-{2-(2, 2-Dimethoxy-phenoxyethoxy)ethyl}-bis-(2-methoxyethyl)]-amine; US Patent Application Publication No. 2007/0224539A1 Paragraph [0066] Illustrated compounds (C1-1) to (C3-3), etc. Examples of compounds having a nitrogen-containing heterocyclic structure include 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, N-hydroxyethylpiperidine, sebacic acid bis(1,2,2 ,6,6-Pentamethyl-4-piperidinyl) ester, 4-dimethylaminopyridine, antipyrine, hydroxyantipyrine, 1,5-diazabicyclo[4.3 .0] Non-5-ene, 1,8-diazabicyclo[5.4.0]-undec-7-ene, tetrabutylammonium hydroxide, etc. In addition, photodegradable basic compounds can also be suitably used (initially, basic nitrogen atoms act as bases to show basicity, but they are decomposed by irradiation with actinic rays or radiation to produce basic nitrogen atoms and Zwitterionic compounds of organic acid sites, and these compounds neutralize within the molecule, thereby reducing or disappearing basicity, for example, Japanese Patent No. 3577743, Japanese Patent Application Publication No. 2001-215689, Japanese Patent Application Publication 2001-166476 A and JP 2008-102383 A onium salt), a photoalkaline generator (for example, a compound described in JP 2010-243773 A). Among these basic compounds, ammonium salts are preferred from the viewpoint of improving resolution. In the present invention, the content of the basic compound relative to the total solid content of the composition is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and particularly preferably 0.05 to 3% by mass.

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

【Chemical 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 the organic group represented by the sum R _A or R _B, for example, include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic hydrocarbon group, an alkoxycarbonyl group, a sulfo group, and a lactone lactone group and the like. These groups may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and the like. The alkyl group represented by the R _A or R _B may be a linear system, also can be tied branched. The number of carbon atoms of the alkyl group is preferably 1-50, more preferably 1-30, and still more preferably 1-20. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, and second Butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl, etc. Cycloalkyl group represented by the sum R _A or R _B may be based monocyclic, polycyclic also be based. As the cycloalkyl group, a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl, can be preferably used. The alkenyl group represented by the R _A or R _B may be a linear system, also can be tied branched. The number of carbon atoms of the alkenyl group is preferably 2-50, more preferably 2-30, and still more preferably 3-20. Examples of such alkenyl groups include vinyl, allyl, and styryl. The aryl group having 6 to 14 carbon atoms, those represented by the sum R _A or R _B is preferred. Examples of such groups include phenyl and naphthyl. Number heterocyclic hydrocarbon-based carbon atoms represented by the sum R _A or R _B 5 ~ 20 persons are preferred, 6 to 15 carbon atoms are more preferred. The heterocyclic hydrocarbon group may be aromatic or not. The heterocyclic hydrocarbon group is preferably aromatic. The heterocyclic ring contained in the above group may be monocyclic or polycyclic. Examples of such heterocyclic rings include imidazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 2H-pyrrole ring, 3H-indole ring, 1H-indazole ring, purine ring, isoquinoline Ring, 4H-quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, phenanthridine ring, acridine ring, phenanthrene Phylazine ring, phenazine ring, pyridine ring, triazine ring, benzisoquinoline ring, thiazole ring, thiadiazine ring, azepine ring, azocine ring, isothiazole ring, iso Oxazole ring and benzothiazole ring. As the lactone group represented by R _A or R _B , for example, a 5- to 7-membered ring lactone group can also be formed in the form of a bicyclic structure or a spiro ring structure on the 5- to 7-membered ring lactone group. Those with ring structure shrinkage. Sultone as the group represented by the R _A or R _B, e.g. sultone group of 5 to 7-membered ring, can also be based on the structure to form a bicyclic 5- to 7-membered ring lactone sulfo group, a spiro ring structures Those who condense other ring structures in the form. Specifically, a group having the structure shown below is preferred.

【Chemical formula 33】

【Chemical formula 34】

The lactone group and the sultone group may have or may not have a substituent (Rb ₂ ). Preferred group as a substituent (Rb _2), there may be mentioned as R _A and R _B substituents are the same substituents described. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, multiple substituents (Rb ₂ ) may be the same or different. In addition, there are multiple substituents (Rb ₂ ) that can be bonded to each other to form a ring. As the linking group represented by X, for example, linear or branched alkylene, cycloalkylene, ether bond, ester bond, amide bond, urethane bond, urea bond, and A group formed by combining two or more of these. X represents a single bond, an alkylene group, a group formed by a combination of an alkylene group and an ether bond, or a group formed by a combination of an alkylene group and an ester bond, more preferably. The number of atoms of the linking group represented by X is preferably 20 or less, and more preferably 15 or less. The linear or branched alkylene group and the cycloalkylene group preferably have 8 or less carbon atoms, and they may have a substituent. As the above-mentioned substituents, those with 8 or less carbon atoms are preferred. Examples include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkyl groups. Oxycarbonyl (2-6 carbon atoms), etc. At least two of R _A , R _B and X may be bonded to each other to form a ring. The number of carbon atoms forming the ring is preferably 4-20, and it may be a monocyclic or polycyclic type, and it may also contain an oxygen atom, a sulfur atom, a nitrogen atom, an ester bond, an amide bond or a carbonyl group in the ring. When the cation portion of the compound (E) contains a nitrogen-containing heterocyclic group, the nitrogen-containing heterocyclic group may or may not have aromaticity. In addition, the nitrogen-containing heterocyclic group may be monocyclic or polycyclic. As the nitrogen-containing heterocyclic group, a group containing a piperidine ring, a morpholine ring, a pyridine ring, an imidazole ring, a pyrazine ring, a pyrrole ring or a pyrimidine ring can be preferably mentioned. The onium salt compound (E) is preferably a compound represented by the following general formula (4).

【Chemical formula 35】

Wherein, A represents a sulfur atom or an iodine atom, R _A represents a hydrogen atom or an organic group, R _B represents a (p + 1) valent organic group, X represents a single bond or a linking group, A represents a nitrogen atom of the _N Alkaline site. When there are a plurality of R _A , R _B , X and A _N respectively, these may be the same or different. When A is a sulfur atom, q is an integer from 1 to 3, and o is an integer satisfying the relationship of o+q=3. When A is an iodine atom, q is 1 or 2, and o is an integer satisfying the relationship of o+q=2. p represents an integer from 1 to 10, and Y ^- represents an anion (the details will be described later as the anion part of the compound (E)). At least two of R _A , X, R _B , and A _N may be bonded to each other to form a ring.

As represented by R _B of the (p + 1) valent organic group, for example, a chain (linear or branched) or cyclic aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic hydrocarbon group, can be more Aromatic hydrocarbon group is preferably mentioned. When R _B is an aromatic hydrocarbon, an aromatic hydrocarbon group in the p- position (position 1,4) are bonded are preferred. The linking group represented by X has the same meaning as the linking group represented by X in the general formula (NI), and the same specific examples can be given. The basic site represented by A _N has the same meaning as the "basic site" contained in the cation portion of the compound (E), and may contain, for example, an amino group or a nitrogen-containing heterocyclic group. When the basic sites comprise amine, amine as, for example, disclosed in the above-described general formula (NI) is _{-N (R A) (R B} ) group.

As the organic group represented by the sum R _A, for example, include an alkyl group, an alkenyl group, an aliphatic cyclic group, an aromatic hydrocarbon group and heterocyclic hydrocarbon group. When o = 2, 2 th R _A may be bonded to each other to form a ring. These groups or rings may further have a substituent. R _A represents an alkyl group of a linear system can also be based branched. The number of carbon atoms of the alkyl group is preferably 1-50, more preferably 1-30, and still more preferably 1-20. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, and second Butyl, tert-butyl, 1-ethylpentyl and 2-ethylhexyl. Alkenyl group R _A may be represented by a system of linear, branched lines can also. The number of carbon atoms of the alkenyl group is preferably 2-50, more preferably 2-30, and still more preferably 3-20. Examples of such alkenyl groups include vinyl, allyl, and styryl. The R _A represents a cyclic aliphatic group such as a cycloalkyl group. The cycloalkyl group may be monocyclic or polycyclic. As the aliphatic cyclic group, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl can be preferably used. Examples of the aromatic hydrocarbon group, the number of carbon atoms represented by the R _A 6 ~ 14 were preferred. Examples of such groups include aryl groups such as phenyl and naphthyl. R _A represents an aromatic hydrocarbon group of a phenyl group is preferred. A heterocyclic hydrocarbon group represented by the sum R _A may have an aromatic, also may not have aromatic properties. The heterocyclic hydrocarbon group is preferably aromatic. The heterocyclic ring contained in the above group may be monocyclic or polycyclic. Examples of such heterocyclic rings include imidazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 2H-pyrrole ring, 3H-indole ring, 1H-indazole ring, purine ring, isoquinoline Ring, 4H-quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, phenanthridine ring, acridine ring, phenanthroline ring, Phenazine ring, piperidine ring, triazine ring, benzisoquinoline ring, thiazole ring, thiadiazine ring, aza ring, azepine ring, isothiazole ring, isoxazole ring and benzothiazole ring. R _A is an aromatic hydrocarbon group, or R _A 2 bonded to form a ring are preferred. The ring formed by at least two of R _A , X, R, and A _N that can be bonded to each other is preferably a 4- to 7-membered ring, more preferably a 5- or 6-membered ring, and particularly preferably a 5-membered ring. In addition, the ring skeleton may contain heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. When the ring when the group represented by the R _A or R _A 2 bonded to each other to form a group of the substituent further includes, as the substituent, for example, by the following. That is, as the substituent, for example, 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, and an amino group can be mentioned. , Acyloxy group, carbamoyloxy group, alkyl sulfoxy group, arylsulfoxy group, sulfoxy group, amide group, ureido group, alkoxycarbonylamino group, aryloxycarbonyl group Amino 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, alkylsulfinyl group, arylsulfonyl group, sulfonate Acid group (-SO ₃ H) and its conjugate base (called sulfonato group), alkoxysulfonyl, aryloxysulfonyl, sulfonamide, and phosphinyl ( phosphono group (-PO ₃ H ₂ ) and its conjugate base (called phosphonate group), phosphonooxy group (-OPO ₃ H ₂ ) and its conjugate base (called phosphonate (Phosphonatooxy), cyano, nitro, aryl, alkenyl, alkynyl, heterocyclic, silyl and alkyl. Among these substituents, hydroxy, alkoxy, cyano, aryl, alkenyl, alkynyl, alkyl, etc. are preferred.

In the general formula (4), p is preferably an integer of 1 to 4, preferably 1 or 2, and even more preferably 1. In one aspect, the compound (E) represented by the formula (4) represented by the formula R _B in the q least one aromatic hydrocarbon group is preferred. In addition, at least one of the p -(XA _N ) groups that are bonded to at least one of the aromatic hydrocarbon groups is a linking group in which at least one of the X system and the above-mentioned aromatic hydrocarbon group is a carbon atom. good. That is, in this aspect of the compound (E), the basic portion of the A _N represents via a carbon atom of the aromatic hydrocarbon group is directly represented by the sum R _B and bonded with the aromatic hydrocarbon.

The aromatic hydrocarbon group represented by the R _B may comprise a heterocyclic aromatic hydrocarbon group in the aromatic ring. In addition, the aromatic ring may be monocyclic or polycyclic. The number of carbon atoms of the aromatic ring group is preferably 6-14. Examples of such groups include aryl groups such as phenyl, naphthyl, and anthryl. When the aromatic ring group contains a heterocyclic ring, examples of the heterocyclic ring include a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, and benzene ring. Biimidazole ring, triazole ring, thiadiazole ring and thiazole ring. The aromatic hydrocarbon group represented by the R _B is a phenyl or naphthyl group are preferred, phenyl group is particularly preferred. The aromatic hydrocarbon group represented by a sum of addition by the R _B described below - group (XA _N) represented by the outside, it may further have a substituent. As the substituent, for example, as in the R _A substituent group can be exemplified those before.

Further, in this aspect, the above-described aromatic ring substituted with at least one of R _B - (XA _N) as a group of linking groups X are bonded with the long-based portion of the aromatic hydrocarbon group represented by the sum R _B is carbon The atom is not particularly limited. The linking group includes, for example, an alkylene group, a cycloalkylene group, an arylene group, -COO-, -CO-, or a combination thereof. The linking group may include each of these groups and selected from -O-, -S-, -OCO-, -S(=O)-, -S(=O) ₂ -, -OS(=O) _2- And a combination of at least one of the group consisting of -NR'-. Here, R'represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. The alkylene group which may be contained in the linking group represented by X may be linear or branched. The number of carbon atoms of the alkylene group is preferably 1-20, more preferably 1-10. As such an alkylene group, for example, a methylene group, an ethylene group, a propylene group, and a butylene group are mentioned. The cycloalkylene group that the linking group represented by X may contain may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkylene group is preferably 3-20, more preferably 3-10. Examples of such cycloalkylene groups include 1,4-cyclohexylene. The number of carbon atoms of the arylene group which may be included in the linking group represented by X is preferably 6-20, more preferably 6-10. Examples of such arylene groups include phenylene and naphthylene. At least one X is preferably represented by the following general formula (N-III) or (N-IV).

【Chemical formula 36】

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

【Chemical 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 of the groups represented by R ₂ and R _3, and those of the substituent may further be provided with, for example, may include before and R _A are the same as those explained. R ₂ and R ₃ can be bonded to form a ring, and the ring, and R ₂ can be formed of at least one of R ₃ and E are bonded from 4 to 7-membered ring is preferred, 5-membered ring or 6-membered ring Better. Preferably, R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group. The linking group represented by E includes, for example, alkylene, cycloalkylene, arylene, -COO-, -CO-, -O-, -S-, -OCO-, -S(=O)-, -S(=O) ₂ -, -OS(=O) ₂ -, -NR- or a combination of these. Here, R represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. The linking group represented by E is selected from alkylene bond, ester bond, ether bond, thioether bond, urethane bond,

【Chemical formula 38】

Urea bond,

【Chemical formula 39】

At least one of the group consisting of an amide bond and a sulfonamide bond is preferable. More preferably, the linking group represented by E is 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 nitrogen atoms. At least one compound having the general formula (NI) e.g., compound (E) may be based of the general formula R _A (4) represented in the structures of. In one aspect, the compound (E) represented by the general formula (4) is represented by the following general formula (NV).

【Chemical formula 40】

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

【Chemical formula 41】

In the general formula (N-VI), A represents a sulfur atom or an iodine atom. R ₁₁ each independently represents an alkyl group, an alkenyl group, an aliphatic cyclic group, an aromatic hydrocarbon group, or a heterocyclic hydrocarbon group. When m=2, two R ₁₁ can be bonded to each other to form a ring. Ar each independently represents an aromatic hydrocarbon group. X ₁ each independently represents a divalent linking group. R ₁₂ each independently represents a hydrogen atom or an organic group. When the above A is a sulfur atom, m is an integer of 1 to 3, and n is an integer satisfying the relationship of m+n=3. When the above A is an iodine atom, m is an integer of 1 or 2, and n is an integer satisfying the relationship of m+n=2. Y ^- represents an anion (the details will be described later as the anion part of the compound (E)). The specific examples and preferred examples of the alkyl group, alkenyl group, aliphatic cyclic group, aromatic hydrocarbon group, and heterocyclic hydrocarbon group of R _{11 are} the same as those of the alkyl group and alkene group of R _A in the general formula (4). The specific examples and preferred examples of the group, aliphatic cyclic group, aromatic hydrocarbon group, and heterocyclic hydrocarbon group are the same. Specific examples of the same, and preferred examples of the aromatic hydrocarbon group Ar in the general formula (4) R _B in the aromatic hydrocarbon group as the specific examples and preferred examples. The specific examples and preferred examples of the divalent linking group as X _{1 are} the same as the specific examples and preferred examples of the linking group as X in the general formula (4). Specific examples and preferred examples of the organic groups R ₁₂ of the specific examples and preferred examples of the above general formula (NI) in the organic group R _A and R _B of the same. From the viewpoint of the temperature dependence of PEB after exposure and the stability of the line width after exposure (PED), X is an alkylene group (for example, a methylene group) and two R ₁₂ are bonded to each other to form a ring It is especially good. The anion part of the compound (E) is not particularly limited. The anion contained in the compound (E) is preferably a non-nucleophilic anion. Here, a non-nucleophilic anion refers to an anion that has a very low ability to cause a nucleophilic reaction, and is an anion that can inhibit decomposition over time caused by an intramolecular nucleophilic reaction. Thereby, the temporal stability of the composition of the present invention is improved. Examples of non-nucleophilic anions include sulfonic acid anions, carboxylic acid anions, sulfoximine anions, bis(alkylsulfonyl)imide anions, tri(alkylsulfonyl)methyl anions, etc. . Examples of sulfonic acid anions include aliphatic sulfonic acid anions, aromatic sulfonic acid anions, and camphor sulfonic acid anions. Examples of carboxylic acid anions include aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions. The aliphatic part in the aliphatic sulfonic acid anion may be an alkyl group or a cycloalkyl group. An alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms are preferred, for example, Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecane Alkyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopropyl , Cyclopentyl, cyclohexyl, adamantyl, norbornyl, camphenyl, etc. As the aromatic group in the aromatic sulfonic acid anion, an aryl group having 6 to 14 carbon atoms is preferred, and examples thereof include phenyl, tolyl, and naphthyl. The alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonic acid anion and the aromatic sulfonic acid anion may have a substituent. Examples of substituents of alkyl, cycloalkyl and aryl groups in aliphatic sulfonic acid anions and aromatic sulfonic acid anions include nitro groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), Carboxy, hydroxy, amino, cyano, alkoxy (preferably with 1 to 15 carbon atoms), cycloalkyl (preferably with 3 to 15 carbon atoms), aryl (with 6 to 14 carbon atoms) Preferred), alkoxycarbonyl group (2-7 carbon atoms is preferred), acyl group (2-12 carbon atoms is preferred), alkoxycarbonyloxy (carbon 2-7 is preferred) ), Alkylthio (C 1-15 is preferred), Alkylsulfonyl (C 1-15 is preferred), Alkyliminosulfonyl (C 2-15 is Preferred), aryloxysulfonyl (6-20 carbon atoms is preferred), alkylaryloxysulfonyl (7-20 carbon atoms is preferred), cycloalkylaryloxysulfonyl Group (10-20 carbon atoms is preferred), alkoxyalkoxy (5-20 carbon atoms is preferred), cycloalkylalkoxyalkoxy (8-20 carbon atoms is preferred) )Wait. Regarding the aryl group and ring structure possessed by each group, examples of the substituent include an alkyl group (preferably having 1 to 15 carbon atoms). Examples of the aliphatic part in the aliphatic carboxylic acid anion include the same alkyl groups and cycloalkyl groups as those in the aliphatic sulfonic acid anion. Examples of the aromatic group in the aromatic carboxylic acid anion include the same aryl groups as those in the aromatic sulfonic acid anion. As the aralkyl group in the aralkylcarboxylic acid anion, an aralkyl group having 6 to 12 carbon atoms is preferred. Examples include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl. . 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 the substituents of the alkyl, cycloalkyl, aryl and aralkyl groups in the aliphatic carboxylic acid anion, aromatic carboxylic acid anion and aralkyl carboxylic acid anion, for example, those with aromatic sulfonic acid anion The same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group, etc. As the sulfoximine anion, for example, a saccharin anion can be given. The alkyl group in the bis(alkylsulfonyl)imide anion and the tri(alkylsulfonyl)methyl anion is preferably an alkyl group with 1 to 5 carbon atoms. For example, methyl, ethyl Group, propyl, isopropyl, n-butyl, isobutyl, second butyl, pentyl, neopentyl, etc. Examples of substituents of these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxy groups. An alkyl group substituted with a fluorine atom is preferred, such as a sulfonyl group. In addition, it is also preferable that the two alkyl groups in the bis(alkylsulfonyl)imide anion are bonded to each other to form a cyclic structure. At this time, it is preferable that the formed cyclic structure is a 5- to 7-membered ring. Examples of other non-nucleophilic anions include phosphorous fluoride, boron fluoride, and antimony fluoride. As a non-nucleophilic anion, it is an aliphatic sulfonic acid anion substituted by a fluorine atom in the α position of a sulfonic acid, an aromatic sulfonic acid anion substituted by a fluorine atom or a group having a fluorine atom, and a double The (alkylsulfonyl) iminium anion and the tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom are preferred. As non-nucleophilic anions, perfluoroaliphatic sulfonic acid anions with 4 to 8 carbon atoms, benzenesulfonic acid anions with fluorine atoms are more preferable, nonafluorobutanesulfonic acid anions, perfluorooctanesulfonic acid anions, pentafluoro Benzenesulfonic acid anion and 3,5-bis(trifluoromethyl)benzenesulfonic acid anion are more preferable. In addition, the non-nucleophilic anion is preferably represented by the following general formula (LD1), for example.

【Chemical formula 42】

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. L each independently represents a divalent linking group. Cy represents a cyclic organic group. x represents an integer of 1-20. y represents an integer of 0-10. z represents an integer of 0-10. Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of the alkyl group is preferably 1-10, more preferably 1-4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Xf is a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ or CH ₂ CH ₂ C ₄ F ₉ is preferred. R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group may have a substituent (a fluorine atom is preferred), and one having 1 to 4 carbon atoms is preferred. A perfluoroalkyl group having 1 to 4 carbon atoms is more preferable. As specific examples of the substituted alkyl group of R 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 , of which CF ₃ is preferred. L represents a divalent linking group. As the divalent linking group, for example, -COO-, -OCO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, alkylene Cycloalkyl and alkenylene. Among them, -CONH-, -CO- or -SO ₂ -is preferable, and -CONH- or -SO ₂ -is more preferable. Cy represents a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, from the viewpoint of suppressing the diffusibility of the film in the PEB (heating after exposure) step and improving the MEEF (Mask Error Enhancement Factor), norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclodecyl Alicyclic groups having a bulky structure with 7 or more carbon atoms, such as alkyl groups and adamantyl groups, are preferred. The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthryl, and anthracenyl. Among them, naphthyl having a relatively low absorbance at 193 nm is preferred. The heterocyclic group can be monocyclic or polycyclic. The polycyclic group can better inhibit the diffusion of acid. In addition, the heterocyclic group may be aromatic or not. Examples of heterocyclic rings having aromaticity include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferred. Further, as an example of a lactone ring include the above general formula (N-1) in respect of R _A and R _B illustrates the lactone ring. The aforementioned cyclic organic group may have a substituent. Examples of the substituent include alkyl groups, cycloalkyl groups, aryl groups, hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, and sulfonamide groups. And sulfonate group. The alkyl group may be linear or branched. In addition, the alkyl group preferably has 1-12 carbon atoms. The cycloalkyl group may be monocyclic or polycyclic. In addition, the number of carbon atoms of the cycloalkyl group is preferably 3-12. The number of carbon atoms of the aryl group is preferably 6-14. x is preferably from 1 to 8, wherein 1 to 4 are preferred, and 1 is particularly preferred. It is preferable that y is 0-4, and 0 is more preferable. It is preferable that z is 0-8, and among them, 0-4 is preferable. In addition, the non-nucleophilic anion is preferably represented by the following general formula (LD2), for example.

【Chemical formula 43】

In the general formula (LD2), Xf, R ₁ , R ₂ , L, Cy, x, y and z have the same meaning as in the general formula (LD1). Rf is a group containing a fluorine atom. Examples of the fluorine atom-containing group 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 containing 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 containing a fluorine atom include, for example, an alkyl group substituted with at least one fluorine atom. In addition, these alkyl groups, cycloalkyl groups, and aryl groups may be further substituted with substituents not containing a fluorine atom. Examples of the substituent include those that do not contain a fluorine atom among those described above regarding Cy. As the alkyl group having at least one fluorine atom represented by Rf, for example, the same as those described above as the alkyl group represented by Xf substituted with at least one fluorine atom can be mentioned. Examples of the cycloalkyl group having at least one fluorine atom represented by Rf include perfluorocyclopentyl and perfluorocyclohexyl. Examples of the aryl group having at least one fluorine atom represented by Rf include perfluorophenyl. As a preferable aspect of the anion part of the compound (E), in addition to the structures represented by the above general formulas (LD1) and (LD2), a preferable anion structure as a photoacid generator can be exemplified. The structure. In addition, in compound (E), the fluorine content represented by (the total mass of all fluorine atoms contained in the compound)/(the total mass of all atoms contained in the compound) is preferably 0.30 or less, and 0.25 or less is More preferably, 0.20 or less is more preferable, 0.15 or less is particularly preferable, and 0.10 or less is most preferable. Below, although the specific example of compound (E) is given, it is not limited to this.

【Chemical formula 44】

【Chemical formula 45】

【Chemical formula 46】

【Chemical formula 47】

【Chemical formula 48】

【Chemical formula 49】

【Chemical formula 50】

【Chemical formula 51】

【Chemical formula 52】

【Chemical formula 53】

Compound (E) may be used alone or in combination of two or more kinds. The content of the compound (E) is based on the total solid content of the composition, and is usually in the range of 0.001 to 10% by mass, preferably 0.1 to 10% by mass, and more preferably 1 to 10% by mass. In addition, from the viewpoint of improving resolution, it is preferable that the volume of the acid generated from the compound (E) be large.

[4] A compound having an acid crosslinkable group different from (C) the polymer compound (A) The composition of the present invention may contain a compound having an acid crosslinkable group different from the above polymer compound (A) (C) (hereinafter, also referred to as "compound (C)" or "acid crosslinking agent (C)"). As the compound (C), a compound containing two or more hydroxymethyl groups or alkoxymethyl groups in the molecule is preferable. In addition, from the viewpoint of improving LER, it is preferable that the compound (C) contains a hydroxymethyl group.

First, the case where the compound (C) is a low-molecular compound (hereinafter also referred to as "compound (C')") will be described. As the compound (C'), preferably hydroxymethylated or alkoxymethylated phenol compounds, alkoxymethylated melamine compounds, alkoxymethyl glycoluril compounds, and alkoxy groups Methylated urea compounds. Particularly preferred compounds (C') include phenol derivatives and alkanes having 3 to 5 benzene rings in the molecule and further having a total of 2 or more hydroxymethyl or alkoxymethyl groups, and a molecular weight of 1200 or less. Oxymethyl glycoluril derivatives. As the alkoxymethyl group, methoxymethyl and ethoxymethyl are preferred.

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

As examples of other preferable compounds (C'), alkoxymethylated melamine-based compounds, alkoxymethylglycerol-based compounds, and alkoxymethylated urea-based compounds can be further cited N-hydroxymethyl or N-alkoxymethyl compound.

Examples of such compounds include hexamethoxymethyl melamine, hexaethoxy methyl melamine, tetramethoxymethyl glycoluril, 1,3-bismethoxymethyl-4,5-dimethoxy Ethylene urea, bismethoxymethyl urea, etc. are disclosed in EP 0,133,216A, West German Patent No. 3,634,671, West German Patent No. 3,711,264, EP 0,212,482A. Hereinafter, among the specific examples of the compound (C'), particularly preferred ones are given.

【Chemical formula 54】

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

【Chemical formula 55】

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

In one aspect of the present invention, R ₁ and R _{6 are} preferably a hydrocarbon group having 5 or less carbon atoms, more preferably a hydrocarbon group having 4 or less carbon atoms, particularly preferably methyl, ethyl, propyl, iso Propyl.

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

Examples of the organic groups having 2 or more carbon atoms represented by R ₃ and R ₄ include alkyl groups having 2 or more carbon atoms, cycloalkyl groups, aryl groups, etc., and R ₃ and R ₄ are bonded to each other It is preferable to form the ring detailed below.

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

These rings may have substituents. Examples of such substituents include alkyl groups, cycloalkyl groups, alkoxy groups, carboxy groups, aryl groups, alkoxymethyl groups, acyl groups, alkoxycarbonyl groups, and nitro groups. , Halogen atom or hydroxyl group, etc.

Hereinafter, specific examples of the ring formed by bonding R ₃ and R _{4 to} each other are given. The * in the formula represents the connection site with the phenol core.

【Chemical formula 56】

In one aspect of the present invention, it is preferable that R ₃ and R ₄ in the general formula (I) are bonded to form a polycyclic condensed ring including a benzene ring, and it is more preferable to form a chlorophyll structure. In the compound (C′), for example, R ₃ and R ₄ in the general formula (I) are bonded to form a chrysene structure represented by the following general formula (Ia).

【Chemical formula 57】

In the formula, R ₇ and R ₈ each independently represent a substituent. Examples of substituents include alkyl groups, cycloalkyl groups, alkoxy groups, aryl groups, alkoxymethyl groups, acyl groups, alkoxycarbonyl groups, nitro groups, halogen atoms, and hydroxyl groups. n1 and n2 each independently represent an integer of 0-4, and 0 or 1 is preferred. * Indicates the connection site with the phenol core.

Moreover, in one aspect of the present invention, the compound (C') is preferably represented by the following general formula (Ib). 【Chemical 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 group of atoms required to form a ring together with the carbon atoms in the formula. The ring formed by Z together with the carbon atom in the formula is the same as the ring formed by bonding R ₃ and R _{4 to} each other in the description of the general formula (I).

In one aspect of the present invention, the compound (C') is preferably a compound having 4 or more aromatic rings in the molecule and 2 alkoxymethyl groups and/or hydroxymethyl groups in total.

Next, a method for producing the compound (C') represented by the general formula (I) will be described. The bisphenol compound that becomes the parent nucleus of the compound (C') represented by the general formula (I) is usually performed by dehydration condensation reaction of corresponding two molecules of phenol compound and corresponding one molecule of ketone in the presence of an acid catalyst To synthesize.

By treating the obtained bisphenol body with paraformaldehyde and dimethylamine to perform amine methylation, an intermediate represented by the following general formula (I-c) is obtained. Then, after acetylation, deacetylation, and alkylation, the target acid crosslinking agent is obtained.

【Chemical formula 59】

In the formula, R ₁ , R ₃ , R ₄ and R ₆ have the same meaning as each group in the general formula (I).

Compared with the conventional synthesis method via hydroxymethyl under alkaline conditions (for example, Japanese Patent Application Laid-Open No. 2008-273844), this synthesis method is difficult to generate oligomers, and therefore has a particle formation inhibitory effect. Below, specific examples of the compound (C') represented by the general formula (I) are shown.

【Chemical formula 60】

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

The compound (C) containing an acid crosslinkable group may be a resin containing a repeating unit having an acid crosslinkable group that is different from the repeating unit represented by the general formula (1) in the polymer compound (A) ( Compound (C”)).

The negative-type sensitizing radiation or radiation-sensitive resin composition of the present invention may contain compound (C) or no compound (C). When it contains compound (C), the content of compound (C) is lower than that of negative-type photosensitive The total solid content of the radiation-sensitive or radiation-sensitive resin composition is preferably 0.5 to 30% by mass, and more preferably 1 to 15% by mass.

[5] (D) Hydrophobic resin The negative sensitizing radiation or radiation sensitive resin composition of the present invention is particularly suitable for liquid immersion exposure, and may also contain a hydrophobic resin (hereinafter, also referred to as "hydrophobic resin" D)" or simply as "resin (D)"). In addition, it is preferable that the hydrophobic resin (D) is different from the above-mentioned polymer compound (A). As a result, the hydrophobic resin (D) is biased toward the surface of the film. When the liquid immersion medium is water, the static/dynamic contact angle of the resist film surface to water can be increased, and the followability of the liquid immersion liquid can be improved. The hydrophobic resin (D) is preferably designed to be biased toward the interface as described above. Unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and it may not help to mix polar/non-polar substances uniformly.

From the viewpoint of being biased toward the surface layer of the film, it is preferable that the hydrophobic resin (D) has at least one of "fluorine atom", "silicon atom" and "CH ₃ partial structure contained in the side chain part of the resin". Two or more types are more preferable.

When the hydrophobic resin (D) contains fluorine atoms and/or silicon atoms, the above-mentioned fluorine atoms and/or silicon atoms in the hydrophobic resin (D) may be contained in the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin (D) contains fluorine atoms, as a partial structure with fluorine atoms, resins with the following groups are preferred: alkyl groups with fluorine atoms, cycloalkyl groups with fluorine atoms, or aryl groups with fluorine atoms . Alkyl groups having fluorine atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms), linear or branched alkyl groups with at least one hydrogen atom substituted by fluorine atoms, and fluorine Substituents other than atoms. The cycloalkyl group having a fluorine atom, a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom, may have a substituent other than a fluorine atom. As the aryl group having a fluorine atom, at least one hydrogen atom of an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and it may have a substituent other than a fluorine atom.

As an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, and an aryl group having a fluorine atom, the groups represented by the following general formulas (F2) to (F4) are preferably mentioned. The invention is not limited to this.

【Chemical formula 61】

In the general formulas (F2) to (F4), R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (straight chain or branch). Wherein, 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 a fluorine atom or an alkane in which at least one hydrogen atom is substituted with a fluorine atom Group (preferably with 1 to 4 carbon atoms). R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably alkyl groups in which at least one hydrogen atom is replaced by a fluorine atom (preferably with 1 to 4 carbon atoms), and perfluoroalkyl groups with 1 to 4 carbon atoms are more preferred good. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

As specific examples of the group represented by the general formula (F2), for example, p-fluorophenyl, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, and the like can be given. Specific examples of the group represented by the general formula (F3) include trifluoromethyl, pentafluoropropyl, pentafluoroethyl, heptafluorobutyl, hexafluoroisopropyl, and heptafluoroisopropyl , Hexafluoro(2-methyl)isopropyl, nonafluorobutyl, octafluoroisobutyl, nonafluorohexyl, nonafluoro-tertiary butyl, perfluoroisopentyl, perfluorooctyl, perfluoro( Trimethyl)hexyl, 2,2,3,3-tetrafluorocyclobutyl, perfluorocyclohexyl, etc. Hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro(2-methyl)isopropyl, octafluoroisobutyl, nonafluoro-tertiary butyl, perfluoroisopentyl are preferred, hexafluoroisopropyl Propyl and heptafluoroisopropyl are further preferred. As 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, etc., -C(CF ₃ ) ₂ OH is preferred.

Part of the structure containing fluorine atoms can be directly bonded to the main chain, and furthermore, can also be selected from alkylene, phenylene, ether bond, thioether bond, carbonyl group, ester bond, amide bond, carbamic acid A group in the group consisting of an ester bond and a ureide bond, or a group formed by combining two or more of these groups, is bonded to the main chain.

Below, specific examples of the repeating unit having a fluorine atom are shown, but the present invention is not limited to this. In a specific example, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ . X ₂ represents -F or -CF ₃ .

【Chemical formula 62】

【Chemical formula 63】

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

【Chemical formula 64】

In the general formulas (CS-1) to (CS-3), R ₁₂ to R ₂₆ each independently represent a linear alkyl group or a branched alkyl group (preferably with 1 to 20 carbon atoms) or a cycloalkyl group (preferably The number of carbon atoms is 3-20). L ₃ to L ₅ represent a single bond or a divalent linking group. The divalent linking group may be selected from the group consisting of alkylene, phenylene, ether bond, thioether bond, carbonyl group, ester bond, amide bond, urethane bond, and urea bond A single or a combination of two or more (preferably 12 or less total carbon atoms). n represents an integer of 1-5. n is preferably an integer of 2-4.

Hereinafter, specific examples of repeating units having groups represented by general formulas (CS-1) to (CS-3) are given, but the present invention is not limited to these. In addition, in the specific example, X ₁ represents a hydrogen atom, -CH ₃ , -F, or -CF ₃ .

【Chemical formula 65】

In addition, as described above, it is also preferable that the hydrophobic resin (D) includes a CH ₃ partial structure in the side chain portion. Here, the CH ₃ partial structure of the side chain part of the resin (D) (hereinafter also referred to as the "side chain CH ₃ partial structure") includes the CH ₃ partial structure of ethyl, propyl, etc. . On the other hand, the methyl group directly bonded to the main chain of the resin (D) (for example, the α-methyl group having the repeating unit of the methacrylic acid structure) is biased on the surface of the resin (D) due to the influence of the main chain The help of chemistry is small, so it is not included in the CH ₃ partial structure.

More specifically, when the resin (D) includes a repeating unit represented by the following general formula (M) and the like, a repeating unit derived from a monomer having a polymerizable site including a carbon-carbon double bond, that is, R _{When 11} to R ₁₄ are CH ₃ "itself", this CH ₃ is not included in the CH ₃ partial structure. ₃ corresponds to the partial structure of the present invention a partial structure CH ₃ other hand, since the presence of the main chain CC via some atoms CH. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed to have "1" CH ₃ partial structure.

【Chemical formula 66】

In the general formula (M), R ₁₁ to R ₁₄ each independently represent a side chain portion. Examples of R ₁₁ to R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group. Regarding the monovalent organic groups of R ₁₁ to R ₁₄ , alkyl, cycloalkyl, aryl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkane An aminocarbonyl group, an arylaminocarbonyl group, etc., these groups may have a substituent.

The hydrophobic resin (D) is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion. As this repeating unit, it has a repeating unit represented by the following general formula (II), and At least one type of repeating unit (x) among the repeating units represented by the general formula (III) is more preferred.

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

【Chemical formula 67】

In the above general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₂ represents an acid-stable organic group having at least one CH ₃ partial structure. Here, the acid-stable organic group is a non-acid-decomposable organic group. The so-called non-acid-decomposable organic group means that it will not be generated by the photoacid generator as explained in the section of the polymer compound (A). The property of acid causing decomposition reaction.

The alkyl group of X _b1 preferably has 1 to 4 carbon atoms, and examples include methyl, ethyl, propyl, hydroxymethyl, or trifluoromethyl, and methyl is preferred. X _{b1 is} preferably a hydrogen atom or a methyl group.

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

₃ partial structure of the alkyl group having one or more of the CH ₂ R is preferably branched alkyl group having a carbon number of 3 to 20. Specifically, preferred alkyl groups include isopropyl, isobutyl, 3-pentyl, 2-methyl-3-butyl, 3-hexyl, 2-methyl-3-pentyl , 3-methyl-4-hexyl, 3,5-dimethyl-4-pentyl, isooctyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-di Methylheptyl, 1,5-dimethyl-3-heptyl, 2,3,5,7-tetramethyl-4-heptyl, etc. More preferably, isobutyl, tertiary butyl, 2-methyl-3-butyl, 2-methyl-3-pentyl, 3-methyl-4-hexyl, 3,5-dimethyl- 4-pentyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-dimethylheptyl, 1,5-dimethyl-3-heptyl, 2,3, 5,7-Tetramethyl-4-heptyl.

R ₃ cycloalkyl group having partial structure of one or more CH ₂ may be a monocyclic, may also be polycyclic. Specifically, groups having a monocyclic, bicyclic, tricyclic, tetracyclic structure and the like having 5 or more carbon atoms are mentioned. The number of carbon atoms is preferably 6 to 30, and particularly preferably 7 to 25 carbon atoms. Examples of preferred cycloalkyl groups include adamantyl, noradamantyl, decahydronaphthalene residues, tricyclodecyl, tetracyclododecyl, norbornyl, cedrol, cyclo Pentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl. More preferable examples include adamantyl, norbornyl, cyclohexyl, cyclopentyl, tetracyclododecyl, and tricyclodecyl. More preferably, norbornyl, cyclopentyl, and cyclohexyl. The alkenyl group having one or more CH ₃ partial structures in R ₂ is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, and more preferably a branched alkenyl group. As aryl group R ₂ is preferably a partial structure of ₃ carbon atoms, an aryl group having one or more CH 6 ~ 20, and may include, for example, a phenyl group, a naphthyl group, preferably a phenyl group. The aralkyl group having one or more CH ₃ partial structures in R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, and naphthylmethyl.

Specifically, examples of the hydrocarbon group having two or more CH ₃ partial structures in R ₂ include isopropyl, isobutyl, tertiary butyl, 3-pentyl, 2-methyl-3-butyl Base, 3-hexyl, 2,3-dimethyl-2-butyl, 2-methyl-3-pentyl, 3-methyl-4-hexyl, 3,5-dimethyl-4-pentyl , Isooctyl, 2,4,4-Trimethylpentyl, 2-Ethylhexyl, 2,6-Dimethylheptyl, 1,5-Dimethyl-3-heptyl, 2,3, 5,7-tetramethyl-4-heptyl, 3,5-dimethylcyclohexyl, 4-isopropylcyclohexyl, 4-tert-butylcyclohexyl, isobornyl, etc. More preferably, isobutyl, tertiary butyl, 2-methyl-3-butyl, 2,3-dimethyl-2-butyl, 2-methyl-3-pentyl, 3-methyl -4-hexyl, 3,5-dimethyl-4-pentyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-dimethylheptyl, 1,5- Dimethyl-3-heptyl, 2,3,5,7-tetramethyl-4-heptyl, 3,5-dimethylcyclohexyl, 3,5-di-tert-butylcyclohexyl, 4- Isopropylcyclohexyl, 4-tertiary butylcyclohexyl, isobornyl.

Preferable specific examples of the repeating unit represented by the general formula (II) are listed below. In addition, the present invention is not limited to this.

【Chemical formula 68】

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

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

【Chemical formula 69】

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

The alkyl group of X _b2 is preferably one having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, hydroxymethyl or trifluoromethyl, and preferably a hydrogen atom. X _{b2 is} preferably a hydrogen atom.

R ₃ is an organic group that is stable to acid, so more specifically, it is preferably an organic group that does not have a "group that decomposes by the action of an acid to generate a polar group" described in the aforementioned resin (A) group.

Examples of R ₃ include alkyl groups having one or more CH ₃ partial structures. The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has one or more and 10 or less CH ₃ partial structures, and more preferably one or more and 8 or less, It is more preferable to have 1 or more and 4 or less.

₃ alkyl group of R ₃ in the partial structure having one or more CH, preferably carbon atoms, branched alkyl having 3 to 20. Specifically, preferred alkyl groups include isopropyl, isobutyl, 3-pentyl, 2-methyl-3-butyl, 3-hexyl, 2-methyl-3-pentyl , 3-methyl-4-hexyl, 3,5-dimethyl-4-pentyl, isooctyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-di Methylheptyl, 1,5-dimethyl-3-heptyl, 2,3,5,7-tetramethyl-4-heptyl, etc. More preferably isobutyl, tertiary butyl, 2-methyl-3-butyl, 2-methyl-3-pentyl, 3-methyl-4-hexyl, 3,5-dimethyl-4 -Pentyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-dimethylheptyl, 1,5-dimethyl-3-heptyl, 2,3,5 ,7-Tetramethyl-4-heptyl.

Specifically, examples of the alkyl group having two or more CH ₃ partial structures in R ₃ include isopropyl, isobutyl, tertiary butyl, 3-pentyl, and 2,3-dimethyl Butyl, 2-methyl-3-butyl, 3-hexyl, 2-methyl-3-pentyl, 3-methyl-4-hexyl, 3,5-dimethyl-4-pentyl, iso Octyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-dimethylheptyl, 1,5-dimethyl-3-heptyl, 2,3,5, 7-Tetramethyl-4-heptyl and the like. More preferably, the number of carbon atoms is more preferably 5-20, which are isopropyl, tertiary butyl, 2-methyl-3-butyl, 2-methyl-3-pentyl, 3-methyl-4 -Hexyl, 3,5-dimethyl-4-pentyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-dimethylheptyl, 1,5-dimethyl 3-heptyl, 2,3,5,7-tetramethyl-4-heptyl, 2,6-dimethylheptyl.

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

Hereinafter, preferred specific examples of the repeating unit represented by the general formula (III) are listed. In addition, the present invention is not limited to this.

【Chemical formula 70】

The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, it is preferred that it does not have a group that is decomposed by an acid to generate a polar group The repeating unit.

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

The resin (D) contains 90 mol% or more of the repeating unit represented by the general formula (II) and at least 1 of the repeating unit represented by the general formula (III) relative to all the repeating units of the resin (D) Kind of repeating unit (x), the surface free energy of resin (D) increases. As a result, the resin (D) is unlikely to be localized on the surface of the resist film, and the static/dynamic contact angle of the resist film with respect to water can be reliably increased, and the liquid immersion followability can be improved.

In addition, when the hydrophobic resin (D) is (i) containing fluorine atoms and/or silicon atoms, and (ii) when the side chain portion contains a CH ₃ partial structure, it can have at least one selected from Groups in the group of (x) to (z) below. (X) acid group, (y) group with lactone structure, acid anhydride group or acid imine group, (z) group decomposed by the action of acid

Examples of acid groups (x) include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, and (alkylsulfonyl groups) (alkylcarbonyl groups). Methylene, (alkylsulfonyl)(alkylcarbonyl)imino, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imino, bis(alkylsulfonyl) Methylene, bis(alkylsulfonyl)imino, tri(alkylcarbonyl)methylene, tri(alkylsulfonyl)methylene, etc. As a preferable acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonylimide group, and a bis(alkylcarbonyl)methylene group can be mentioned.

Examples of the repeating unit having an acid group (x) include repeating units derived from acrylic acid and methacrylic acid, which are directly bonded to the main chain of the resin with an acid group, or are bonded to the resin via a linking group. A repeating unit or the like having an acid group bonded to the main chain; furthermore, a polymerization initiator or chain transfer agent having an acid group may be used during polymerization to be introduced to the end of the polymer chain, and either case is preferable. The repeating unit having an acid group (x) may have at least any one of a fluorine atom and a silicon atom. The content of the repeating unit having an acid group (x) relative to all repeating units in the hydrophobic resin (D) is preferably 1-50 mol%, more preferably 3-35 mol%, and still more preferably 5 ~20 mol%.

Although the specific example of the repeating unit which has an acid group (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.

【Chemical formula 71】

【Chemical formula 72】

As "a group having a lactone structure, an acid anhydride group or an acid imine group (y)", a group having a lactone structure is particularly preferred. The repeating unit containing these groups is, for example, a repeating unit derived from an acrylate and a methacrylate and the like, which is directly bonded to the main chain of the resin. Alternatively, the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced to the end of the resin using a polymerization initiator or a chain transfer agent having the group during polymerization.

As the repeating unit containing a group having a lactone structure, for example, the same repeating unit as the repeating unit having a lactone structure described in the section of the acid-decomposable resin (A) can be cited.

Based on all the repeating units in the hydrophobic resin (D), the content of the repeating unit containing "a group having a lactone structure, an acid anhydride group, or an acid imine group (y)" is preferably 1-100 moles Ear% is more preferably 3 to 98 mol%, still more preferably 5 to 95 mol%.

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

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

【Chemical formula 73】

In the general formula (III), R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a -CH ₂ -O-Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _{c31 is} preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom and 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 by groups including fluorine atoms and silicon atoms. L _c3 represents a single bond or a divalent linking group.

The alkyl group of R _c32 in the general formula (III) 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 and a naphthyl group, and these groups may have a substituent. R _{c32 is} preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom. The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenylene group, and an ester bond (a group represented by -COO-). Based on all the repeating units in the hydrophobic resin, the content of the repeating unit represented by the general formula (III) is preferably 1-100 mol%, more preferably 10-90 mol%, and still more preferably 30 ~70 mol%.

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

【Chemical 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' represents a group of atoms containing 2 carbon atoms (CC) that are bonded to form an alicyclic structure. Based on all the repeating units in the hydrophobic resin, the content of the repeating unit represented by the general formula (CII-AB) is preferably 1-100 mol%, more preferably 10-90 mol%, and more preferably It is 30 to 70 mole%.

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

【Chemical formula 75】

When the hydrophobic resin (D) has fluorine atoms, the content of the fluorine atoms is preferably 5 to 80% by mass, more preferably 10 to 80% by mass relative to the weight average molecular weight of the hydrophobic resin (D). In addition, among all the repeating units contained in the hydrophobic resin (D), the repeating unit containing a fluorine atom is preferably 10-100 mol%, more preferably 30-100 mol%. In the case where the hydrophobic resin (D) has silicon atoms, the content of the silicon atoms is preferably 2-50% by mass, more preferably 2-30% by mass relative to the weight average molecular weight of the hydrophobic resin (D). In addition, among all the repeating units contained in the hydrophobic resin (D), the repeating unit containing silicon atoms is preferably 10-100 mol%, more preferably 20-100 mol%.

On the other hand, especially in the case where the resin (D) contains a CH ₃ partial structure in the side chain portion, the resin (D) is also preferably in a form that does not substantially contain fluorine atoms and silicon atoms. In this case, specifically, Relative to all the repeating units in the resin (D), the content of the repeating units having fluorine atoms or silicon atoms is preferably 5 mol% or less, more preferably 3 mol% or less, and still more preferably 1 mol% or less , Ideally 0 mol%, that is, it does not contain fluorine atoms and silicon atoms. In addition, the resin (D) preferably contains substantially only a repeating unit composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms. More specifically, among all the repeating units of the resin (D), the repeating unit composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms is preferably 95 mol% or more. It is more preferably 97 mol% or more, still more preferably 99 mol% or more, and ideally 100 mol%.

The weight average molecular weight in terms of standard polystyrene of the hydrophobic resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. In addition, one type of hydrophobic resin (D) may be used, or multiple types may be used in combination. The content of the hydrophobic resin (D) in the composition is preferably 0.01-10% by mass, more preferably 0.05-8% by mass, and still more preferably 0.1-7% relative to the total solid content in the composition of the present invention. quality%.

Of course, the hydrophobic resin (D) has less impurities such as metals, and the residual monomer or oligomer component is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and still more preferably 0.05 to 1% by mass. Thereby, a sensitizing ray-sensitive or radiation-sensitive resin composition free from foreign matter in the liquid or no change in sensitivity over time is obtained. In addition, in terms of resolution, resist shape, sidewall of resist pattern, roughness, etc., the molecular weight distribution (Mw/Mn, also referred to as dispersion) is preferably in the range of 1 to 5, more preferably The range of 1 to 3 is more preferably the range of 1 to 2.

The hydrophobic resin (D) can also use various commercially available products, or can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, there is a general polymerization method in which the monomer species and initiator are dissolved in a solvent and heated to perform polymerization; the monomer is added dropwise to the heating solvent for 1 to 10 hours The dropwise polymerization method of the solution of the species and the initiator is preferably the dropwise polymerization method. The reaction solvent, polymerization initiator, reaction conditions (temperature, concentration, etc.), and the purification method after the reaction are the same as those described in the resin (A). In the synthesis of the hydrophobic resin (D), the reaction concentration is better It is 30-50% by mass.

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

【Chemical formula 76】

【Chemical formula 77】

【Chemical formula 78】

【table 5】

【Chemical formula 79】

【Chemical formula 80】

【Chemical formula 81】

【Chemical formula 82】

【Table 6】

【Table 7】

[6] Surfactant In order to improve coatability, the negative sensitizing radiation or radiation-sensitive composition of the present invention may further contain a surfactant. Examples of surfactants are not particularly limited, and include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, and sorbitan fatty acid esters. Type, non-ionic surfactants such as polyoxyethylene sorbitan fatty acid ester, Magafac F171 (manufactured by DIC Corporation) or Fluorad FC430 (manufactured by Sumitomo 3M Limited) or Surfynol E1004 (manufactured by ASAHI GLASS CO., LTD.), OMNOVA Fluorine-based surfactants and organosiloxane polymers such as PF656 and PF6320 manufactured by Solutions Inc. When the negative sensitizing radiation or radiation-sensitive composition of the present invention may or may not contain a surfactant, when it contains a surfactant, its content is preferably relative to the total amount of the composition (excluding the solvent) 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass.

[7] Organic carboxylic acid The negative sensitizing radiation or radiation sensitive composition of the present invention preferably contains an organic carboxylic acid in addition to the above-mentioned components. Examples of such organic carboxylic acid compounds include aliphatic carboxylic acids, alicyclic carboxylic acids, unsaturated aliphatic carboxylic acids, hydroxycarboxylic acids, alkoxycarboxylic acids, ketone carboxylic acids, benzoic acid derivatives, o-benzene Dicarboxylic acid, terephthalic acid, isophthalic acid, 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, etc. When electron beam exposure is performed under vacuum, it may volatilize from the surface of the resist film and contaminate the drawing room. Therefore, the preferred compound is an aromatic organic carboxylic acid, such as benzoic acid and 1-hydroxy-2-naphthalene. Formic acid and 2-hydroxy-3-naphthoic acid are preferred. The negative sensitizing radiation-sensitive or radiation-sensitive composition of the present invention may or may not contain organic carboxylic acid. When organic carboxylic acid is contained, the mixing ratio of organic carboxylic acid is relative to 100 mass of polymer compound (A) The part is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.01 to 3 parts by mass. The negative sensitizing radiation-sensitive or radiation-sensitive composition of the present invention may further contain dyes, plasticizers, and acid proliferation agents as necessary (described in International Publication No. 95/29968, International Publication No. 98/24000, Japan Japanese Patent Application Publication No. 8-305262, Japanese Patent Application Publication No. 9-34106, Japanese Patent Application Publication No. 8-248561, Japanese Patent Application Publication No. 8-503082, U.S. Patent No. 5,445,917 Specification, Japanese Patent Application Publication No. 8-503081 Publication No. 5,534,393 Specification, U.S. Patent No. 5,395,736 Specification, U.S. Patent No. 5,741,630 Specification, U.S. Patent No. 5,334,489 Specification, U.S. Patent No. 5,582,956 Specification, U.S. Patent No. 5,578,424 Specification, U.S. Patent No. 5,453,345 Specification, U.S. Patent No. 5,445,917 Specification, European Patent No. 665,960 Specification, European Patent No. 757,628 Specification, European Patent No. 665,961 Specification, U.S. Patent No. 5,667,943 Specification, Japanese Patent Laid-Open No. 10-1508, Japanese Patent Laid-Open No. 10 -282642, Japanese Patent Application Publication No. 9-512498, Japanese Patent Application Publication No. 2000-62337, Japanese Patent Application Publication No. 2005-17730, Japanese Patent Application Publication No. 2008-209889, etc.). Regarding these compounds, each compound described in JP 2008-268935 A can be cited.

[8] Onium carboxylate The negative sensitizing radiation or radiation-sensitive composition of the present invention may contain an onium carboxylate. Examples of the onium carboxylate include sulfonium carboxylate, iodonium carboxylate, and ammonium carboxylate. As the onium carboxylate, sulfonium carboxylate and iodonium carboxylate are particularly preferred. In addition, in the present invention, it is preferable that the carboxylate residue of the onium carboxylate does not contain an aromatic group and has carbon-carbon double bonds. As a particularly preferred anion part, a linear, branched, monocyclic or polycyclic cyclic alkyl carboxylic acid anion having 1 to 30 carbon atoms is preferred. More preferably, the anion of a carboxylic acid in which a part or all of the alkyl group is substituted with fluorine is preferable. The alkyl chain may also contain oxygen atoms. By this, transparency to light below 220 nm can be ensured, sensitivity and resolution are improved, and density dependence and exposure margin are improved.

The negative sensitizing radiation or radiation-sensitive composition of the present invention may contain an onium carboxylate salt or not. When it contains an onium carboxylate, the negative sensitizing radiation or radiation-sensitive composition is Based on the total solid content, the content of the onium carboxylate is preferably 0.5 to 20% by mass, more preferably 0.7 to 15% by mass, and still more preferably 1.0 to 10% by mass.

[9] Solvent The negative sensitizing radiation or radiation sensitive composition of the present invention preferably contains a solvent. Solvents that can be used when preparing negative sensitizing radiation or radiation-sensitive compositions include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, Alkoxypropionic acid alkyl esters, cyclic lactones (preferably with 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably with 4 to 10 carbon atoms), alkylene carbonate, Organic solvents such as alkyl alkoxyacetate and alkyl pyruvate. Specific examples of these solvents include the solvents described in the specifications [0441] to [0455] of US Patent Application Publication No. 2008/0187860.

In the present invention, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group can also be used as an organic solvent. As a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group, the aforementioned exemplified compounds can be appropriately selected. The solvent containing a hydroxyl group is preferably alkylene glycol monoalkyl ether, alkyl lactate, alkyl butyrate, etc., more preferably propylene glycol Propylene Glycol Monomethyl Ether (PGME, alias 1-methoxy-2-propanol), ethyl lactate, methyl 2-hydroxyisobutyrate. In addition, as a solvent that does not contain a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, ring-containing monoketone compound, cyclic lactone, alkyl acetate Among these compounds, propylene glycol monomethyl ether acetate (PGMEA, alias 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ -Butyrolactone, cyclohexanone, butyl acetate, most preferably propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone. The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. In terms of coating uniformity, it is particularly preferable to contain 50% by mass or more of a hydroxyl-free mixed solvent. The solvent preferably contains propylene glycol monomethyl ether acetate, preferably a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate. The solid content concentration of the negative sensitizing radiation or radiation sensitive composition of the present invention is preferably 1 to 40% by mass. It is more preferably 1 to 30% by mass, and still more preferably 3 to 20% by mass.

<Negative sensitizing radiation or radiation sensitive film> The present invention also relates to a negative sensitizing radiation or radiation sensitive film formed by the negative sensitizing radiation or radiation sensitive composition of the present invention. The film is, for example, a film formed by coating the composition of the present invention on a support such as a substrate. The thickness of the film is preferably 0.02 to 0.1 μm. As the method of coating on the substrate, it can be coated on the substrate by suitable coating methods such as spin coating, roll coating, curtain coating, dip coating, spray coating, and blade coating. Preferably, the rotation speed is preferably 1000 to 3000 rpm. The coating film is pre-baked at 60-150°C for 1-20 minutes (pre-baked at 80-120°C for 1-10 minutes is preferred) to form a thin film. Regarding the material constituting the substrate to be processed and its outermost layer, for example, in the case of using a semiconductor wafer, a silicon wafer can be used. Examples of materials that form the outermost layer include Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflection film, etc.

An anti-reflection film can also be pre-coated on the substrate before forming the negative sensitizing radiation or radiation sensitive film. As the anti-reflection film, it is possible to use inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, etc.; and any of organic film types including light absorbers and polymer materials. In addition, as the organic anti-reflection film, commercially available organic anti-reflection films such as DUV30 series and DUV-40 series manufactured by Brewer Science, Inc., AR-2, AR-3, AR-5 manufactured by Shiply, and the like can be used.

<Blank Mask> In addition, the present invention also relates to a blank mask provided with a negative-type photosensitive ray-sensitive or radiation-sensitive film formed by a negative-type photosensitive ray-sensitive or radiation-sensitive composition. In order to obtain a blank mask with this negative sensitizing radiation or radiation-sensitive film, when patterning the blank mask for mask production, the transparent substrate used can be quartz, calcium fluoride And other transparent substrates. Generally, a light-shielding film, an anti-reflection film, a phase shift film are further laminated on the above-mentioned substrate, and functional films such as an etching stop film and an etching mask film are additionally laminated. Examples of materials for the functional film include films containing transition metals such as silicon or chromium, molybdenum, zirconium, tantalum, tungsten, titanium, and niobium. In addition, as the material used in the outermost layer, examples include: silicon or a material containing oxygen and/or nitrogen in silicon as the main constituent material; and a material further containing transition metal as the main constituent material. Silicon compound material; or one or more selected from transition metals, especially selected from chromium, molybdenum, zirconium, tantalum, tungsten, titanium, niobium, etc., or further including one or more selected from oxygen and nitrogen in these , The material of the element in carbon is the transition metal compound material which is the main constituent material. The light-shielding film may be a single layer, but a multilayer structure obtained by repeatedly coating multiple materials is better. In the case of a multilayer structure, the thickness of each layer of the film is not particularly limited, but it is preferably 5 to 100 nm, and more preferably 10 to 80 nm. The thickness of the entire light-shielding film is not particularly limited, but is preferably 5 to 200 nm, and more preferably 10 to 150 nm.

Generally, among these materials, when patterning is performed on a blank mask with a material containing oxygen or nitrogen in chromium on the outermost layer, it is easy to become a so-called under-cut shape in which a reduced diameter shape is formed near the substrate. However, when using the present invention, compared with the conventional ones, the undercut problem can be improved. The negative sensitizing or radiation-sensitive film is irradiated with actinic rays or radiation (electron beam, etc.), preferably after baking (usually 80-150°C, more preferably 90-130°C) . Thereby, a good pattern can be obtained. In addition, the pattern is used as a mask, and etching treatment, ion implantation, etc. are suitably performed to produce semiconductor microcircuits and mold structures for imprinting. In addition, the manufacturing process when using the negative sensitizing radiation-sensitive or radiation-sensitive composition of the present invention to produce an imprint mold is described in, for example, Japanese Patent No. 4109085, Japanese Patent Laid-Open No. 2008-162101, and The foundation and technology development and application development of rice imprinting-the development of substrate technology and the latest technology of nano imprinting-edited by Yoshihiko Hirai (Frontier Publishing)".

The composition of the present invention dissolves the above-mentioned components in a predetermined organic solvent, preferably dissolved in the above-mentioned mixed solvent, filtered through a filter, and coated on a predetermined substrate for use. The filter used for filter filtration has a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon that is 0.03 μm or less. In filter filtration, as described in Japanese Patent Application Laid-Open No. 2002-62667, for example, it is possible to perform cyclic filtration, or to perform filtration by connecting a plurality of filters in series or in parallel. In addition, the composition may be filtered multiple times. Furthermore, the composition can be degassed before and after filtration by the filter.

<Pattern forming method using negative sensitizing radiation or radiation-sensitive composition> The present invention also relates to a pattern forming method including the steps of: coating the negative sensitizing radiation or radiation-sensitive composition on a substrate The step of forming a film; the step of exposing the film; and the step of developing the exposed film to form a negative pattern. In addition, the present invention also relates to a resist pattern forming method including the steps of: exposing a blank mask with the negative sensitizing radiation or radiation-sensitive film; developing the exposed blank mask的步。 The steps. In the present invention, the above-mentioned exposure is preferably carried out using electron beams or extreme ultraviolet rays.

In the manufacture of precision integrated circuit components, the exposure (pattern formation step) on the negative sensitizing radiation or radiation sensitive film is first to pattern the negative sensitizing radiation or radiation sensitive film of the present invention. Irradiation of electron beam or extreme ultraviolet (EUV) is preferred. On exposure amount, in the case where the electron beams to be 0.1 ~ 20μC / cm ² or so, be 3 ~ 10μC / cm ² was exposed to approximately the preferred embodiment, in the case of extreme ultraviolet to become 0.1 ~ 20mJ / cm ² or so, it is 3 ~ 15mJ / cm ² was exposed to approximately the preferred embodiment. Then, on a hot plate, heat at 60-150°C for 1-20 minutes (preferably at 80-120°C for 1-10 minutes) post-exposure heating (Post exposure bake), and then develop, Rinse and dry to form patterns. The developer can be appropriately selected, and it is preferable to use an alkaline developer (typically an alkaline aqueous solution) or a developer containing an organic solvent (also referred to as an organic developer). When the developer is an alkaline aqueous solution, use an alkaline aqueous solution of 0.1 to 5 mass%, preferably 2 to 3 mass%, such as tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), etc. A conventional method such as a dip method, a puddle method, and a spray method is used to perform development for 0.1 to 3 minutes, preferably 0.5 to 2 minutes. Alcohols and/or surfactants can also be added in an appropriate amount to the alkaline developer. In this way, the unexposed part of the film is dissolved, and the exposed part is difficult to dissolve in the developing solution, forming a target pattern on the substrate.

When the resist pattern forming method of the present invention has a step of developing with an alkaline developer, as the alkaline developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, Inorganic bases such as ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; Alcoholamines such as methylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexyl hydroxide Ammonium, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, etc. Ammonium; tertiary ammonium salts such as trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide; alkaline aqueous solutions of cyclic amines such as pyrrole and piperidine . Furthermore, it can also be used by adding an appropriate amount of alcohols and surfactants to the alkaline aqueous solution. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0. Particularly preferred is a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

Pure water can also be used as the rinsing liquid in the rinsing treatment performed after alkali development, and an appropriate amount of surfactant can be added for use. In addition, after the development process or the rinse process, a process of using a supercritical fluid to remove the developer or rinse adhering to the pattern may be performed.

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

In the present invention, the so-called ester solvent refers to a solvent having an ester group in the molecule, the ketone solvent refers to a solvent having a ketone group in the molecule, and the alcohol solvent refers to a solvent having an alcoholic hydroxyl group in the molecule. The amine solvent refers to a solvent having an amide group in the molecule, and the ether solvent refers to a solvent having an ether bond in the molecule. Among these solvents, there are also solvents having a plurality of the above-mentioned functional groups in one molecule. In this case, it is also equivalent to any solvent type containing the functional groups of the solvent. For example, diethylene glycol monomethyl ether is also equivalent to any one of alcohol solvents and ether solvents in the above classification. In addition, the term "hydrocarbon solvent" refers to a hydrocarbon solvent that does not have a substituent. Particularly preferably, it is a developer containing at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, and an ether solvent.

From the viewpoint of suppressing the swelling of the negative sensitizing radiation or radiation-sensitive film, the developer is used with carbon atoms of 7 or more (7-14 is preferable, 7-12 is more preferable, 7-10 is more preferable Preferably), and ester-based solvents with a heteroatom number of 2 or less are preferred. The heteroatom of the above-mentioned ester-based solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms is preferably 2 or less. Preferable examples of ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, and 1 -Methyl butyl, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, etc. It is particularly preferred to use isoamyl acetate.

The developer can use a mixed solvent of the above-mentioned ester solvent and the above-mentioned hydrocarbon solvent, or a mixed solvent of the above-mentioned ketone solvent and the above-mentioned hydrocarbon solvent, instead of the above-mentioned ester solvent having 7 or more carbon atoms and 2 or less heteroatoms . In this case, there is also an effect of suppressing swelling of the negative sensitizing radiation or radiation sensitive film. When an ester solvent and a hydrocarbon solvent are used in combination, it is preferable to use isoamyl acetate as the ester solvent. In addition, from the viewpoint of the solubility of the negative sensitizing radiation or radiation-sensitive film, saturated hydrocarbon solvents (such as octane, nonane, decane, dodecane, undecane, decane, etc.) are used as the hydrocarbon solvent. Hexane, etc.) is preferred. Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylpentyl ketone), 4-heptanone, 1-hexanone , 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone (Ionone), diacetone alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, etc. Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, and propylene glycol monomethyl ether ethyl. Ester, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutane Glycol acetate, 3-methyl-3-methoxy butyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate , 2-hydroxyisobutyrate, etc. Examples of alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, 4-methyl-2-pentanol, tert-butanol, isobutanol, n-hexanol, Alcohols such as n-heptanol, n-octanol, n-decanol, or glycol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and ethylene glycol Glycol ether solvents such as monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethyl butanol. As the ether solvent, for example, in addition to the aforementioned glycol ether solvent, anisole, dioxane, tetrahydrofuran, etc. may be mentioned. Amine-based solvents can be used, for example: N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone), N,N-dimethylacetamide, N,N-dimethylformamide, hexamethyl Hexamethyl phosphoric triamide, 1,3-dimethyl-2-imidazolinone, etc. Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane. The above-mentioned solvents may be mixed with plural kinds, and may be used in combination with solvents or water other than the above. Among them, in order to fully exhibit the effects of the present invention, it is preferable that the moisture content of the entire developer is less than 10% by mass, and it is more preferable that it contains substantially no moisture. That is, relative to the total amount of the developer, the usage amount of the organic solvent to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less. The organic developer is particularly 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 at 20°C, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the organic developer to 5kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensional uniformity in the wafer surface is reduced. Well. Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methylpentyl ketone), 4-heptanone, Ketone solvents such as 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl isobutyl ketone; butyl acetate, amyl acetate, isoamyl acetate, acetic acid Amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3-ethoxy Ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, lactic acid Ester solvents such as propyl ester; n-propanol, isopropanol, n-butanol, second butanol, tertiary butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, n-decanol and other alcohols Solvent; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, methoxymethyl butanol and other glycol ether solvents; tetrahydrofuran and other ether solvents; N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone), N,N- Amine solvents such as dimethylacetamide and N,N-dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as octane and decane. Specific examples of a vapor pressure below 2 kPa in a particularly preferred range include: 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone Ketone solvents such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3- Methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate and other ester solvents; n-butanol, second butanol, tertiary butanol, isobutanol, n-hexanol , N-heptanol, n-octanol, n-decyl alcohol and other alcohol solvents; ethylene glycol, diethylene glycol, triethylene glycol and other glycol solvents or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene two Alcohol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol and other glycol ether solvents; N-methyl-2-pyrrolidone (N-methyl- 2-pyrrolidone), N,N-dimethylacetamide, N,N-dimethylformamide solvents; aromatic hydrocarbon solvents such as xylene; octane, decane, undecane, etc. Aliphatic hydrocarbon solvent.

The organic developer may also contain an alkaline compound. The specific examples and preferred examples of the alkaline compound that the developer used in the present invention can contain are the same as the specific examples and preferred examples of the alkaline compound that the aforementioned sensitizing radiation or radiation-sensitive composition can contain .

An appropriate amount of surfactant can be added to the organic developer as needed. The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and/or silicon-based surfactants can be used. The fluorine and/or silicon-based surfactants include, for example, the surfactants described in the following patent documents: Japanese Patent Application Publication No. 62-36663, Japanese Patent Application Publication No. 61-226746, Japanese Patent Application Publication No. 61- 226745, JP 62-170950, JP 63-34540, JP 7-230165, JP 8-62834, JP 9-54432 , Japanese Patent Laid-Open No. 9-5988, U.S. Patent No. 5405720, U.S. Patent No. 5360692, U.S. Patent No. 5,529,881, U.S. Patent No. 5296330, U.S. Patent No. 5,36098, U.S. Patent No. 5576143 The specification, US Patent No. 5,294,511, and US Patent No. 5,824,451 are preferably nonionic surfactants. The nonionic surfactant is not particularly limited, and it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant. The amount of the surfactant used is preferably 0 to 2% by mass relative to the total amount of the developer, more preferably 0.0001 to 2% by mass, and particularly preferably 0.0005 to 1% by mass.

For example, the following methods can be applied to the development method: a method of immersing the substrate in a tank filled with developer for a predetermined time (dipping method); a method of using surface tension to pile up the developer on the surface of the substrate and rest for a predetermined time for development ( Liquid coating method); a method of spraying developer on the surface of the substrate (spraying method); a method of continuously spraying the developer while scanning the nozzle of the developer on a substrate rotating at a predetermined speed (dynamic distribution method) dispense method)) etc. In the case where the above-mentioned various developing methods include the step of ejecting the developer from the developing nozzle of the developing device to the negative-type sensitized radiation or radiation-sensitive film, the ejection pressure of the ejected developer (each amount of the ejected developer is The flow rate per unit area) is preferably 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, and still more preferably 1 mL/sec/mm ² or less. There is no particular lower limit for the flow rate, and if throughput is considered, it is preferably 0.2 mL/sec/mm ² or more. By setting the ejection pressure of the ejected developer to the above range, pattern defects caused by resist residue after development can be significantly reduced. The details of this mechanism are not certain, but it is thought that the reason may be: by setting the ejection pressure within the above range, the pressure exerted by the developer on the negative-type sensitizing radiation or radiation-sensitive film is reduced, thereby suppressing the negative-type The sensitized radiation or radiation-sensitive film/pattern was accidentally cut off or disintegrated. In addition, the discharge pressure (mL/sec/mm ² ) of the developer is the value at the outlet of the developing nozzle in the developing device.

The method of adjusting the ejection pressure of the developer includes, for example, a method of adjusting the ejection pressure with a pump or the like, or a method of adjusting the pressure by supply from a pressure tank to change the pressure.

In addition, after the step of developing using a developer containing an organic solvent, a step of stopping the development while replacing it with another solvent can be implemented.

After the step of developing with a developer containing an organic solvent, it may include the step of washing with eluent, but from the viewpoint of throughput (productivity) and eluent usage, it may not include the use of eluent. Steps of cleaning.

The rinsing solution used in the rinsing step after the step of developing using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. The above-mentioned eluent is preferably an eluent containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents liquid. Specific examples of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents include the same solvents as those described in the organic solvent-containing developer. After the step of using a developer containing an organic solvent for development, it is more preferable to perform the process using an eluent containing at least one organic solvent selected from the group consisting of ester solvents, alcohol solvents, and hydrocarbon solvents. The cleaning step is further preferably a step of cleaning using an eluent containing an alcohol solvent or a hydrocarbon solvent.

As the organic solvent contained in the eluent, a hydrocarbon-based solvent is also preferably used among the organic solvents, and an aliphatic hydrocarbon-based solvent is more preferably used. As the aliphatic hydrocarbon solvent used in the eluent, from the viewpoint of further improving its effect, aliphatic hydrocarbon solvents with 5 or more carbon atoms (such as pentane, hexane, octane, decane, undecane) , Dodecane, hexadecane, etc.) are preferred, aliphatic hydrocarbon solvents with 8 or more carbon atoms are more preferred, and aliphatic hydrocarbon solvents with 10 or more carbon atoms are more preferred. In addition, the upper limit of the number of carbon atoms of the aliphatic hydrocarbon-based solvent is not particularly limited. For example, it is 16 or less, preferably 14 or less, and more preferably 12 or less. Among the aforementioned aliphatic hydrocarbon solvents, decane, undecane, and dodecane are particularly preferred, and undecane is most preferred. In this way, by using hydrocarbon solvents (especially aliphatic hydrocarbon solvents) as the organic solvent contained in the eluent, the developer that slightly penetrates into the negative sensitizing radiation or radiation sensitive film after development is washed away, and further It has the effect of suppressing swelling and suppressing pattern collapse.

The above-mentioned components may be mixed in plural, or may be mixed and used with organic solvents other than the above.

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

The vapor pressure of the eluent used after the step of developing using a developer containing an organic solvent is preferably 0.05kPa or more and 5kPa or less, more preferably 0.1kPa or more and 5kPa or less, and most preferably 0.12 at 20°C kPa or more and 3kPa or less. By setting the vapor pressure of the eluent to 0.05kPa or more and 5kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling caused by the penetration of the eluent is suppressed, and the dimensional uniformity in the wafer surface is reduced. Well.

An appropriate amount of surfactant can also be added to the eluent.

In the rinsing step, the wafer that has been developed with a developer containing an organic solvent is cleaned with the above-mentioned rinsing solution containing an organic solvent. The cleaning method is not particularly limited. For example, the following methods can be applied: a method of continuously spraying rinsing liquid on a substrate rotating at a predetermined speed (spin coating method); immersing the substrate in a tank filled with rinsing liquid. Time method (dipping method); method of spraying rinse liquid on the substrate surface (spray method), etc. Among them, it is preferable to use a spin coating method for cleaning treatment. After cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm to remove the eluent from the substrate. In addition, it is also preferable to include a heating step (PostBake) after the rinsing step. The developer and rinsing liquid remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40-160°C, preferably 70-95°C, usually for 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

In addition, the pattern forming method of the present invention may have a development step using an organic developer and a development step using an alkaline developer. The part with weak exposure intensity is removed by development using an organic developer, and the part with strong exposure intensity is also removed by development using an alkaline developer. By performing the multiple development process of multiple developments in this way, the pattern can be formed without dissolving only the area of the intermediate exposure intensity, so a finer pattern than usual can be formed (and Japanese Patent Laid-Open No. 2008-292975 Paragraph [0077] of the communiqué same mechanism).

In addition, the present invention also relates to a mask obtained by exposing and developing the blank mask having the negative radiation-sensitive or sensitized radiation film. The steps described above can be applied to exposure and development. The aforementioned photomask is suitable for semiconductor manufacturing. The photomask in the present invention may be a light transmission type mask used in ArF excimer lasers, etc., or a light reflection type mask used in a reflection system lithography using EUV light as a light source.

In addition, the composition of the present invention can also be used to produce a mold for imprinting. For details, refer to Japanese Patent No. 4109085 and Japanese Patent Application Laid-Open No. 2008-162101 for details. The resist pattern forming method of the present invention can also be used to form guided patterns in DSA (Directed Self-Assembly) (for example, refer to ACSNanoVol. 4 No. 8 Page 4815-4823). In addition, the resist pattern formed by the above-mentioned method can be used as a core for the spacer process disclosed in, for example, Japanese Patent Application Laid-Open No. 3-270227 and Japanese Patent Application Publication No. 2013-164509.

In addition, the present invention also relates to a manufacturing method of an electronic component including the pattern forming method of the present invention and an electronic component manufactured by the manufacturing method. The electronic component (preferably a semiconductor component) of the present invention is suitable for installation in electrical and electronic equipment (home appliances, OA/media-related equipment, optical equipment, communication equipment, etc.). [Example]

Hereinafter, the present invention will be described in more detail based on examples, but the content of the present invention is not limited thereto.

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

【Chemical formula 83】

(Synthesis of polymer 1a) 10 g of poly(p-hydroxystyrene) (VP2500, dispersion 1.10) manufactured by Nippon Soda Co., Ltd. and potassium hydroxide aqueous solution (dissolve 5.7 g of potassium hydroxide in 49 g of water) For mixing, 20 g of methanol was added thereto and stirred at 40°C for several minutes. 7.5 g of paraformaldehyde was added thereto, and the mixture was stirred at 40°C for 5 hours. After the reaction, the reaction solution was returned to room temperature, and 80 ml of ethyl acetate and 80 ml of dilute hydrochloric acid (1N) were added to perform liquid separation. After the organic layer was washed with distilled water until the water layer became neutral, 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 (the peaks are broad)

(Synthesis of polymer compound A1) 7 g of 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, and the mixture was stirred at 55°C for 3 hours. After the reaction, the reaction liquid was returned to room temperature, and 200 g of ethyl acetate and 200 g of distilled water were added to perform liquid separation. After the organic layer was washed with distilled water three times, the organic layer was concentrated. A solution of the obtained powder dissolved in 70 g of ethyl acetate was dropped into 700 g of n-hexane. After the powder was filtered and vacuum dried, 5.4 g of the polymer compound (A1) was obtained. ¹ H-NMR (DMSO-d6: ppm) δ: 9.02, 8.09, 6.49, 4.27, 3.13, 0.81-2.22 (the peaks are all broad) Other polymer compounds A2～A8 were also synthesized in the same way as above . On the other hand, the polymer compound A9 was prepared based on the method described in Japanese Patent Application Laid-Open No. 2-170165.

In the above-mentioned synthesis example, the synthesized polymer compound may become more than the two-component system. For example, the above Synthesis Example 1 includes a three-component system, that is, a repeating unit with a crosslinkable group of 0, a repeating unit with a crosslinkable group of 1, and a crosslinkable group of 2. The repeating unit. It is complicated to distinguish and calculate the ratio of the repeating unit with the number of crosslinkable groups of 1 and the ratio of the repeating unit with the number of crosslinkable groups of 2. Therefore, the ratio of crosslinkable groups defined below is used to evaluate the polymer The number of crosslinkable groups contained in the compound.

(Crosslinkable group rate)=(number of points where crosslinkable groups are introduced)/(number of reaction points where crosslinkable groups can be introduced)×100 (%)

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

The following table shows the crosslinkable group ratio, weight average molecular weight, and degree of dispersion of the polymer compound. The weight average molecular weight and the degree of dispersion are calculated by GPC (solvent: THF) measurement. The structures of the polymer compounds A1 to A8 sometimes become three-component systems as described above, but for simplicity, only the structure of the repeating unit with a crosslinkable group number of 0 and the largest number of crosslinkable groups (means the The two components of the structure of the repeating unit when all reaction points are reacted. On the other hand, the polymer compound A9 is obtained by polymerization of monomers corresponding to the repeating units described in the following table, and actually has only one component of the repeating units described in the following table.

【Table 8】

[Examples 1E to 33E, and Comparative Examples 1ER to 5ER] (1) Preparation of the support body Prepare a 6-inch silicon wafer vapor-deposited with Cr oxide (a masking film processed article used in a normal blank mask) .

(2) Preparation of the resist coating solution. The components shown in Table 9 below were dissolved in the solvents shown in Table 9, and they were micronized using a polytetrafluoroethylene filter with a pore size of 0.04 μm. Filter to obtain a resist coating solution.

(3) Formation of resist film Use the spin coater Mark8 manufactured by Tokyo Electronics Co., Ltd. to coat the resist coating solution on the 6-inch silicon wafer, and dry it on a hot plate at 110°C for 90 seconds. A resist film with a film thickness of 50 nm was obtained as a negative sensitizing radiation or radiation sensitive film. That is, a blank mask with negative sensitizing radiation or radiation sensitive film is obtained.

(4) Preparation of negative resist pattern An electron beam drawing device (manufactured by ELIONIX INC.; ELS-7500, acceleration voltage of 50 KeV) was used to pattern the resist film. After irradiation, it was heated on a hot plate at 120°C for 90 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and then dried.

(5) Evaluation of resist pattern The sensitivity, resolution, PED stability, and line edge roughness (LER) performance of the obtained pattern were evaluated by the following methods.

[Sensitivity] A scanning electron microscope (manufactured by Hitachi, Ltd., S-4300) was used to observe the cross-sectional shape of the obtained pattern. The exposure amount (electron beam irradiation amount) when analyzing a resist pattern of a 1:1 line and a gap with a line width of 50 nm was taken as the sensitivity. The smaller the value, the higher the sensitivity. Among them, for Comparative Examples 1ER to 5ER, because the 1:1 line and gap pattern with a line width of 50 nm cannot be analyzed, the 1:1 line and gap pattern with a line width of 100 nm will be analyzed for Comparative Example 1ER, and the line width will be analyzed for Comparative Example 2ER. 80nm 1:1 line and gap pattern, for Comparative Example 3ER, analyze the 1:1 line and gap pattern with a line width of 70nm, for Comparative Example 4ER, analyze the 1:1 line and gap pattern with a line width of 60nm, for Comparative Example 5ER, analyze the line The irradiated energy in a 65nm width 1:1 line and gap pattern is used as sensitivity (Eop).

[Resolving power] The resolution (nm) is the limit resolution (minimum line width for separation of lines and gaps) at the exposure level (electron beam exposure) that shows the above sensitivity.

[Line Edge Roughness (LER) Performance] A 1:1 line and gap pattern with a line width of 50nm is formed by the exposure amount (electron beam irradiation amount) showing the above sensitivity. In addition, for any 30 points contained in the length direction of 10μm, the distance from the reference line that should exist on the edge is measured using a scanning electron microscope (manufactured by Hitachi, Ltd., S-9220). Then, the standard deviation of the distance is obtained, and 3σ is calculated. The smaller the value, the better the performance. Among them, for Comparative Examples 1ER to 5ER, because the 1:1 line and gap pattern with a line width of 50 nm cannot be analyzed, in Comparative Example 1ER, for the 1:1 line and gap pattern with a line width of 100 nm, compared to the line in Comparative Example 2ER. A 1:1 line and gap pattern with a width of 80nm, a 1:1 line and gap pattern with a line width of 70nm in Comparative Example 3ER, and a 1:1 line and gap pattern with a line width of 60nm in Comparative Example 4ER. In 5ER, for a 1:1 line and gap pattern with a line width of 65 nm, the standard deviations of the above-mentioned distances are respectively obtained, and 3σ is calculated.

[PED (Post Exposure time Delay) stability] After exposing at an exposure amount where the line width of the 1:1 line and gap pattern with a line width of 50nm becomes 50nm, quickly measure the lines on the PEB-treated wafer Width (0h), and after 5 hours, measure the line width dimension (5.0h) of the line on the PEB-treated wafer, and calculate the line width change rate by the following formula. Line width change rate (%)=|ΔCD(5.0h-0h)|nm/50nm The smaller the value, the better the performance, which is an indicator of PED stability. Among them, for Comparative Examples 1ER to 5ER, because the 1:1 line and gap pattern with a line width of 50 nm cannot be resolved, in Comparative Example 1ER, the line width of the 1:1 line and gap pattern with a line width of 100 nm is 100 nm. Calculate the above-mentioned rate of change of line width under the measurement. In Comparative Example 2ER, the line width change rate was calculated when the line width dimension of the 1:1 line and gap pattern with a line width of 80 nm became 80 nm. In Comparative Example 3ER, the line width change rate was calculated when the line width dimension of the 1:1 line and gap pattern with a line width of 70 nm became 70 nm. In Comparative Example 4ER, the line width change rate was calculated when the line width dimension of the 1:1 line and gap pattern with a line width of 60 nm was 60 nm. In Comparative Example 5ER, the line width change rate was calculated when the line width dimension of the 1:1 line and gap pattern with a line width of 65 nm was 65 nm.

【Table 9】

[Photo acid generator] The structure of the photo acid generator used in the examples and the volume value of the acid generated by the photo acid generator are shown together below. Here, the volume value of the acid is obtained by the same calculation method as the volume value of the acid produced by the above-mentioned compound (B).

【Chemical formula 84】

【Chemical formula 85】

【Chemical formula 86】

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

【Chemical formula 87】

〔Crosslinking agent〕

【Chemical formula 88】

[Other polymer compounds] The composition ratio (molar ratio; corresponding from the left) of each repeating unit in other polymer compound P1 and the weight average molecular weight (Mw) of other polymer compounds P1 and P2 are also shown below. ) And degree of dispersion (Mw/Mn).

【Chemical formula 89】

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

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

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

【Table 10】

As can be seen from the above table, according to Examples 1E to 33E using the pattern forming method of the present invention, compared with Comparative Examples 1ER to 5ER not using the pattern forming method of the present invention, it is possible to achieve a high degree of sensitivity, resolution, PED stability, And LER performance.

[Examples 1F to 10F and Comparative Examples 1FR to 4FR] (Preparation of resist film) The above 6-inch silicon wafer was coated with the above-prepared resist coating using a spin coater Mark8 manufactured by Tokyo Electronics Co., Ltd. The solution was dried on a hot plate at 110°C for 90 seconds to obtain a resist film with a film thickness of 50 nm as a negative sensitizing radiation or radiation sensitive film. That is, a blank mask with negative sensitizing radiation or radiation sensitive film is obtained.

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

[Sensitivity] For the obtained resist film, use EUV exposure equipment (MicroExposure Tool manufactured by Exitech, NA0.3, Quadrupole, External Sigma 0.68, Internal Sigma 0.36), and the exposure amount is 0～20.0mJ/cm ² Change the range by 0.1 mJ/cm ² each time, and at the same time expose it through a reflective mask with a line width of 50nm and a 1:1 line and gap pattern, and then bake at 110°C for 90 seconds. After that, development was performed using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. The amount of exposure that reproduces the mask pattern of a 1:1 line and gap with a line width of 50 nm is used as the sensitivity. The smaller the value, the higher the sensitivity. Among them, for Comparative Examples 1FR to 4FR, because the 1:1 line and gap pattern with a line width of 50 nm cannot be analyzed, the 1:1 line and gap pattern with a line width of 350 nm will be analyzed for Comparative Example 1FR, and the line for Comparative Example 2FR will be analyzed. A 100nm wide 1:1 line and gap pattern, a 1:1 line and gap pattern with a line width of 85nm for Comparative Example 3FR, and a 1:1 line and gap pattern with a 60nm line width for Comparative Example 4FR as sensitivity. (Eop).

[Resolving power] The limit resolution (minimum line width for separation analysis between lines and gaps (line: gap=1:1)) at the exposure level showing the above sensitivity is used as resolution (nm).

[Line edge roughness (LER) performance] A 1:1 line and gap pattern with a line width of 50nm was formed by the exposure level showing the above sensitivity. In addition, for any 30 points contained in the length direction of 50μm, the distance from the edge should be measured using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Then, the standard deviation of the distance is obtained, and 3σ is calculated. The smaller the value, the better the performance. Among them, for Comparative Examples 1FR to 4FR, because the 1:1 line and gap pattern with a line width of 50 nm cannot be resolved, in Comparative Example 1FR for the 1:1 line and gap pattern with a line width of 350 nm, compared to the line in Comparative Example 2FR. A 1:1 line and gap pattern with a width of 100 nm, a 1:1 line and gap pattern with a line width of 85 nm in Comparative Example 3FR, and a 1:1 line and gap pattern with a line width of 60 nm in Comparative Example 4FR. The standard deviation of the distance is calculated as 3σ.

[PED (Post Exposure time Delay) stability] After the line width dimension of the 50nm line and gap 1:1 pattern becomes the exposure amount of 50nm, the line width dimension of the PEB-treated line is quickly measured (0h), And after 5 hours, measure the line width dimension (5.0h) of the line on the PEB processed wafer, and calculate the line width change rate by the following formula. Line width change rate (%)=|ΔCD(5.0h-0h)|nm/50nm The smaller the value, the better the performance, which is an indicator of PED stability. Among them, for Comparative Examples 1FR to 4FR, because the 1:1 line and gap pattern with a line width of 50 nm cannot be resolved, the exposure in Comparative Example 1FR where the line width of the 1:1 line and gap pattern with a line width of 350 nm is 350 nm Calculate the above-mentioned rate of change of line width under the measurement. In Comparative Example 2FR, the line width change rate was calculated when the line width dimension of the 1:1 line and gap pattern with a line width of 100 nm was 100 nm. In Comparative Example 3FR, the line width change rate was calculated when the line width dimension of the 1:1 line and gap pattern with a line width of 85 nm was 85 nm. In Comparative Example 4FR, the line width change rate was calculated when the line width dimension of the 1:1 line and gap pattern with a line width of 60 nm was 60 nm.

【Table 11】

As can be seen from the above table, according to Examples 1F to 10F using the pattern forming method of the present invention, compared with Comparative Examples 1ER to 4FR not using the pattern forming method of the present invention, the sensitivity, resolution, and PED stability are highly compatible. , And LER performance.

no

Claims (17)

A negative sensitizing radiation or radiation-sensitive resin composition comprising: (A) a polymer compound having a repeating unit represented by the following general formula (2); (B) by irradiating actinic rays or radiation and generating an acid compound of 2000Å ³ or less on a volume of more than 130Å ^3,

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, Cycloalkyl, aryl or acyl, m'represents 1 or 2, and n'represents an integer of 1 to 3. The negative-type sensitizing radiation-sensitive or radiation-sensitive resin composition as described in item 1 of the scope of patent application, wherein the repeating unit represented by the above general formula (2) is the repeating unit represented by the following general formula (3) unit,

Wherein, R _2, R ₃ and R ₄ in the general formula R (2) is _2, R _3, and R ₄ the same meaning; n 'represents an integer of 1 to 3. The negative sensitizing radiation or radiation-sensitive resin composition as described in item 1 or item 2 of the scope of patent application, wherein the aforementioned compound (B) is a sulfonium salt. The negative-type sensitizing radiation or radiation-sensitive resin composition as described in item 1 or 2 of the scope of patent application, which also includes basic compounds or ammonium salt compounds whose alkalinity decreases due to irradiation with actinic rays or radiation (C). The negative-type sensitizing radiation-sensitive or radiation-sensitive resin composition described in item 4 of the scope of patent application, wherein the aforementioned compound (C) is an onium salt compound represented by the following general formula (4),

Wherein, A represents a sulfur atom or an iodine atom, R _A represents a hydrogen atom or an organic group, R _B represents a (p + 1) valent organic group, X represents a single bond or a linking group, A represents a nitrogen atom of the _N Basic parts, when there are multiple R _A , R _B , X and A _N respectively, these may be the same or different. When A is a sulfur atom, q is an integer from 1 to 3, and o satisfies o+q =3, when A is an iodine atom, q is 1 or 2, o is an integer satisfying the relationship of o+q=2, p represents an integer from 1 to 10, Y ^- represents an anion, R _A , X, At least two of R _B and A _N may be bonded to each other to form a ring. The negative-type sensitizing radiation or radiation-sensitive resin composition described in item 1 or item 2 of the scope of patent application, wherein the dispersion degree of the aforementioned polymer compound (A) is 1.0 to 1.40. The negative-type sensitizing radiation or radiation-sensitive resin composition described in item 1 or item 2 of the scope of patent application, wherein the aforementioned polymer compound (A) is represented by the following general formula (5) The polymer compound produced by the method of manufacturing the polymer of the repeating unit as the raw material,

In the _formula, R ₁ meaning _same as in the general formula R (2) it is. The negative-type sensitizing radiation-sensitive or radiation-sensitive resin composition as described in item 7 of the scope of patent application, wherein the polymer dispersion degree of the repeating unit represented by the general formula (5) is 1.0 to 1.20. The negative-type sensitizing radiation or radiation-sensitive resin composition as described in item 2 of the scope of patent application, wherein R ₂ and R ₃ in the above general formula (3) are both hydrogen atoms. The negative-type sensitizing radiation-sensitive or radiation-sensitive resin composition as described in item 1 of the scope of the patent application, wherein m'is 1, and n'is 1 or 2 in the general formula (2). The negative-type sensitizing radiation-sensitive or radiation-sensitive resin composition described in item 1 of the scope of patent application, wherein the content of the repeating unit represented by the general formula (2) is relative to that in the polymer compound (A) All repeating units contained are 40-100 mol%. The negative sensitizing radiation-sensitive or radiation-sensitive resin composition described in item 2 of the scope of the patent application, wherein the content of the repeating unit represented by the above general formula (3) is relative to that in the polymer compound (A) All repeating units contained are 40-100 mol%. The negative-type sensitizing radiation-sensitive or radiation-sensitive resin composition as described in item 5 of the scope of patent application, wherein in the general formula (4), p is an integer of 1 to 4. A negative sensitizing radiation or radiation-sensitive film, which is formed by using the negative sensitizing radiation or radiation-sensitive resin composition as described in any one of items 1 to 13 in the scope of the patent application. A blank mask provided with a negative sensitized radiation or radiation sensitive film as described in item 14 of the scope of patent application. A pattern forming method, comprising: coating a negative-type sensitizing radiation-sensitive or radiation-sensitive resin composition as described in any one of items 1 to 13 of the scope of patent application on a substrate to form a film; The step of exposing the film; and the step of developing the exposed film to form a negative pattern. A manufacturing method of an electronic component includes the pattern forming method as described in item 16 of the scope of patent application.