TW202246892A - Radiation-sensitive resin composition and pattern formation method - Google Patents

Abstract

Provided is a radiation sensitive resin composition that can form a resist film having sufficient levels of sensitivity, CDU performance, and development residue-inhibiting properties when next generation technology is used. Also provided is a pattern formation method. Provided is a radiation sensitive resin composition that contains: a resin comprising a structural unit represented by formula (1); one or at least two onium salts comprising an organic acid anion part and an onium cation part; and a solvent, wherein at least a portion of the onium cation part in the onium salt comprises an aromatic ring structure having a fluorine atom. (In formula (1), R is a hydrogen atom, an alkyl group having 1-5 carbon atoms, or a halogenated alkyl group having 1-5 carbon atoms, Y1 is a divalent linking group, and X1 is an acid dissociating group.).

Description

Radiation sensitive resin composition and pattern forming method

The invention relates to a radiation-sensitive resin composition and a pattern forming method.

Photolithography using a resist composition is used to form a fine circuit of a semiconductor element. As a typical procedure, for example, by exposing the film of the resist composition by radiation irradiation through a mask pattern to generate acid, and reacting with the acid as a catalyst, the chemical reaction between the exposed part and the unexposed part is carried out. A difference in the solubility of the resin with respect to an alkali-based or organic-solvent-based developer is generated in the portion, thereby forming a resist pattern on the substrate.

In the photolithography technique, pattern miniaturization is promoted by using short-wavelength radiation such as ArF excimer laser, or combining the reflected radiation with a liquid immersion exposure method (liquid immersion lithography). As a next-generation technology, it is possible to use shorter-wavelength radiation such as electron beams, X-rays, and extreme ultraviolet (extreme ultraviolet, EUV), and acid generators containing benzene rings that improve the absorption efficiency of such radiation are also being developed. Research on resist materials (Japanese Patent Laid-Open No. 2014-2359). [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-2359

[Problem to be Solved by the Invention]

In the next-generation technology, sensitivity and critical dimension uniformity (CDU) performance, which is an index of uniformity of line width or aperture, and development residue suppression ability to suppress residue generation during development are required to be different from those of previous technologies. The performance of the resist is equal to or higher than that of the resist.

An object of the present invention is to provide a radiation-sensitive resin composition and a pattern forming method capable of forming a resist film having sensitivity, CDU performance, and development residue suppression at a sufficient level even when next-generation technology is applied. [Means to solve the problem]

The inventors of the present invention have diligently studied to solve the present problem, and as a result, have found that the object can be achieved by adopting the following structure, and have completed the present invention.

（於所述式（1）中， R為氫原子、碳數1～5的烷基或碳數1～5的鹵化烷基，Y ¹為二價連結基，X ¹為酸解離性基。） In one embodiment, the present invention relates to a radiation-sensitive resin composition comprising: a resin comprising a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (I)"); One or more kinds of onium salts comprising an organic acid anion portion and an onium cation portion; and a solvent, wherein at least a part of the onium cation portion in the onium salt contains an aromatic ring structure having a fluorine atom. [chemical 1]

(In the formula (1), R is a hydrogen atom, an alkyl group with 1 to 5 carbons or a halogenated alkyl group with 1 to 5 carbons, Y ¹ is a divalent linking group, and X ¹ is an acid dissociative group. )

According to this radiation sensitive resin composition, the resist film which satisfies sensitivity, CDU performance, and development residue suppression property can be constructed. The reason for this is not certain, but it is presumed as follows. Fluorine atoms absorb very large radiation such as EUV with a wavelength of 13.5 nm, thereby making the radiation-sensitive resin composition highly sensitive. In addition, the water repellency of the resist film is improved by utilizing the aromatic ring structure having a fluorine atom contained in the onium cation part, and the intermixing between the resist film and the underlying film is also suppressed, and the development residue suppression property can be exhibited . Furthermore, the acid dissociative group possessed by the structural unit (I) in the resin has a high probability of contact with the acid generated by exposure due to the degree of freedom generated by the intervening linking group or the ester bond, so acid is easily generated. dissociation reaction. Therefore, the dissolution contrast between the exposed part and the unexposed part is improved, and excellent pattern formability can be exhibited. It is presumed that the above-mentioned resist performance can be exhibited by the composite action of these. Furthermore, the "aromatic ring structure having fluorine" includes not only the structure in which the fluorine atom is directly bonded to the aromatic ring structure, but also the structure in which the fluorine atom is bonded to the aromatic ring structure through other atoms (for example, a fluorine atom bonded to the aromatic ring structure). A structure bonded to a substituent of an aromatic ring structure, etc.).

In another embodiment, the present invention relates to a method for forming a pattern, comprising: directly or indirectly coating the radiation-sensitive resin composition on a substrate to form a resist film; exposing the resist film to light; and and developing the exposed resist film with a developer.

In this pattern forming method, since the radiation-sensitive resin composition excellent in sensitivity, CDU performance, and development residue suppression is used, a high-quality resist pattern can be efficiently formed.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments.

"Radiation Sensitive Resin Composition" The radiation-sensitive resin composition of the present embodiment (hereinafter also simply referred to as “composition”) includes a resin, one or two or more onium salts, and a solvent. The composition may contain other arbitrary components as long as the effect of the present invention is not impaired. When the radiation-sensitive resin composition contains a predetermined resin and an onium salt, high-level sensitivity, CDU performance, and development residue suppression can be imparted to the obtained resist film.

＜Resin＞ The resin is an aggregate of polymers including the structural unit (I) (hereinafter, this resin is also referred to as "base resin."). In addition to the structural unit (I), the base resin may also contain a structural unit having a phenolic hydroxyl group or a structural unit that provides a phenolic hydroxyl group through the action of an acid (hereinafter, the two are also collectively referred to as "structural unit (II) )".), Structural unit (III) containing a lactone structure, etc. Each structural unit will be described below.

（於所述式（1）中， R為氫原子、碳數1～5的烷基或碳數1～5的鹵化烷基，Y ¹為二價連結基，X ¹為酸解離性基。） (Structural Unit (I)) The structural unit (I) is represented by the following formula (1). [Chem 2]

(In the formula (1), R is a hydrogen atom, an alkyl group with 1 to 5 carbons or a halogenated alkyl group with 1 to 5 carbons, Y ¹ is a divalent linking group, and X ¹ is an acid dissociative group. )

In the above-mentioned formula (1), the alkyl group having 1 to 5 carbon atoms represented by R is preferably a linear or branched alkyl group, specifically, methyl, ethyl, propyl, etc. Base, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

In the above formula (1), examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R include those obtained by substituting a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms with halogen atoms. base. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, among which a fluorine atom is particularly preferred.

The divalent linking group of ^Y1 is not particularly limited, and a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like can be mentioned as preferable ones. The term "a hydrocarbon group having a substituent" means that some or all of the hydrogen atoms in the hydrocarbon group are substituted with substituents (groups or atoms other than hydrogen atoms). The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group refers to a hydrocarbon group not having aromaticity. The aliphatic hydrocarbon group as the divalent hydrocarbon group in Y ¹ may be saturated or unsaturated, and is usually preferably saturated. As this aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in a structure, etc. are mentioned more specifically.

The carbon number of the linear or branched aliphatic hydrocarbon group is preferably 1-10, more preferably 1-6, further preferably 1-4, most preferably 1-3. The straight-chain aliphatic hydrocarbon group is preferably a straight-chain alkylene group, specifically, methylene [-CH ₂ -], ethylidene [-(CH2) ₂ -], triethylene Methyl [-(CH ₂ ) ₃ -], tetramethylene [-(CH ₂ ) ₄ -], pentamethylene [-(CH ₂ ) ₅ -], etc. The branched aliphatic hydrocarbon group is preferably a branched alkylene group. Specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -etc. alkylmethylene ; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C( CH ₂ CH ₃ ) ₂ -CH ₂ -equal alkylethylidene; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -equal alkyltrimethylene; -CH(CH ₃ ) Alkyl alkylene such as CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, tetramethylene, etc. The alkyl group in the alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms. The linear or branched aliphatic hydrocarbon group may or may not have a substituent.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include: alicyclic hydrocarbon group (group obtained by removing two hydrogen atoms from the aliphatic hydrocarbon ring), alicyclic hydrocarbon group bonded to a straight or branched chain The terminal group of an aliphatic hydrocarbon group. The carbon number of the alicyclic hydrocarbon group is preferably 3-20, more preferably 3-12. The alicyclic hydrocarbon group can be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. As the monocycloalkane, one having 3 to 6 carbon atoms is preferable, and specifically, cyclopentane, cyclohexane, and the like are exemplified. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms. Specifically, diamond alkanes, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. The alicyclic hydrocarbon group may or may not have a substituent.

The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. The carbon number of the aromatic hydrocarbon group as the divalent hydrocarbon group in ^Y1 is preferably 3-30, more preferably 5-30, further preferably 5-20, particularly preferably 6-15, most preferably 6 ~10. However, the carbon number is set not including the carbon number in the substituent. As the aromatic ring possessed by the aromatic hydrocarbon group, specifically, aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene can be cited; Substituted aromatic heterocycles, etc. As a heteroatom in an aromatic heterocycle, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. As the aromatic hydrocarbon group, specifically, a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon group ring (aryl group); a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group); group) with one hydrogen atom replaced by an alkylene group (for example, from benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl The aryl group in the arylalkyl group such as the group after further removing a hydrogen atom) and the like. The carbon number of the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1-4, more preferably 1-2, particularly preferably 1. The aromatic hydrocarbon group may or may not have a substituent.

The heteroatom in the "divalent linking group including a heteroatom" in ^Y1 refers to an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, and the like. Examples of divalent linking groups containing heteroatoms include: -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O )-NH-, -NH- (H can be substituted by substituents such as alkyl, acyl, aryl, etc.), -S-, -S(=O) ₂ -, -S(=O) ₂ -O- , -NH-C(=O)-, =N-, general formula -Y ²¹ -OY ²² -, -[Y ²¹ -C(=O)-O] _mp -Y ²² -or -Y ²¹ -OC( A group represented by =O)-Y ²² -[wherein, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and mp is an integer of 0-3. ]Wait. When ^Y1 is -NH-, its H may be substituted with substituents such as alkyl, acyl, and aryl (aromatic groups). Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same groups as those listed above as the "divalent hydrocarbon group which may have a substituent" in ^Y1 . Y ²¹ is preferably a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, further preferably a straight-chain alkylene group having 1 to 5 carbon atoms, particularly preferably a methylene group. or ethylidene. Y ²² is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylidene group or an alkylmethylene group. As the divalent linking group containing a heteroatom, it is preferably a straight-chain group having an oxygen atom as a heteroatom, such as a group containing an ether bond or an ester bond, more preferably represented by the formula -Y ²¹ -OY ²² - , -[Y ²¹ -C(=O)-O] _mp -Y ²² - or -Y ²¹ -OC(=O)-Y ²² - represents a group.

Among the above, the divalent linking group of ^Y1 is particularly preferably a linear or branched chain alkylene group, a divalent alicyclic hydrocarbon group, or a divalent linking group containing a heteroatom. Among these, a linear or branched alkylene group, or a divalent linking group containing a heteroatom is preferred.

In the above-mentioned formula ( ¹ ), the so-called acid dissociative group represented by X1 means that at least the bond between the acid dissociative group and the atom adjacent to the acid dissociative group can be broken by the action of acid. acid dissociative base.

The acid-dissociating group is not particularly limited, but is widely known as a group that forms a cyclic or chain-like tertiary alkyl ester with a carboxyl group in (meth)acrylic acid, etc.; an acetal-type acid-dissociating group such as an alkoxyalkyl group Wait. Here, the so-called "tertiary alkyl ester" shows the following structure: an ester is formed by substituting a hydrogen atom of a carboxyl group with a chain or cyclic alkyl group, and in its carbonyloxy group (-C(=O) -O-) The tertiary carbon atom of the chain or cyclic alkyl group is bonded to the terminal oxygen atom. In this tertiary alkyl ester, when an acid acts, the bond between the oxygen atom and the tertiary carbon atom is cut to form a carboxyl group. The chain or cyclic alkyl group may have a substituent. Hereinafter, for the sake of convenience, a group that becomes acid-dissociable by constituting a carboxyl group and a tertiary alkyl ester is referred to as a "tertiary alkyl ester-type acid-dissociative group".

Examples of the tertiary alkyl ester-type acid-dissociating group include aliphatic branched-chain acid-dissociating groups and acid-dissociating groups containing aliphatic cyclic groups. Here, "aliphatic branched" means having a branched structure that does not have aromaticity. The structure of the "aliphatic branched acid-dissociating group" is not limited to a group (hydrocarbon group) containing carbon and hydrogen, but is preferably a hydrocarbon group. In addition, the "hydrocarbyl group" may be either saturated or unsaturated, but is usually preferably saturated. Examples of the aliphatic branched acid-dissociating group include groups represented by -C(R ⁷¹ )(R ⁷² )(R ⁷³ ). In the formula, R ⁷¹ to R ⁷³ are each independently a linear alkyl group having 1 to 5 carbons. Regarding the group represented by -C(R ⁷¹ )(R ⁷² )(R ⁷³ ), the number of carbon atoms is preferably 4 to 8, specifically, tert-butyl, 2-methyl-2-butyl , 2-methyl-2-pentyl, 3-methyl-3-pentyl, etc. Especially preferred is tert-butyl.

The "aliphatic cyclic group" means a monocyclic or polycyclic group that does not have aromaticity. The aliphatic cyclic group in the "acid dissociative group containing an aliphatic cyclic group" may have a substituent or may not have a substituent. The basic ring structure other than the substituent in the aliphatic ring group is not limited to a group (hydrocarbon group) containing carbon and hydrogen, but is preferably a hydrocarbon group. In addition, the hydrocarbon group may be either saturated or unsaturated, but is usually preferably saturated. The aliphatic cyclic group may be monocyclic or polycyclic. Examples of the aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from monocycloalkane, groups obtained by removing one or more hydrogen atoms from polycycloalkane such as bicycloalkane, tricycloalkane, and tetracycloalkane. In addition, some of the carbon atoms constituting the rings of these alicyclic hydrocarbon groups may be substituted with ether bonds (—O—).

Examples of acid-dissociating groups containing aliphatic ring groups include those represented by the following formulas (1-1) to (1-9), and the following formulas (2-1) to (2-6). Base etc.

[式中，R ¹⁴為烷基，g為0～8的整數。] [Chem 3]

[wherein, R ¹⁴ is an alkyl group, and g is an integer of 0-8. ]

[式中，R ¹⁵及R ¹⁶分別獨立地為烷基。] [chemical 4]

[wherein, R ¹⁵ and R ¹⁶ are each independently an alkyl group. ]

In formulas (1-1) to (1-9), the alkyl group of R ¹⁴ may be any of linear, branched, and cyclic, and is preferably linear or branched. The number of carbon atoms in the linear alkyl group is preferably 1-5, more preferably 1-4, still more preferably 1 or 2. The carbon number of the branched alkyl group is preferably 3-10, more preferably 3-5. Examples of the cyclic alkyl group include the same ones as those described above for the aliphatic cyclic group. g is preferably an integer of 0-3, more preferably an integer of 1-3, still more preferably 1 or 2. In formula (2-1) to formula (2-6), examples of the alkyl group for R ¹⁵ to R ¹⁶ include the same ones as the alkyl group for R ¹⁴ described above. In the formulas (1-1) to (1-9) and formulas (2-1) to (2-6), a part of the carbon atoms constituting the ring can also be passed through an etheric oxygen atom (-O-) replace. In addition, in formulas (1-1) to (1-9) and formulas (2-1) to (2-6), hydrogen atoms bonded to carbon atoms constituting the ring may be substituted with substituents.

In general, the "acetal-type acid dissociative group" is substituted with a hydrogen atom at the end of an OH-containing polar group such as a carboxyl group or a hydroxyl group, and bonded to an oxygen atom. Then, the acid acts to cut the bond between the acetal-type acid-dissociating group and the oxygen atom to which the acetal-type acid-dissociating group is bonded to form an OH-containing polar group such as a carboxyl group or a hydroxyl group.

（所述式（s1）中， Cy是與碳原子一起形成的脂肪族環式基。 Ra ⁰¹～Ra ⁰³分別獨立地為氫原子、碳數1～10的經取代或未經取代的一價鏈狀飽和烴基或碳數3～20的經取代或未經取代的一價脂肪族環狀飽和烴基，或者表示該些中的兩個以上彼此結合而形成的脂肪族環式結構，其中，該脂肪族環式結構不會形成交聯結構。 所述式（s2）中， Cy與所述式（s1）為相同含義。 Ra ⁰⁴為經取代或未經取代的芳香族烴基。 所述式中，＊均表示與氧原子的結合鍵。） X ¹ in the formula (1) is preferably represented by the following formula (s1) or formula (s2) in addition to the acid dissociative group. [chemical 5]

(In the formula (s1), Cy is an aliphatic ring group formed together with a carbon atom. Ra ⁰¹ to Ra ⁰³ are each independently a hydrogen atom, a substituted or unsubstituted monovalent group with 1 to 10 carbon atoms A chain saturated hydrocarbon group or a substituted or unsubstituted monovalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms, or an aliphatic ring structure formed by combining two or more of these, wherein the The aliphatic ring structure will not form a crosslinked structure. In the formula (s2), Cy has the same meaning as the formula (s1). Ra ⁰⁴ is a substituted or unsubstituted aromatic hydrocarbon group. In the formula , * all represent the bond with the oxygen atom.)

The aliphatic cyclic group represented by Cy may be a monocyclic group or a polycyclic group. Examples of the monocyclic aliphatic ring group include groups obtained by removing one or more hydrogen atoms from monocycloalkane. As the monocycloalkane, one having 3 to 6 carbon atoms is preferable, and specifically, cyclopentane, cyclohexane, and the like are exemplified. Examples of the polycyclic aliphatic ring group include groups obtained by removing one or more hydrogen atoms from polycycloalkane. Among these, a monocyclic aliphatic ring group is preferable, and a group obtained by removing one or more hydrogen atoms from cyclopentane or cyclohexane is more preferable.

A part or all of hydrogen atoms contained in the alicyclic group may be substituted.

In formula (s1), examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra ⁰¹ to Ra ⁰³ include an alkyl group having 1 to 10 carbon atoms. Examples of the monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms in Ra ⁰¹ to Ra ⁰³ include monocyclic aliphatic saturated hydrocarbon groups, polycyclic aliphatic saturated hydrocarbon groups, and the like. Among them, Ra ⁰¹ to Ra ⁰³ are particularly preferably hydrogen atoms from the viewpoint of easiness of synthesis of the monomer compound from which the structural unit (I) is derived.

The chain saturated hydrocarbon groups or aliphatic cyclic saturated hydrocarbon groups represented by Ra ⁰¹ to Ra ⁰³ may have substituents or may not have substituents.

The aliphatic cyclic group not having a crosslinked structure represented by Cy in formula (s2) is the same as the aliphatic cyclic group represented by Cy in formula (s1).

In formula (s2), examples of the aromatic hydrocarbon group in Ra ⁰⁴ include groups obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra ⁰⁴ is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, and most preferably a group obtained by removing one or more hydrogen atoms from benzene.

Specific examples of the acid-dissociating group represented by the formula (s1) are given below. * Indicates a bond.

[chemical 6]

[chemical 7]

Specific examples of the acid-dissociative group represented by the formula (s2) are given below. ＊Indicates a binding bond.

[chemical 8]

Specific examples of the structural unit represented by the formula (1) are shown below. In each formula, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[chemical 9]

[chemical 10]

[chemical 11]

[chemical 12]

Specific examples of the structural unit (I) having the acid dissociative group represented by the formula (s1) or the formula (s2) are shown below. In the following formulae, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

[chemical 13]

[chemical 14]

[chemical 15]

In the illustration, the structural unit (I) is preferably selected from the formula (a1-3-13) to the formula (a1-3-24), the formula (a1-3-33) to the formula (a1-3 -34), formula (s1-1) to formula (s1-4), formula (s2-1) to formula (s2-6), and at least one of the group consisting of structural units respectively represented.

In the resin, the content ratio of the structural unit (I) (total when there are multiple structural units (I)) is preferably at least 10 mol %, more preferably 20 mol %, relative to all the structural units constituting the resin. Mole % or more, and more preferably 30 Mole % or more. The content ratio is preferably not more than 70 mol%, more preferably not more than 60 mol%, and still more preferably not more than 50 mol%. By setting the content ratio of the structural unit (I) within the above-mentioned range, the radiation-sensitive resin composition can achieve further improvement in sensitivity and CDU performance.

(structural unit (II)) The structural unit (II) is a structural unit having a phenolic hydroxyl group or a structural unit provided with a phenolic hydroxyl group by the action of an acid. In the present invention, the phenolic hydroxyl group generated by deprotection by the action of acid generated by exposure is also included as the phenolic hydroxyl group of the structural unit (II). When the resin contains the structural unit (II), the solubility to the developer can be adjusted more appropriately, and as a result, the sensitivity and the like of the radiation-sensitive resin composition can be further improved. In addition, in the case of using KrF excimer laser light, EUV, electron beam, etc. as the radiation irradiated in the exposure step in the resist pattern forming method, the structural unit (II) contributes to the improvement of etching resistance, and Improvement of the developer solubility difference (dissolution contrast) between the exposed part and the unexposed part. In particular, it can be suitably applied to patterning using exposure to radiation with a wavelength of 50 nm or less such as an electron beam or EUV. The structural unit (II) is preferably represented by the following formula (2).

（所述式（2）中， R ^α為氫原子、氟原子、甲基或三氟甲基。 L ^CA為單鍵、-COO-*或-CONH-。*為芳香環側的結合鍵。 R ¹⁰¹為氫原子或於酸的作用下脫保護的保護基。於R ¹⁰¹存在多個的情況下，多個R ¹⁰¹彼此相同或不同。 R ¹⁰²為氰基、硝基、烷基、氟化烷基、烷氧基羰基氧基、醯基或醯氧基。於R ¹⁰²存在多個的情況下，多個R ¹⁰²彼此相同或不同。 n ₃為0～2的整數，m ₃為1～8的整數，m ₄為0～8的整數。其中，滿足1≦m ₃+m ₄≦2n ₃+5。） [chemical 16]

(In the formula (2), R ^α is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. L ^CA is a single bond, -COO-* or -CONH-. * is a bonding bond on the aromatic ring side. R ¹⁰¹ is a hydrogen atom or a protecting group that is deprotected under the action of an acid. When there are multiple R ^101s , the multiple R ^101s are the same or different from each other. R ¹⁰² is cyano, nitro, alkyl, fluorinated Alkyl, alkoxycarbonyloxy, acyl or acyloxy. When there are multiple R ¹⁰² , multiple R ¹⁰² are the same or different from each other. n ₃ is an integer of 0 to 2, m ₃ is 1 to 2 An integer of 8, and m ₄ is an integer of 0 to 8. Among them, 1≦m ₃ +m ₄ ≦2n ₃ +5 is satisfied.)

R ^α is preferably a hydrogen atom or a methyl group from the viewpoint of the copolymerizability of the monomer providing the structural unit (II).

L ^CA is preferably a single bond or -COO-*.

Examples of the protecting group deprotected by the action of an acid represented by R ¹⁰¹ include the same acid-dissociating groups as X ¹ in the formula (1).

Examples of the alkyl group in R ¹⁰² include linear or branched alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, and propyl groups. Examples of the fluorinated alkyl group include linear or branched fluorinated alkyl groups having 1 to 8 carbon atoms, such as trifluoromethyl and pentafluoroethyl. Examples of the alkoxycarbonyloxy group include chain or alicyclic alkoxy groups having 2 to 16 carbon atoms such as methoxycarbonyloxy, butoxycarbonyloxy, and adamantyl methoxycarbonyloxy. ylcarbonyloxy. Examples of the acyl group include aliphatic or aromatic acyl groups having 2 to 12 carbon atoms, such as an acetyl group, a propionyl group, a benzoyl group, and an acryl group. Examples of the acyloxy group include aliphatic or aromatic acyloxy groups having 2 to 12 carbon atoms such as acetyloxy, propionyloxy, benzoyloxy, and acryloxy.

As said n ₃ , 0 or 1 is more preferable, and 0 is still more preferable.

As said m ₃ , it is preferably an integer of 1-3, more preferably 1 or 2.

The m ₄ is preferably an integer of 0-3, more preferably an integer of 0-2.

The structural unit (II) is preferably a structural unit represented by the following formula (2a-1) to formula (2a-10) (hereinafter also referred to as "structural unit (2a-1) to structural unit ( 2a-10)".), etc.

[chemical 17]

In the formulas (2a-1) to (2a-10), R ^α is the same as the formula (2).

Among these, the structural unit (2a-1) to structural unit (2a-4), structural unit (2a-6), structural unit (2a-8) and structural unit (2a-9) are preferred.

The content ratio of the structural unit (II) (total when a plurality of structural units (II) are present) is preferably 5 mol% or more, more preferably 8 mol% with respect to all the structural units constituting the resin More than above, more preferably at least 10 mol%, particularly preferably at least 15 mol%. The content ratio is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 35 mol% or less, particularly preferably 30 mol% or less. By setting the content ratio of the structural unit (II) within the above-mentioned range, the radiation-sensitive resin composition can achieve further improvement in sensitivity and CDU performance.

In the case of polymerizing a monomer having a phenolic hydroxyl group such as hydroxystyrene, it is preferable to carry out the polymerization in a state where the phenolic hydroxyl group is protected by a protecting group such as an alkali dissociative group, and then perform hydrolysis and deprotection. This gives structural unit (II).

(structural unit (III)) The structural unit (III) is a structural unit including at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure. By further having the structural unit (III), the base resin can adjust the solubility to the developer, and as a result, the radiation-sensitive resin composition can improve lithography performance such as resolution. In addition, the adhesiveness between the resist pattern formed of the base resin and the substrate can be improved.

As a structural unit (III), the structural unit represented by following formula (T-1) - a formula (T-10), etc. are mentioned, for example.

[chemical 18]

In the above formula, R ^L1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ^L2 to R ^L5 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbons, a cyano group, a trifluoromethyl group, a methoxy group, a methoxycarbonyl group, a hydroxyl group, a hydroxymethyl group, and a dimethylamino group. R ^L4 and R ^L5 may be a bivalent alicyclic group having 3 to 8 carbons that is bonded to each other and constituted together with these bonded carbon atoms. L ² is a single bond or a divalent linking group. X is an oxygen atom or a methylene group. k is an integer of 0-3. m is an integer of 1-3.

As the divalent alicyclic group having 3 to 8 carbon atoms that is bonded to each other and constitutes the bonded carbon atoms above R ^L4 and R ^L5 , as long as it is a monocyclic or polycyclic group that constitutes the above carbon number The group obtained by removing two hydrogen atoms from the same carbon atom of the carbocyclic ring of the alicyclic hydrocarbon is not particularly limited. It can be any one of monocyclic hydrocarbon group and polycyclic hydrocarbon group. As a polycyclic hydrocarbon group, it can be any one of bridged ring alicyclic hydrocarbon group and condensed alicyclic hydrocarbon group, and it can also be a saturated hydrocarbon group and not Any of the saturated hydrocarbon groups. In addition, the condensed alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group constituted such that a plurality of alicyclic rings share a side (a bond between two adjacent carbon atoms).

As the divalent linking group represented by L ² , for example, a divalent linear or branched hydrocarbon group having 1 to 10 carbons, a divalent alicyclic hydrocarbon group having 4 to 12 carbons, or a divalent alicyclic hydrocarbon group composed of A group composed of one or more of these hydrocarbon groups and at least one of -CO-, -O-, -NH-, and -S-, etc.

As the structural unit (III), among these, a structural unit containing a lactone structure is preferable, a structural unit containing a norbornane lactone structure is more preferable, and a structural unit derived from norbornane (meth)acrylate is more preferable. Ester - The structural unit of an ester.

The content ratio of the structural unit (III) (total when a plurality of structural units (III) are present) is preferably at least 5 mol %, more preferably 10 mol %, based on all the structural units constituting the base resin % or more, and more preferably 15 mol% or more. The content ratio is preferably not more than 50 mol%, more preferably not more than 40 mol%, and still more preferably not more than 35 mol%. By making the content ratio of the structural unit (III) into the said range, this radiation-sensitive resin composition can further improve the lithography performance, such as resolution, and the adhesiveness of the formed resist pattern and a board|substrate.

(other structural units) The base resin optionally has other structural units other than the structural units (I) to (III) described above. As the other structural unit, for example, a structural unit (IV) containing a polar group (except for those corresponding to the structural unit (II) and structural unit (III).) or other structural unit having an acid dissociative group ( V) (except for those corresponding to the structural unit (I).), etc.

(structural unit (IV)) The base resin further has a structural unit (IV), whereby the solubility to a developer can be adjusted, and as a result, the lithography performance such as resolution of the radiation-sensitive resin composition can be improved. As said polar group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a sulfonamide group etc. are mentioned, for example. Among these, a hydroxyl group and a carboxyl group are preferable, and a hydroxyl group is more preferable.

As a structural unit (IV), the structural unit etc. which are represented by the following formula are mentioned, for example.

[chemical 19]

In the above formula, R ^A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

When the base resin has a structural unit (IV), the lower limit of the content ratio of the structural unit (IV) (total when multiple structural units (IV) exist) is preferable to all structural units constituting the base resin It is 1 mol%, more preferably 5 mol%, and still more preferably 10 mol%. In addition, the upper limit of the content ratio is preferably 40 mol%, more preferably 30 mol%, and still more preferably 25 mol%. By setting the content ratio of the structural unit (IV) within the above-mentioned range, the lithography performance such as resolution of the radiation-sensitive resin composition can be further improved.

(structural unit (V)) The structural unit (V) is a structural unit containing an acid dissociative group (however, it is different from the structural unit (I) and the structural unit (II).). The structural unit (V) is not particularly limited as long as it contains an acid-dissociating group, for example, a structural unit having a tertiary alkyl ester moiety, a structure having a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a tertiary alkyl group Units, structural units having an acetal bond, etc., are preferably structural units represented by the following formula (3) (hereinafter also referred to as " Structural Unit (V-1)").

[chemical 20]

In the formula (3), R ⁷ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ⁸ is a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ⁹ and R ¹⁰ are each independently a monovalent chain hydrocarbon group with 1 to 10 carbons or a monovalent alicyclic hydrocarbon group with 3 to 20 carbons, or represents that these groups are combined with each other and the carbons to which these groups are bonded A divalent alicyclic group having 3 to 20 carbon atoms constituted by atoms together.

R ⁷ is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of the copolymerizability of the monomer providing the structural unit (V-1).

As the monovalent hydrocarbon group having 1 to 20 carbons represented by R ⁸ , for example, a chain hydrocarbon group having 1 to 10 carbons, a monovalent alicyclic hydrocarbon group having 3 to 20 carbons, a monovalent alicyclic hydrocarbon group having 6 to 20 carbons, Monovalent aromatic hydrocarbon groups, etc.

Examples of the chain hydrocarbon groups having 1 to 10 carbons represented by R ⁸ to R ¹⁰ include linear or branched saturated hydrocarbon groups with 1 to 10 carbons, or linear or branched saturated hydrocarbon groups with 1 to 10 carbons. Saturated hydrocarbon group.

Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ⁸ to R ¹⁰ include a monocyclic or polycyclic saturated hydrocarbon group, or a monocyclic or polycyclic unsaturated hydrocarbon group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ⁸ include: aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracenyl; benzyl, phenethyl, Aralkyl groups such as naphthylmethyl, etc.

R ⁸ is preferably a linear or branched saturated hydrocarbon group with 1 to 5 carbons, a linear or branched unsaturated hydrocarbon group with 1 to 5 carbons, an alicyclic hydrocarbon group with 3 to 12 carbons, a carbon A monovalent aromatic hydrocarbon group with a number of 6-12.

The groups represented by R ⁹ and R ¹⁰ are combined with each other and the divalent alicyclic group with 3 to 20 carbon atoms formed together with these bonded carbon atoms can be a monocyclic hydrocarbon group or a polycyclic hydrocarbon group. either of.

Among these, R ⁸ is preferably an alkyl group with 1 to 4 carbon atoms, R ⁹ and R ¹⁰ are combined with each other and the alicyclic structure formed together with these bonded carbon atoms is a polycyclic or monocyclic ring alkane structure.

As the structural unit (V-1), for example, structural units represented by the following formula (3-1) to formula (3-6) (hereinafter also referred to as "structural unit (V-1-1) to structural unit (V-1-6)"), etc.

[chem 21]

In the formula (3-1) to the formula (3-6), R ⁷ to R ¹⁰ have the same meaning as the formula (3). i and j are each independently an integer of 1-4. k and l are 0 or 1.

As i and j, 1 is preferable. R ⁸ is preferably methyl, ethyl or isopropyl. R ⁹ and R ¹⁰ are preferably methyl or ethyl.

The base resin may contain one kind or two or more kinds of structural units (V) in combination.

When the base resin contains the structural unit (V), the lower limit of the content ratio of the structural unit (V) to all the structural units constituting the base resin (in the case of including multiple types, the total content ratio) is preferably 3 Mole %, more preferably 5 Mole %, further preferably 10 Mole %. In addition, the upper limit of the content ratio is preferably 50 mol%, more preferably 40 mol%, and still more preferably 30 mol%. By making the content ratio of a structural unit (V) into the said range, the pattern formability of this radiation sensitive resin composition can be improved further.

(Synthesis method of resin) The resin as the base resin can be synthesized by, for example, using a known radical polymerization initiator or the like to polymerize monomers providing each structural unit in an appropriate solvent.

The molecular weight of the resin used as the base resin is not particularly limited, but the lower limit of the polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) is preferably 1,000, more preferably 2,000 , and more preferably 3,000, particularly preferably 4,000. In addition, the upper limit of Mw is preferably 50,000, more preferably 30,000, further preferably 15,000, and most preferably 12,000. When the Mw of resin exists in the said range, the heat resistance and developability of the resist film obtained are favorable.

The ratio (Mw/Mn) of the Mw of the resin as the base resin to the polystyrene-equivalent number average molecular weight (Mn) obtained by GPC is usually 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably Preferably, it is 1 or more and 2 or less.

The measuring methods of Mw and Mn of the resin in this specification are as described in an Example.

The content of the resin is preferably at least 70% by mass, more preferably at least 75% by mass, and still more preferably at least 80% by mass, based on the total solid content of the radiation-sensitive resin composition.

＜Other resins＞ The radiation-sensitive resin composition of the present embodiment may contain, as another resin, a resin having a mass content ratio of fluorine atoms higher than that of the base resin (hereinafter also referred to as "high fluorine content resin"). In the case where the radiation-sensitive resin composition contains a resin with a high fluorine content, it may exist in a biased manner on the surface layer of the resist film relative to the base resin. As a result, the state of the surface of the resist film or the state of the resist film may be changed The component distribution in the film is controlled to a desired state.

As the high fluorine content resin, it is preferable to have, for example, a structural unit represented by the following formula (6) in addition to the structural unit (I) to structural unit (V) in the base resin alone or in combination, if necessary. (Hereinafter, it is also referred to as "structural unit (VI)".). [chem 22]

In the formula (6), R ¹³ is a hydrogen atom, a methyl group or a trifluoromethyl group. G is a single bond, an oxygen atom, a sulfur atom, -COO-, -SO ₂ ONH-, -CONH- or -OCONH-. R ¹⁴ is a monovalent fluorinated chain hydrocarbon group with 1 to 20 carbons or a monovalent fluorinated alicyclic hydrocarbon group with 3 to 20 carbons.

When the high fluorine content resin has a structural unit (VI), the lower limit of the content ratio of the structural unit (VI) is preferably 50 mole %, more preferably 60 mol%, more preferably 70 mol%, especially preferably 80 mol%. The upper limit of the content ratio is preferably 100 mol%, more preferably 98 mol%, and still more preferably 95 mol%. By setting the content ratio of the structural unit (VI) within the above-mentioned range, the mass content ratio of fluorine atoms in the high-fluorine content resin can be adjusted more appropriately, and the biased presence in the surface layer of the resist film can be further promoted.

In addition to the structural unit (VI), the high fluorine content resin may also contain structural units with (x) alkali-soluble groups or (y) groups that are dissociated by the action of alkali and have increased solubility in alkaline developing solutions ( Hereinafter, it is also referred to as a structural unit (VII).). Since the resin with high fluorine content has the structural unit (VII), the solubility to the alkaline developing solution is improved, and the generation of developing defects can be suppressed.

In the case where the high fluorine content resin has a structural unit (VII), the lower limit of the content ratio of the structural unit (VII) is preferably 10 mol %, more preferably 20 mol%, more preferably 30 mol%, especially preferably 35 mol%. The upper limit of the content ratio is preferably 90 mol%, more preferably 75 mol%, and still more preferably 60 mol%. By setting the content ratio of the structural unit (VII) within the above range, the water repellency of the resist film during liquid immersion exposure can be further improved.

The lower limit of the content of the high fluorine content resin is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, still more preferably 1 part by mass, particularly preferably 1.5 parts by mass, based on 100 parts by mass of the base resin. The upper limit of the content is preferably 12 parts by mass, more preferably 10 parts by mass, further preferably 8 parts by mass, and particularly preferably 5 parts by mass.

(Synthesis method of resin with high fluorine content) The high fluorine content resin can be synthesized by the same method as that of the base resin.

＜Onium salt＞ The onium salt includes an organic acid anion portion and an onium cation portion, and is a component that generates an acid upon exposure. When at least a part of the onium cation moiety in the onium salt contains an aromatic ring structure having a fluorine atom, high sensitivity and development residue suppression by improving acid generation efficiency can be achieved.

The content form of the onium salt in the radiation-sensitive resin composition is not particularly limited, but the onium salt is preferably at least one selected from the group consisting of the organic acid anion moiety and the onium salt. A radiation-sensitive acid generator of a cationic moiety; and an acid comprising the organic acid radical anion moiety and the onium cation moiety, and generating an acid having a higher pKa than an acid generated from the radiation-sensitive acid generator by irradiation with radiation acid diffusion controller. The difference between these functions will be described below.

It is considered that the acid generated by exposure to the onium salt performs two functions in the radiation-sensitive resin composition according to the strength of the acid. As the first function, when the resin includes a structural unit having an acid-dissociable group, the acid generated by exposure dissociates the acid-dissociable group contained in the structural unit to generate a carboxyl group or the like. Onium salts having this first function are called radiation-sensitive acid generators. As the second function, the following function can be cited: Under the pattern forming conditions using the above-mentioned radiation-sensitive resin composition, the acid dissociative group possessed by the resin is not substantially dissociated, and the unexposed part is replaced by a salt. to inhibit the diffusion of acid generated from the radiation-sensitive acid generator. Onium salts having this second function are called acid diffusion controllers. The acid generated from the acid diffusion controller can be said to be a relatively weak acid (acid with high pKa) than the acid generated from the self-induced radioactive acid generator. Whether the onium salt functions as a radiation-sensitive acid generator or as an acid diffusion control agent depends on the energy required for dissociation of the acid-dissociative group of the resin, the acidity of the onium salt, and the like. The form in which the radiation-sensitive acid generator is contained in the radiation-sensitive resin composition is preferably a form in which the onium salt structure exists alone as a (low molecular weight) compound.

By containing the radiation-sensitive acid generator in the radiation-sensitive resin composition, the polarity of the resin in the exposed portion increases, and the resin in the exposed portion becomes soluble in a developing solution in the case of developing with an alkaline aqueous solution. On the other hand, , in the case of organic solvent development, it becomes insoluble in the developing solution.

In addition, the radiation-sensitive resin composition can suppress the diffusion of acid in the unexposed part by containing the above-mentioned acid diffusion control agent, and can form a resist pattern more excellent in pattern developability and CDU performance.

In the radiation-sensitive resin composition, it is preferable that at least one of the organic acid anion portion of the radiation-sensitive acid generator and the organic acid anion portion of the acid diffusion controller includes an iodine-substituted aromatic ring structure. Iodine atoms absorb very large radiation such as EUV with a wavelength of 13.5 nm, thereby making it highly sensitive. In addition, if the organic acid anion part of the onium salt contains an iodine-substituted aromatic ring structure, the large molecular weight of the iodine atom can be used to control the acid diffusion and improve the performance of the CDU. When the organic acid anion portion of the onium salt contains an iodine-substituted aromatic ring structure, the iodine-substituted aromatic ring structure and the aromatic ring structure having a fluorine atom may exist in the same compound or in different compounds.

Regardless of the content form of the onium salt, the organic acid anion portion preferably has at least one selected from the group consisting of sulfonate anions, carboxylate anions, and sulfonimide anions. In addition, the onium cation is preferably at least one selected from the group consisting of perium cations and odonium cations. The onium salt can efficiently exhibit the above-mentioned functions by having these structures in combination.

Examples of the acid generated by exposure include those that generate sulfonic acid, carboxylic acid, and sulfonimide by exposure, corresponding to the above-mentioned organic acid radical anion.

For example, examples of onium salts that provide sulfonic acid by exposure include: (1) Compounds with more than one fluorine atom or fluorinated hydrocarbon group bonded to the carbon atom adjacent to the sulfonate anion, (2) A compound in which neither a fluorine atom nor a fluorinated hydrocarbon group is bonded to a carbon atom adjacent to a sulfonate anion.

Examples of onium salts that provide carboxylic acid by exposure include: (3) Compounds with more than one fluorine atom or fluorinated hydrocarbon group bonded to the carbon atom adjacent to the carboxylate anion, (4) A compound in which neither a fluorine atom nor a fluorinated hydrocarbon group is bonded to a carbon atom adjacent to a carboxylate anion.

Among these, those corresponding to (1) above are preferable as the radiation-sensitive acid generator. The acid diffusion controller is preferably one corresponding to (2), (3) or (4) above, and particularly preferably one corresponding to (2) or (4).

＜Radiation sensitive acid generator＞ The onium salt as a radiation-sensitive acid generator contains an organic acid anion moiety and an onium cation moiety. The radiation-sensitive acid generator is preferably represented by the following formula (A-1) or the following formula (A-2).

[chem 23]

In formulas (A-1) and (A-2), L ¹ is a single bond, an ether bond, or an ester bond, or a C1-6 alkylene group that may contain an ether bond or an ester bond. The alkylene group may be linear, branched, or cyclic.

R1 is ^a hydroxyl group, a carboxyl group, a fluorine atom, a chlorine atom, a bromine atom or an amino group, or a carbon number 1 that may contain a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, an amino group, or an alkoxy group with 1 to 10 carbon atoms Alkyl with ∼20 carbons, alkoxy with 1 to 20 carbons, alkoxycarbonyl with 2 to 10 carbons, acyloxy with 2 to 20 carbons or alkylsulfonyloxy with 1 to 20 carbons , or -NR ⁸ -C(=O)-R ⁹ or -NR ⁸ -C(=O)-OR ⁹ , R ⁸ is a hydrogen atom or may contain a halogen atom, hydroxyl, or an alkoxy group with 1 to 6 carbons , an acyl group with 2 to 6 carbons or an alkyl group with 1 to 6 carbons in an acyloxy group with 2 to 6 carbons, ^R9 is an alkyl group with 1 to 16 carbons, an alkenyl group with 2 to 16 carbons or The aryl group having 6 to 12 carbons may contain a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbons, an acyl group having 2 to 6 carbons or an acyloxy group having 2 to 6 carbons. The alkyl, alkoxy, alkoxycarbonyl, acyloxy, acyl and alkenyl groups may be linear, branched or cyclic.

Among these, R ¹ is preferably a hydroxyl group, -NR ⁸ -C(=O)-R ⁹ , a fluorine atom, a chlorine atom, a bromine atom, a methyl group, or a methoxy group.

When p is ¹ , R2 is a single bond or a divalent linking group with 1 to 20 carbons; when p is ² or 3, R2 is a trivalent or tetravalent linking group with 1 to 20 carbons, and the linking The radical may contain an oxygen atom, a sulfur atom or a nitrogen atom.

Rf ¹ to Rf ⁴ are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, but at least one of these is a fluorine atom or a trifluoromethyl group. In addition, Rf ¹ and Rf ² can also combine to form a carbonyl group. It is especially preferable that both Rf ³ and Rf ⁴ are fluorine atoms.

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a monovalent hydrocarbon group having 1 to 20 carbons which may contain heteroatoms. R ³ , R ⁴ and R ⁵ contain one or more fluorine atoms, and R ⁶ and R ⁷ contain one or more fluorine atoms. In addition, any two of R ³ , R ⁴ and R ⁵ may be bonded to each other and form a ring together with the bonded sulfur atoms. The monovalent hydrocarbon group may be any of linear, branched, and cyclic, and specific examples thereof include: an alkyl group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, an alkenyl group having 2 to 12 carbons, Alkynyl with 2 to 12 carbons, aryl with 6 to 20 carbons, aralkyl with 7 to 12 carbons, etc. In addition, a part or all of the hydrogen atoms of these groups may be substituted by hydroxyl, carboxyl, halogen atom, cyano, amido, nitro, mercapto, sultone, sulfo, or a group containing alumium salt. A part of the carbon atoms of the group may be substituted by an ether bond, an ester bond, a carbonyl group, a carbonate group or a sulfonate bond.

p is an integer satisfying 1≦p≦3. q and r are integers satisfying 0≦q≦5, 0≦r≦3, and 0≦q+r≦5. q is preferably an integer satisfying 1≦q≦3, more preferably 2 or 3. r is preferably an integer satisfying 0≦r≦2.

Examples of the organic acid anion moiety of the radiation-sensitive acid generator represented by the formula (A-1) and the formula (A-2) include those shown below, but are not limited thereto. Furthermore, the ones shown below are organic acid radical anion moieties having an iodine-substituted aromatic ring structure, but as organic acid radical anion moieties that do not have an iodine-substituted aromatic ring structure, hydrogen atoms or other substituents, etc. can be preferably used. A structure in which the iodine atom in the following formula is substituted by an atom or group other than an iodine atom.

[chem 24]

[chem 25]

[chem 26]

[chem 27]

[chem 28]

[chem 29]

[chem 30]

[chem 31]

[chem 32]

[chem 33]

[chem 34]

[chem 35]

[chem 36]

[chem 37]

The onium cation moiety in the radiation-sensitive acid generator represented by the formula (A-1) is preferably represented by the following formula (Q-1).

[chem 38]

In the formula (Q-1), Ra1 and Ra2 each independently represent a substituent. n1 represents the integer of 0-5, and when n1 is 2 or more, Ra1 which exists in some numbers may be the same or different. n2 represents the integer of 0-5, and when n2 is 2 or more, Ra2 which exists in some numbers may be the same or different. n3 represents the integer of 0-5, and when n3 is 2 or more, Ra3 which exists in some numbers may be the same or different. Ra3 represents a fluorine atom or a group having one or more fluorine atoms. Ra1 and Ra2 may be connected to each other to form a ring. When n1 is 2 or more, some Ra1 may connect mutually and form a ring. When n2 is 2 or more, several Ra2 may connect mutually and form a ring.

The substituent represented by Ra1 and Ra2 is preferably an alkyl group, cycloalkyl group, alkoxy group, cycloalkyloxy group, alkoxycarbonyl group, alkylsulfonyl group, hydroxyl group, halogen atom, or halogenated hydrocarbon group.

The alkyl groups of Ra1 and Ra2 may be linear or branched. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably a methyl group, ethyl group, n-butyl group and tert-butyl group.

Examples of the cycloalkyl group for Ra1 and Ra2 include monocyclic or polycyclic cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms). Among these, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl are particularly preferred.

As the alkyl moiety of the alkoxy group of Ra1 and Ra2, for example, those mentioned above as the alkyl group of Ra1 and Ra2 are mentioned. As the alkoxy group, particularly preferred are methoxy, ethoxy, n-propoxy and n-butoxy.

As the cycloalkyl moiety of the cycloalkyloxy group of Ra1 and Ra2, for example, those mentioned above as the cycloalkyl group of Ra1 and Ra2 are mentioned. As the cycloalkyloxy group, cyclopentyloxy group and cyclohexyloxy group are particularly preferable.

As an alkoxy part of the alkoxycarbonyl group of Ra1 and Ra2, what was mentioned previously as an alkoxy group of Ra1 and Ra2 is mentioned, for example. As the alkoxycarbonyl group, particularly preferred are methoxycarbonyl, ethoxycarbonyl and n-butoxycarbonyl.

As the alkyl moiety of the alkylsulfonyl group of Ra1 and Ra2, for example, those mentioned above as the alkyl group of Ra1 and Ra2 are mentioned. In addition, examples of the cycloalkyl moiety of the cycloalkylsulfonyl group of Ra1 and Ra2 include those listed above as the cycloalkyl group of Ra1 and Ra2. As these alkylsulfonyl or cycloalkylsulfonyl groups, particularly preferred are methylsulfonyl, ethanesulfonyl, n-propanesulfonyl, n-butanesulfonyl, cyclopentylsulfonyl, and cyclohexanesulfonyl. Acyl group.

Each group of Ra1 and Ra2 may further have a substituent. Examples of such substituents include halogen atoms such as fluorine atoms (preferably fluorine atoms), hydroxyl groups, carboxyl groups, cyano groups, nitro groups, alkoxy groups, cycloalkyloxy groups, alkoxyalkyl groups, and cycloalkane groups. oxyalkyl, alkoxycarbonyl, cycloalkyloxycarbonyl, alkoxycarbonyloxy, and cycloalkyloxycarbonyloxy.

Examples of the halogen atom for Ra1 and Ra2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom.

The halogenated hydrocarbon groups of Ra1 and Ra2 are preferably halogenated alkyl groups. Examples of the alkyl group and the halogen atom constituting the halogenated alkyl group include the same ones as those described above. Among them, fluorinated alkyl groups are preferred, and CF ₃ is more preferred.

As described above, Ra1 and Ra2 may be connected to each other to form a ring (ie, a heterocyclic ring including a sulfur atom). In this case, Ra1 and Ra2 preferably form a single bond or a divalent linking group, and examples of the divalent linking group include -COO-, -OCO-, -CO-, -O-, -S-, -SO -, -SO ₂ -, an alkylene group, a cycloalkylene group, an alkenylene group, or a combination of two or more thereof, preferably having a total carbon number of 20 or less. Moreover, when n1 is 2 or more, several Ra1 may connect mutually and form a ring, and when n2 is 2 or more, several Ra2 may connect mutually and form a ring. As such an example, for example, an aspect in which two Ra1 are linked to each other to form a naphthalene ring together with these linked benzene rings can be mentioned.

Ra3 is a fluorine atom or a group having a fluorine atom. Examples of the group having a fluorine atom include groups in which the alkyl group, cycloalkyl group, alkoxy group, cycloalkyloxy group, alkoxycarbonyl group and alkylsulfonyl group of Ra1 and Ra2 are substituted with a fluorine atom. Among them, preferably fluorinated alkyl groups, more preferably 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 , particularly preferably CF ₃ .

Ra3 is preferably a fluorine atom or CF ₃ , more preferably a fluorine atom.

n1 and n2 are each independently preferably an integer of 0-3, more preferably an integer of 0-2.

n3 is preferably an integer of 1-3, more preferably 1 or 2.

(n1+n2+n3) is preferably an integer of 1-15, more preferably an integer of 1-9, further preferably an integer of 2-6, particularly preferably an integer of 3-6. When (n1+n2+n3) is 1, preferably n3=1 and Ra3 is a fluorine atom or CF ₃ . When (n1+n2+n3) is 2, preferably n1=n3=1 and Ra1 and Ra3 are each independently a combination of a fluorine atom or CF ₃ , and n3=2 and Ra3 is a fluorine atom or CF ₃ The combination. When (n1+n2+n3) is 3, preferably n1=n2=n3=1 and Ra1 to Ra3 are each independently a combination of a fluorine atom or CF ₃ .

Specific examples of the onium cation moiety represented by such formula (Q-1) include the following. Furthermore, the ones shown below are all cation moieties containing an aromatic ring structure having a fluorine atom, but as the onium cation moiety not containing an aromatic ring structure having a fluorine atom, it is preferable to use a hydrogen atom or other substitutions. A structure in which a fluorine atom or CF ₃ in the following formula is substituted by an atom or group other than a fluorine atom such as a group.

[chem 39]

[chemical 40]

[chem 41]

In the case where the onium cation moiety in the radiation-sensitive acid generator represented by the formula (A-2) contains an aromatic ring structure having a fluorine atom, the onium cation moiety is preferably a diaryl ring structure having one or more fluorine atoms. Odonium cations.

Specific examples of such onium cation moieties include the following. Furthermore, the ones shown below are all oxonium cation moieties containing an aromatic ring structure having a fluorine atom, but as an onium cation moiety not containing an aromatic ring structure having a fluorine atom, it is preferable to use a hydrogen atom or other substituted A structure in which a fluorine atom or CF ₃ in the following formula is substituted by an atom or group other than a fluorine atom such as a group.

[chem 42]

The synthesis method of the radiation sensitive acid generator represented by said formula (A-1) and formula (A-2) can also synthesize|combine by a well-known method, especially a salt exchange reaction. Known radiation-sensitive acid generators can also be used as long as the effects of the present invention are not impaired.

These radiation-sensitive acid generators may be used alone or in combination of two or more. The lower limit of the content of the radiation-sensitive acid generator is preferably 0.5 parts by mass, more preferably 1 part by mass, further preferably 2 parts by mass, particularly preferably 4 parts by mass, based on 100 parts by mass of the base resin. In addition, the upper limit of the content is preferably 20 parts by mass, more preferably 18 parts by mass, further preferably 15 parts by mass, particularly preferably 12 parts by mass. Thereby, excellent sensitivity or CDU performance can be exhibited when forming a resist pattern.

＜Acid diffusion control agent＞ The onium salt as an acid diffusion control agent contains an anion portion of an organic acid group and an onium cation portion, and generates an acid having a higher pKa than the acid generated from the radiation-sensitive acid generator when irradiated with radiation. The acid diffusion controller is preferably represented by the following formula (S-1) or the following formula (S-2).

[chem 43]

In formula (S-1) and formula (S-2), R ¹ is hydrogen atom, hydroxyl, fluorine atom, chlorine atom, amino group, nitro group or cyano group; Alkyl, alkoxy with 1 to 6 carbons, acyloxy with 2 to 6 carbons or alkylsulfonyloxy with 1 to 4 carbons; or -NR ^1A -C(=O)-R ^1B or -NR ^1A -C(=O)-OR ^1B . R ^1A is a hydrogen atom or an alkyl group having 1 to 6 carbons, and R ^1B is an alkyl group having 1 to 6 carbons or an alkenyl group having 2 to 8 carbons.

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a monovalent hydrocarbon group having 1 to 20 carbons which may contain heteroatoms. R ³ , R ⁴ and R ⁵ are preferably monovalent hydrocarbon groups containing one or more fluorine atoms or groups having fluorine atoms, and R ⁶ and R ⁷ are preferably one group containing one or more fluorine atoms or groups having fluorine atoms. Valence hydrocarbon group. In addition, any two of R ³ , R ⁴ and R ⁵ may be bonded to each other and form a ring together with the bonded sulfur atoms. The monovalent hydrocarbon group may be any of linear, branched, and cyclic, and specific examples thereof include: an alkyl group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, an alkenyl group having 2 to 12 carbons, Alkynyl with 2 to 12 carbons, aryl with 6 to 20 carbons, aralkyl with 7 to 12 carbons, etc. In addition, some or all of the hydrogen atoms in these groups may be substituted with substituents.

L is a single bond, or a divalent linking group with ¹ to 20 carbons, and may also include an ether bond, a carbonyl group, an ester bond, an amide bond, a sultone ring, a lactamide ring, a carbonate bond, a halogen atom, hydroxyl or carboxyl.

m and n are integers satisfying 0≦m≦5, 0≦n≦3, and 0≦m+n≦5, but preferably integers satisfying 1≦m≦3 and 0≦n≦2.

Examples of the anion of the acid diffusion controller represented by the formula (S-1) or formula (S-2) include those shown below, but are not limited thereto. Furthermore, the ones shown below are organic acid radical anion moieties having an iodine-substituted aromatic ring structure, but as organic acid radical anion moieties that do not have an iodine-substituted aromatic ring structure, hydrogen atoms or other substituents, etc. can be preferably used. A structure in which the iodine atom in the following formula is substituted by an atom or group other than an iodine atom.

[chem 44]

[chem 45]

[chem 46]

[chem 47]

[chem 48]

As the onium cation moiety in the acid diffusion control agent represented by the above formula (S-1) and formula (S-2), the onium cation moiety in the radiation-sensitive acid generator can be preferably used.

The acid diffusion control agents represented by the formulas (S-1) and (S-2) can also be synthesized by known methods, especially salt exchange reactions. Known acid diffusion control agents can also be used as long as the effect of the present invention is not impaired. In addition, the case where the organic acid anion part and the onium cation part share the same aromatic ring structure is also included in the acid diffusion control agent of this embodiment.

These acid diffusion control agents may be used alone or in combination of two or more. The lower limit of the content of the acid diffusion controller is preferably 0.5 parts by mass, more preferably 1 part by mass, and still more preferably 1.5 parts by mass relative to 100 parts by mass of the base resin. In addition, the upper limit of the content is preferably 15 parts by mass, more preferably 12 parts by mass, and still more preferably 8 parts by mass. Thereby, excellent sensitivity or CDU performance can be exhibited when forming a resist pattern.

(Structure (1) of the anion moiety of other organic acids) Radiation-sensitive acid generators (including both radiation-sensitive strong acid generators and acid diffusion control agents.) can also be used in the radiation-sensitive strong acid generators represented by the above-mentioned formula (A-1) and formula (A-2). On the basis of or instead of the organic acid anion part of the organic acid anion part or the acid diffusion control agent represented by the formula (S-1) or formula (S-2), the following formula (bd1) is included The structure of the organic acid radical anion part.

[chem 49]

為雙鍵或單鍵。 R ^z1～R ^z4分別獨立地為氫原子、經取代或未經取代的烴基，或者表示該些中的兩個以上彼此結合而形成的環結構。但是，R ^x1～R ^x4、R ^y1～R ^y2及R ^z1～R ^z4中的至少一個具有酸根陰離子結構。 In the formula (bd1), R ^x1 to R ^x4 are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a ring structure formed by combining two or more of these. R ^y1 to R ^y2 are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a ring structure formed by combining with each other. [chemical 50]

for double or single bonds. R ^z1 to R ^z4 are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a ring structure formed by combining two or more of these. However, at least one of R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 has an acid anion structure.

The hydrocarbon groups in R ^x1 to R ^x4 , R ^y1 to R ^y2 and R ^z1 to R ^z4 may be aliphatic hydrocarbon groups, aromatic hydrocarbon groups, cyclic hydrocarbon groups, or chain hydrocarbon groups . For example, examples of hydrocarbon groups which may have substituents among R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 include cyclic groups which may have substituents, chain-like alkyl groups which may have substituents group, or a chain alkenyl group which may have a substituent.

The cyclic group which may have a substituent is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group refers to a hydrocarbon group not having aromaticity. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, but saturation is generally preferred. In addition, the cyclic hydrocarbon groups in R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 may contain heteroatoms such as heterocycles.

The aromatic hydrocarbon groups in R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 are hydrocarbon groups having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbons, more preferably 5 to 30 carbons, further preferably 5 to 20 carbons, particularly preferably 6 to 15 carbons, most preferably 6 to 12 carbons . However, the carbon number is set not including the carbon number in the substituent.

As the aromatic ring possessed by the aromatic hydrocarbon group in R ^x1 to R ^x4 , R ^y1 to R ^y2 and R ^z1 to R ^z4 , specifically, benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or An aromatic heterocyclic ring in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, and the like.

Specific examples of the aromatic hydrocarbon group in R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 include groups obtained by removing one hydrogen atom from the aromatic ring.

The cyclic aliphatic hydrocarbon groups in R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 include aliphatic hydrocarbon groups containing a ring in their structure. Examples of the aliphatic hydrocarbon group including a ring in this structure include: alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from the aliphatic hydrocarbon ring), alicyclic hydrocarbon group bonded to a straight-chain or branched aliphatic A terminal group of a hydrocarbon group, a group present in the middle of a linear or branched aliphatic hydrocarbon group through an alicyclic hydrocarbon group, and the like.

The carbon number of the alicyclic hydrocarbon group is preferably 3-20, more preferably 3-12 carbons.

The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.

Among them, the cyclic aliphatic hydrocarbon groups in R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 are preferably groups obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane.

The straight-chain aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group preferably has 1 to 10 carbons, more preferably 1 to 6 carbons, further preferably 1 to 4 carbons, most preferably 1 carbons ~3.

The branched aliphatic hydrocarbon group that can be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbons, more preferably 3 to 6 carbons, further preferably 3 or 4 carbons, most preferably 3 carbons .

Examples of substituents in the cyclic groups of R ^x1 to R ^x4 , R ^y1 to R ^y2 and R ^z1 to R ^z4 include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, nitro groups, Carbonyl etc.

The chain alkyl groups for R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 may be linear or branched.

The linear alkyl group preferably has 1 to 20 carbons, more preferably 1 to 15 carbons, most preferably 1 to 10 carbons.

The branched alkyl group preferably has 3 to 20 carbons, more preferably 3 to 15 carbons, most preferably 3 to 10 carbons.

The chain alkenyl groups of R ^x1 to R ^x4 , R ^y1 to R ^y2 and R ^z1 to R ^z4 can be either linear or branched, and the number of carbons is preferably 2 to 10, more preferably It has 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms, particularly preferably 3 carbon atoms.

Examples of the substituents in the chain alkyl or chain alkenyl of R ^x1 to R ^x4 , R ^y1 to R ^y2 and R ^z1 to R ^z4 include: alkoxy groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atom, iodine atom, etc.), halogenated alkyl group, hydroxyl group, carbonyl group, nitro group, amino group, cyclic groups in R ^x1 to R ^x4 , R ^y1 to R ^y2 and R ^z1 to R ^z4 , etc.

As the hydrocarbon groups in R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 , among the above hydrocarbon groups, a cyclic group which may have a substituent or a chain alkyl group which may have a substituent are preferable.

In the formula (bd1), R ^y1 to R ^y2 may be bonded to each other to form a ring structure. The ring structure may be an alicyclic hydrocarbon or an aromatic hydrocarbon. In addition, this ring structure may be a polycyclic structure further including other ring structures.

The alicyclic hydrocarbons formed by R ^y1 to R ^y2 may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon is preferably monocycloalkane. The polycyclic alicyclic hydrocarbon is preferably polycycloalkane.

Examples of the aromatic hydrocarbon ring formed by R ^y1 to R ^y2 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms.

The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by R ^y1 to R ^y2 may have a substituent. Examples of the substituent here include the same substituents as the substituents in the cyclic groups of R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 described above.

Among them, the ring structure formed by R ^y1 to R ^y2 is more preferably an aromatic hydrocarbon which may have a substituent in terms of short diffusion of acid by exposure and controllability of acid diffusion.

In the formula (bd1), two or more of R ^z1 to R ^z4 may be bonded to each other to form a ring structure. For example, R ^z1 may form a ring structure together with any of R ^z2 to R ^z4 . The ring structure can be alicyclic hydrocarbon or aromatic hydrocarbon.

The alicyclic hydrocarbon formed by two or more of R ^z1 to R ^z4 may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon is preferably monocycloalkane. The polycyclic alicyclic hydrocarbon is preferably polycycloalkane.

The aromatic hydrocarbon rings formed by two or more of R ^z1 to R ^z4 include: benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic hydrocarbons in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Heterocycle etc.

The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by R ^z1 to R ^z4 may have a substituent.

In the formula (bd1), two or more of R ^x1 to R ^x4 may be bonded to each other to form a ring structure. For example, R ^x1 may form a ring structure together with any one of R ^x2 to R ^x4 . The ring structure can be alicyclic hydrocarbon or aromatic hydrocarbon.

The alicyclic hydrocarbon formed by two or more of R ^x1 to R ^x4 may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon is preferably monocycloalkane. The polycyclic alicyclic hydrocarbon is preferably polycycloalkane.

The aromatic hydrocarbon rings formed by two or more of R ^x1 to R ^x4 include: benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic hydrocarbons in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Heterocycle etc.

The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by R ^x1 to R ^x4 may have a substituent.

Among them, the ring structures formed by two or more of R ^x1 to R ^x4 are preferably alicyclic hydrocarbons from the viewpoint of acid diffusion controllability.

In the formula (bd1), at least one of R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 has an acid anion structure, and the organic acid anion part is an n-valent anion as a whole. n is an integer of 1 or more. The organic acid radical anion part represented by the formula (bd1) functions as a radiation-sensitive strong acid generator or as an acid diffusion control agent in the composition by selecting the acid radical anion structure in the molecule. The radiation-sensitive strong acid generates The agent generates an acid that acts on the acid dissociative groups in the base resin, and the acid diffusion control agent captures the acid generated from the radioactive strong acid generator by exposure (controls the diffusion of the acid).

Examples of acid anion structures possessed by R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 include sulfonate anion structures, carboxylate anion structures, imide anion structures, and methides. Anion structure, carbanion structure, borate anion structure, halide anion structure, phosphate anion structure, antimonate anion structure, arsenate anion structure, etc. Among these, those having a sulfonate anion structure and those having a carboxylate anion structure are preferable.

In the organic acid anion portion represented by the formula (bd1), R ^x1 to R ^x4 , R ^y1 to R ^y2 and R ^z1 to R ^z4 may also be the acid anion structure respectively. When two or more of R ^x1 to R ^x4 are bonded to each other to form a ring structure, the carbon atoms forming the ring structure or the hydrogen atoms bonded to the carbon atoms may be substituted by the acid anion structure. The same applies to R ^y1 to R ^y2 and R ^z1 to R ^z4 .

Specific examples of the organic acid radical anion moiety represented by the formula (bd1) include those shown below, but are not limited thereto.

[Chemical 51]

[Chemical 52]

（所述式（b1）中， R ^b1為具有類固醇骨架的碳數17～50的一價烴基。 Y ^b1為包含雜原子的二價連結基或單鍵。 V ^b1為伸烷基、氟化伸烷基或單鍵。 R ^fa及R ^fb分別獨立地為氫原子、氟原子或碳數1～5的氟化烷基。 Z ^b1為酸根陰離子結構。） (Structure (2) of the other organic acid anion moiety) As the structure of the other organic acid anion moiety, in addition to the above-mentioned structure (1) of the other organic acid anion moiety, a structure represented by the following formula (b1) is also exemplified. . [Chemical 53]

(In the formula (b1), R ^b1 is a monovalent hydrocarbon group with a carbon number of 17 to 50 having a steroid skeleton. Y ^b1 is a divalent linking group or a single bond including a heteroatom. V ^b1 is an alkylene group, fluorinated alkylene group or single bond. R ^fa and R ^fb are independently hydrogen atom, fluorine atom or fluorinated alkyl group with 1 to 5 carbons. Z ^b1 is an acid anion structure.)

In the formula (b1), R ^b1 represents a monovalent hydrocarbon group having 17 to 50 carbon atoms having a steroid skeleton. The steroid skeleton may have substituents. Here, the "steroid skeleton" refers to one having a ring structure represented by the following chemical formula (St) formed by condensing three six-membered rings and one five-membered ring.

[Chemical 54]

In the above-mentioned formula (St), the numbers adjacent to the carbon atoms represent the carbon numbers. In this specification, when referring to the positions of carbon atoms in the steroid skeleton, the carbon numbers shown in the formula (St) are used.

The steroid skeleton of the monovalent hydrocarbon group in R ^b1 preferably has at least one hydroxyl group. That is, the steroid skeleton of R ^b1 is preferably such that at least one hydrogen atom in the ring structure represented by the formula (St) is substituted with a hydroxyl group.

When the steroid skeleton has hydroxyl groups, the number of hydroxyl groups is not particularly limited, and examples thereof include 1 to 10, 1 to 5, or 1 to 3. The number of hydroxyl groups is preferably 1 to 3, more preferably 2 or 3, and still more preferably 3.

The steroid skeleton possessed by R ^b1 may contain substituents other than hydroxyl groups. For example, in the ring structure represented by the chemical formula (St), an alkyl group, a carboxyl group, a pendant oxygen group (=O), an alkoxy group, an alkylcarbonyloxy group, a formyloxy group (HC (=O)-O-), lactone-containing cyclic groups, etc. as substituents.

When the steroid skeleton in R ^b1 has an alkyl group as a substituent, the position of the alkyl group is not particularly limited, and examples thereof include the 10-position, 13-position, and 17-position. The alkyl group is preferably present at the 10-position and the 13-position.

When the steroid skeleton in R ^b1 has a substituent other than an alkyl group and a hydroxyl group, the position of the substituent is not particularly limited, and examples thereof include any of the 3-position, 7-position, and 12-position. For example, the substituent may be present at any one or both of the 3-position, 7-position, and 12-position. In addition, when the substituent is a lactone-containing cyclic group, the 17-position may be used.

R ^b1 has 17-50 carbon atoms, preferably 17-40 carbon atoms, more preferably 17-30 carbon atoms, particularly preferably 17-22 carbon atoms. In addition, the carbon number of R ^b1 here includes the carbon atom which comprises a steroid skeleton, and is set to include the carbon atom in the substituent bonded to a steroid skeleton.

R ^b1 is preferably a group represented by the following formula (R ^b1 -1) to formula (R ^b1 -3). In addition, when there are enantiomers (enantiomers) or diastereomers (diastereomers), the following formulas typically represent these stereoisomers and are assumed to include these stereoisomers Construct.

[Chemical 55]

[In formula (R ^b1-1 ), R ^S11 , R ^S12 , and R ^S13 each independently represent a hydrogen atom, a hydroxyl group, or a substituent other than a hydroxyl group including a heteroatom. In the formula (R ^b1 -2), R ^S21 and R ^S22 are each independently a substituent other than a hydrogen atom, a hydroxyl group, or a hydroxyl group including a heteroatom. R ^S23 represents an alkyl group which may contain heteroatoms. In formula (R ^b1-3 ), R ^S31 , R ^S32 , and R ^S33 each independently represent a hydrogen atom, a hydroxyl group, or a substituent other than a hydroxyl group including a heteroatom. R ^S34 represents a lactone-containing cyclic group. * represents a bonding bond to Y ^b1 in the formula (b1). ]

In the above-mentioned formula (R ^b1-1 ), examples of the substituents other than the hydroxyl group containing heteroatoms in R ^S11 to R ^S13 include carboxyl group, pendant oxy group (=O), alkoxy group, and alkylcarbonyloxy group. , formyloxy (HC(=O)-O-), etc. In the formula (R ^b1 -2), the same applies to the substituents other than the hydroxyl group containing a heteroatom in R ^S21 and R ^S22 . In addition, in the above-mentioned formula (R ^b1 -3), the same applies to the substituents other than the hydroxyl group including a heteroatom in R ^S31 to R ^S33 .

In the formula (R ^b1 -1), at least one of R ^S11 to R ^S13 is preferably a hydroxyl group, and preferably any two or more of R ^S11 to R ^S13 are hydroxyl groups, and more preferably all of R ^S11 to R ^S13 are hydroxyl. Among R ^S11 to R ^S13 , those other than hydroxyl groups are preferably hydrogen atoms.

In the formula (R ^b1-2 ), at least one of R ^S21 and R ^S22 is preferably a hydroxyl group, and it is preferable that both R ^S21 and R ^S22 are a hydroxyl group. In R ^S21 and R ^S22 , the non-hydroxyl group is preferably a hydrogen atom. In the formula (R ^b1-2 ), R ^S23 represents an alkyl group which may contain a heteroatom. This alkyl group may be linear or branched. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms.

In the formula (R ^b1 -3), at least one of R ^S31 to R ^S33 is preferably a hydroxyl group, and preferably any two or more of R ^S31 to R ^S33 are hydroxyl groups, more preferably R ^S31 to R ^S33 All are hydroxyl groups. Among R ^S31 to R ^S33 , those other than hydroxyl groups are preferably hydrogen atoms.

Among them, R ^b1 is more preferably a group represented by the formula (R ^b1 -1).

Specific examples of R ^b1 are shown below, but are not limited thereto. In the following formula, * represents a bond to Y ^b1 in the formula (b1).

[Chemical 56]

[Chemical 57]

[Chemical 58]

Among the above, R ^b1 is preferably formula (Rb-1-1) to formula (Rb-1-19), more preferably formula (Rb-1-1) to formula (Rb-1-7).

In the formula (b1), R ^fa and R ^fb are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbons.

In the formula (b1), Y ^b1 represents a divalent linking group or a single bond including a heteroatom. Examples of the divalent linking group containing a heteroatom in Y ^b1 include the same groups as those listed in the divalent linking group containing a heteroatom in ^Y1 in the formula (1).

Y ^b1 is preferably a divalent linking group containing an ester bond or an ether bond.

In the formula (b1), V ^b1 represents an alkylene group, a fluorinated alkylene group or a single bond. The alkylene group or fluorinated alkylene group in V ^b1 may be linear or branched, but is preferably linear. The alkylene group or fluorinated alkylene group in V ^b1 preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.

As the acid anion structure represented by Z ^b1 , the acid anion structures of R ^x1 to R ^x4 , R ^y1 to R ^y2 , and R ^z1 to R ^z4 in the formula (bd1) can be preferably used.

Specific examples of the organic acid radical anion moiety represented by the formula (b1) are listed below, but are not limited to these specific examples. In the formula, k and k' each independently represent an integer of 0-5, and k'' represents an integer of 1-5. In addition, what is shown below is an organic acid anion moiety having a sulfonate anion, but a structure in which a sulfonate anion is replaced by a carboxylate anion can also be preferably employed. When the organic acid anion part has a carboxylate anion, the fluorine atom may not be bonded to the carbon atoms at the α-position and β-position of the carboxylate anion.

[Chemical 59]

[Chemical 60]

[Chemical 61]

[chem 62]

The organic acid anion moiety represented by the formula (b1) is preferably represented by the following formula (b1-an1). In addition, what is shown below is an organic acid anion moiety having a sulfonate anion, but a structure in which a sulfonate anion is replaced by a carboxylate anion can also be preferably employed. When the organic acid anion part has a carboxylate anion, the fluorine atom may not be bonded to the carbon atoms at the α-position and β-position of the carboxylate anion.

[式中，R ^S11～R ^S13與所述通式（R ^b1-1）中的R ^S11～R ^S13相同。V ^b11表示單鍵、-CHF-或-CF ₂-。k表示1～5的整數。] [chem 63]

[In the formula, R ^S11 to R ^S13 are the same as R ^S11 to R ^S13 in the general formula (R ^b1 -1). V ^b11 represents a single bond, -CHF- or -CF ₂ -. k represents an integer of 1-5. ]

In the formula (b1-an1), R ^S11 to R ^S13 are the same as R ^S11 to R ^S13 in the general formula (R ^b1 -1).

<Solvent> The radiation sensitive resin composition of this embodiment contains a solvent. The solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing at least the onium salt, the base resin (at least one of the radiation-sensitive acid generating resin and the resin), and optionally contained additives.

Examples of the solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents.

Examples of alcohol-based solvents include: Isopropanol, 4-methyl-2-pentanol, 3-methoxybutanol, n-hexanol, 2-ethylhexanol, furfuryl alcohol, cyclohexanol, 3,3,5-trimethylcyclohexanol , diacetone alcohol and other monoalcohol solvents with 1 to 18 carbon atoms; Ethylene glycol, 1,2-propanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc. carbon number 2 ~18 polyol solvents; A polyol partial ether-based solvent obtained by etherifying a part of hydroxyl groups in the polyol-based solvent, or the like.

Examples of ether solvents include: Dialkyl ether solvents such as diethyl ether, dipropyl ether, and dibutyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; Diphenyl ether, anisole (methyl phenyl ether) and other ether solvents containing aromatic rings; A polyol ether-based solvent obtained by etherifying a hydroxyl group contained in the polyol-based solvent, or the like.

As the ketone-based solvent, for example, chain ketone-based solvents such as acetone, butanone, and methyl-isobutyl ketone can be cited; Cyclic ketone solvents such as cyclopentanone, cyclohexanone, and methylcyclohexanone; 2,4-pentanedione, acetonylacetone, acetophenone, etc.

Examples of amide-based solvents include cyclic amide-based solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide Chain amide-based solvents such as amide and N-methylacrylamide, etc.

Examples of ester-based solvents include: Monocarboxylate solvents such as n-butyl acetate and ethyl lactate; Diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and other polyol partial ether acetate solvents; Lactone solvents such as γ-butyrolactone and valerolactone; Diethyl carbonate, ethylene carbonate, propylene carbonate and other carbonate-based solvents; Polycarboxylic acid diester solvents such as propylene glycol diacetate, methoxytriethylene glycol acetate, diethyl oxalate, ethyl acetylacetate, ethyl lactate, and diethyl phthalate.

Examples of hydrocarbon solvents include: Aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbon solvents such as benzene, toluene, diisopropylbenzene, n-pentylnaphthalene, etc.

Among them, alcohol-based solvents, ester-based solvents, and ketone-based solvents are preferable, and monoalcohol-based solvents, polyol partial ether acetate-based solvents, polycarboxylic acid diester-based solvents, and cyclic ketone-based solvents are more preferable. , Lactone-based solvents, more preferably diacetone alcohol, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and γ-butyrolactone. The radiation-sensitive resin composition may also contain one or two or more solvents.

＜Other optional ingredients＞ The radiation-sensitive resin composition may contain other optional components in addition to the above-mentioned components. As said other arbitrary components, a crosslinking agent, a biased presence accelerator, a surfactant, an alicyclic frame|skeleton containing compound, a sensitizer, etc. are mentioned, for example. These other arbitrary components can be used individually by 1 type or in combination of 2 or more types.

＜Preparation method of radiation-sensitive resin composition＞ The radiation-sensitive resin composition can be prepared, for example, by mixing an onium salt, a base resin (at least one of a radiation-sensitive acid-generating resin and a resin), a solvent, and other optional components as necessary in a predetermined ratio. The radiation-sensitive resin composition is preferably filtered, for example, with a filter having a pore size of about 0.05 μm to 0.2 μm after mixing. The solid content concentration of the radiation-sensitive resin composition is usually 0.1% by mass to 50% by mass, preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 20% by mass.

"Pattern Formation Method" The pattern forming method of the present embodiment comprises: Step (1) of forming a resist film by directly or indirectly coating the radiation-sensitive resin composition on a substrate (hereinafter also referred to as "resist film forming step"); step (2) of exposing the resist film (hereinafter, also referred to as "exposure step"); and Step (3) of developing the exposed resist film (hereinafter also referred to as "development step").

According to the pattern forming method, a high-quality resist pattern can be formed by using the radiation-sensitive resin composition that is excellent in sensitivity or CDU performance in the exposure step and excellent in development residue suppression in the development step. Each step will be described below.

[Resist Film Formation Step] In this step (the step (1)), a resist film is formed using the radiation-sensitive resin composition. Examples of substrates on which the resist film is formed include conventionally known ones such as silicon wafers, silicon dioxide, and aluminum-coated wafers. In addition, an organic or inorganic antireflection film disclosed in, for example, Japanese Patent Publication No. 6-12452 or Japanese Patent Application Publication No. 59-93448 may also be formed on the substrate. Examples of coating methods include spin coating (spin coating), cast coating, and roll coating. After coating, if necessary, prebake (PB) may be performed in order to volatilize the solvent in the coating film. The PB temperature is usually 60°C to 140°C, preferably 80°C to 120°C. The PB time is usually 5 seconds to 600 seconds, preferably 10 seconds to 300 seconds. The film thickness of the formed resist film is preferably from 10 nm to 1,000 nm, more preferably from 10 nm to 500 nm.

In the case of liquid immersion exposure, regardless of the presence or absence of water-repellent polymer additives such as the high-fluorine-content resin in the radiation-sensitive resin composition, it is possible to avoid direct contact between the liquid immersion liquid and the resist film. For the purpose of forming a protective film for immersion that is insoluble in the immersion liquid on the formed resist film. As the protective film for liquid immersion, a solvent-peelable protective film that is peeled off with a solvent before the development step (for example, refer to Japanese Patent Application Laid-Open No. 2006-227632 ), a developer-solution peelable protective film that is peeled off simultaneously with the development of the developing step, etc., can be used. Any of films (for example, refer to WO2005-069076 and WO2006-035790). Among them, it is preferable to use a developing solution peeling type protective film for immersion from the viewpoint of the amount of treatment.

In addition, in the case of performing the exposure step as the next step with radiation having a wavelength of 50 nm or less, it is preferable to use a compound having the above-mentioned structural unit (I) to structural unit (IV), and optionally a structural unit (V). The resin serves as the base resin in the composition.

[Exposure steps] In this step (the step (2)), the resist film formed in the step (1), that is, the resist film forming step is Exposure is performed by irradiating radiation. Examples of radiation used for exposure include electromagnetic waves such as visible rays, ultraviolet rays, extreme ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, and γ-rays; charged particle beams such as electron beams and α-rays, etc., depending on the line width of the target pattern. . Among these, far ultraviolet rays, electron beams, and EUV are preferred, ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), electron beams, and EUV are more preferred, and positioning Electron beam and EUV with a wavelength of 50 nm or less are next-generation exposure technologies.

When performing exposure by liquid immersion exposure, water, a fluorine-type inert liquid, etc. are mentioned as an immersion liquid to be used, for example.

It is preferable to carry out post exposure bake (post exposure bake, PEB) after the said exposure, and use the acid generated by the self-induced radioactive acid generator by the exposure to accelerate the resin on the exposed part of the resist film. The dissociation of the acid dissociative group possessed by etc. By the PEB, a difference in solubility with respect to a developing solution occurs between the exposed part and the unexposed part. The PEB temperature is usually 50°C to 180°C, preferably 80°C to 130°C. The PEB time is usually 5 seconds to 600 seconds, preferably 10 seconds to 300 seconds.

[Development procedure] In this step (the step (3)), the resist film exposed in the step (2), that is, the exposure step is developed. Thereby, a predetermined resist pattern can be formed. Generally, after developing, rinse with water or alcohol, and then dry.

As the developer used for the development, in the case of alkali development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propyl Diethylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), Pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene and other bases An alkaline aqueous solution of at least one active compound, etc. Among these, TMAH aqueous solution is preferable, and 2.38 mass % TMAH aqueous solution is more preferable.

In addition, in the case of organic solvent development, organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, and alcohol solvents, or solvents containing organic solvents are mentioned. Examples of the organic solvent include one, two or more of the solvents listed as the solvent for the radiation-sensitive resin composition. Among these, ester-based solvents and ketone-based solvents are preferable. The ester-based solvent is preferably an acetate-based solvent, more preferably n-butyl acetate or amyl acetate. The ketone solvent is preferably a chain ketone, more preferably 2-heptanone. The content of the organic solvent in the developer is preferably at least 80% by mass, more preferably at least 90% by mass, further preferably at least 95% by mass, and most preferably at least 99% by mass. As components other than the organic solvent in a developing solution, water, silicone oil, etc. are mentioned, for example.

Examples of developing methods include: a method of immersing a substrate in a tank filled with a developer for a certain period of time (dipping method); a method of developing by using surface tension to deposit a developer on the surface of the substrate and standing still for a certain period of time (coating). solution (puddle) method); method of spraying developer on the substrate surface (spray method); method of continuously spraying developer on a substrate rotating at a constant speed while scanning the developer spray nozzle at a constant speed (dynamic distribution method) Wait. [Example]

Hereinafter, the present invention will be specifically described by showing synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. The measurement methods of various physical property values are shown below.

[Mw and Mn] The Mw and Mn of the polymer were determined by gel permeation chromatography (GPC) using GPC columns manufactured by Tosoh Corporation (two "G2000HXL", one "G3000HXL", one "G4000HXL"), and the following conditions to measure. Eluent: Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0 mL/min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Column temperature: 40°C Detector: Differential refractometer Standard material: monodisperse polystyrene

The structures of the radiation-sensitive acid generators PAG1 to PAG13 of the permeic and iodonium salts used in the radiation-sensitive resin compositions of Examples are shown below.

[chem 64]

[chem 65]

[Synthesis Example] Synthesis of Base Polymer (P-1) ~ Base Polymer (P-9) Combining individual monomers, carrying out copolymerization reaction in tetrahydrofuran (THF) solvent, crystallizing in methanol, and then utilizing After repeated washing with alkane, separation and drying were carried out to obtain base polymers (P-1) to base polymers (P-9) having the compositions shown below. The composition of the obtained base polymer was confirmed by hydrogen spectrum nuclear magnetic resonance ( ¹ H-nuclear magnetic resonance, ¹ H-NMR), and the Mw and dispersion (Mw/Mn) were determined by the GPC (solvent: THF, standard : polystyrene) to confirm. P-1: Mw=7,700, Mw/Mn=1.7 P-2: Mw=8.000, Mw/Mn=1.7 P-3: Mw=8,200, Mw/Mn=1.7 P-4: Mw=7,600, Mw/Mn =1.7 P-5: Mw=7,500, Mw/Mn=1.7 P-6: Mw=7,900, Mw/Mn=1.7 P-7: Mw=7,600, Mw/Mn=1.7 P-8: Mw=8,000, Mw /Mn=1.8 P-9: Mw=7,100, Mw/Mn=1.6

[chem 66]

[chem 67]

[Example, comparative example] Each component was dissolved in a solvent of 100 ppm of FC-4430 manufactured by 3M Company as a surfactant in the composition shown in Table 1 to prepare a solution, and the solution was filtered through a filter with a size of 0.2 μm to prepare Radiation sensitive resin composition.

In Table 1, each component is as follows. Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) GBL (gamma-butyrolactone) CHN (cyclohexanone) PGME (Propylene Glycol Monomethyl Ether) DAA (Diacetone Alcohol) EL (ethyl lactate)

Acid diffusion control agent (Q-1)～Acid diffusion control agent (Q-5) [Chemical 68]

High fluorine content resin F-1: Mw=8,900, Mw/Mn=2.0 [Chemical 69]

[Evaluation of Sensitivity by EUV Exposure] Using a spin coater ("CLEAN TRACK ACT12" of Tokyo Electron Co., Ltd.) Brewer Science's "ARC66") is coated on a 12-inch silicon wafer and heated at 205°C for 60 seconds to form a bottom anti-reflection film with an average thickness of 105 nm. Each radiation-sensitive resin composition shown in Table 1 was coated on the underlying antireflection film using the spin coater, and PB was performed at 130° C. for 60 seconds. Thereafter, cooling was performed at 23° C. for 30 seconds, whereby a resist film having an average thickness of 55 nm was formed. For this resist film, an EUV scanner ("NXE3300" of ASML Corporation (numerical aperture (NA) 0.33, σ 0.9/0.6, quadrupole illumination, on-wafer dimensions with a pitch of 46 nm, +20% deviation) was used. mask of the hole pattern)) for exposure. PEB was performed on a hot plate at 120°C for 60 seconds, and development was performed for 30 seconds with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution to form a resist pattern with 23 nm holes and a 46 nm pitch. The exposure amount at the time of forming the resist pattern with 23 nm holes and 46 nm pitch was defined as the optimal exposure amount (Eop), and the optimal exposure amount was defined as the sensitivity (mJ/cm ² ).

[Evaluation of CDU] The exposure amount of Eop obtained above was irradiated, and the same operation as above was performed to form a resist pattern with 23 nm holes and a pitch of 46 nm. The formed resist pattern was observed from the top of the pattern using a scanning electron microscope ("CG-5000" manufactured by Hitachi High-Technologies). The pore diameter was measured at 16 points in the range of 500 nm, and the average value was calculated. Moreover, the average value of 500 points in total was measured at arbitrary points. The 3-sigma value was obtained from the distribution of the measured values, and the obtained 3-sigma value was used as the evaluation value (nm) of the CDU performance. With regard to the CDU performance, the smaller the evaluation value, the smaller the variation in the hole diameter in the long cycle, and the better it is. The results are shown in Table 1.

[Evaluation of development residue] The same operations as above were performed up to the operation of forming a resist film having an average thickness of 55 nm, whereby a wafer on which a resist film was formed was produced. Next, without performing pattern exposure using an EUV scanner, PEB was directly performed on a hot plate at 120° C. for 60 seconds. Next, image development was performed for 30 seconds with 2.38 mass % TMAH aqueous solution, it rinsed with pure water for 30 seconds, and it dried. In this way, a wafer for development residue evaluation was produced. The wafer was observed with a defect inspection device COMPLUS (manufactured by AMAT), and the presence or absence of residue defects was confirmed and counted using a defect review SEM RS5500 (manufactured by Hitachi High-Technologies Co., Ltd.) number of defects. Based on the number of counted residue defects, evaluation was performed using the following indexes. A: Below 5 B: 6~10 C: 11~20 D: 21~50 E: above 51

[Table 1] Base resin (parts by mass) PAG (parts by mass) Acid diffusion control agent (parts by mass) Solvent (parts by mass) Additives (parts by mass) Sensitivity[mJ/cm ² ] CDU [nm] Development residue Example 1 P-1 (100) PAG1 (6.0) Q-1 (3.0) PGMEA/DAA (2,000/500) F-1 (2.0) 14 2.4 D. Example 2 P-1 (100) PAG2 (6.0) Q-1 (3.0) PGMEA/DAA (2,000/500) F-1 (2.0) 13 2.4 C Example 3 P-1 (100) PAG3 (6.0) Q-1 (3.0) PGMEA/DAA (2,000/500) F-1 (2.0) 13 2.4 B Example 4 P-1 (100) PAG4 (6.0) Q-1 (3.0) PGMEA/DAA (2,000/500) F-1 (2.0) 12 2.4 A Example 5 P-1 (100) PAG5 (6.0) Q-1 (3.0) PGMEA/DAA (2,000/500) F-1 (2.0) 12 2.4 A Example 6 P-1 (100) PAG6 (6.0) Q-1 (3.0) PGMEA/DAA (2,000/500) F-1 (2.0) 12 2.4 A Example 7 P-2 (100) PAG7 (5.0) Q-1 (3.0) PGMEA/PGME (2,000/500) F-1 (2.0) 13 2.4 B Example 8 P-3 (100) PAG8 (5.5) Q-1 (3.0) PGMEA/PGME (1,000/1,000) F-1 (2.0) 13 2.4 B Example 9 P-4 (100) PAG9 (6.5) Q-2 (3.0) PGMEA/GBL (2,200/300) F-1 (2.5) 13 2.4 B Example 10 P-5 (100) PAG1 (7.0) Q-2 (3.0) PGME/EL (2,000/500) F-1 (2.5) 13 2.4 B Example 11 P-6 (100) PAG9 (7.5) Q-2 (3.0) PGME/CHN (2,100/400) F-1 (2.5) 13 2.3 B Example 12 P-7 (100) PAG10 (6.0) Q-1 (3.5) PGME/GBL (2,100/400) F-1 (2.5) 13 2.3 B Example 13 P-8 (100) PAG3 (6.0) Q-1 (2.5) PGMEA/PGME/EL (1,500/500/500) F-1 (2.5) 13 2.3 B Example 14 P-1 (100) PAG11 (6.0) Q-1 (2.5) PGMEA/EL (2,000/500) F-1 (2.5) 13 2.3 B Example 15 P-1 (100) PAG3 (6.0) Q-3 (3.0) PGMEA/EL (2,000/500) F-1 (2.5) 13 2.3 B Example 16 P-1 (100) PAG12 (6.0) Q-2 (2.5) PGMEA/EL (2,000/500) F-1 (3.0) 13 2.3 B Example 17 P-1 (100) PAG9 (6.0) Q-4 (2.5) PGMEA/EL (2,000/500) F-1 (3.0) 13 2.3 B Example 18 P-1 (100) PAG12 (6.0) Q-5 (2.5) PGMEA/EL (2,000/500) F-1 (3.0) 13 2.1 B Example 19 P-1 (100) PAG13 (6.0) Q-1 (3.0) PGMEA/DAA (2,000/500) F-1 (2.0) 12 2.2 A Comparative example 1 P-9 (100) PAG3 (6.0) Q-1 (3.0) PGMEA/DAA (2,000/500) F-1 (3.0) 14 2.5 B Comparative example 2 P-1 (100) PAG9 (6.0) Q-1 (4.0) PGMEA/DAA (2,000/500) F-1 (3.0) 15 2.4 E.

As a result of evaluating the resist pattern formed by the said EUV exposure, the sensitivity, CDU performance, and development residue suppression property of the radiation sensitive resin composition of Example were favorable. [Industrial availability]

According to the radiation-sensitive resin composition and resist pattern forming method described above, a resist pattern having good sensitivity to exposure light and excellent CDU performance and development residue suppression can be formed. Therefore, these can be preferably used in the processing of semiconductor devices expected to be further miniaturized in the future.

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Claims (9)

A radiation-sensitive resin composition comprising: a resin comprising a structural unit represented by the following formula (1); one or more than two kinds of onium salts comprising an organic acid anion and an onium cation; and a solvent, the onium at least a portion of said onium cation moieties in the salt comprise an aromatic ring structure having a fluorine atom,

In the formula (1), R is a hydrogen atom, an alkyl group having 1 to 5 carbons, or a halogenated alkyl group having 1 to 5 carbons, Y ¹ is a divalent linking group, and X ¹ is an acid dissociating group. The radiation-sensitive resin composition according to Claim 1, wherein the onium salt is selected from: a radiation sensitive acid generator comprising said organic acid anion moiety and said onium cation moiety; and An acid diffusion control agent comprising the organic acid anion moiety and the onium cation moiety, and generating an acid having a higher pKa than the acid generated from the radiation-sensitive acid generator by irradiation with radiation at least one of the group consisting of, At least one of the onium cation moiety in the radiation-sensitive acid generator and the onium cation moiety in the acid diffusion controller includes the aromatic ring structure having a fluorine atom. The radiation-sensitive resin composition according to Claim 1 or Claim 2, wherein the organic acid anion part comprises a structure represented by the following formula (bd1) or formula (b1),

In the formula (bd1), R ^x1 to R ^x4 are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a ring structure formed by combining two or more of these; R ^y1 to R ^y2 are independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or represent a ring structure formed by combining with each other;

is a double bond or a single bond; R ^z1 ~ R ^z4 are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a ring structure formed by combining two or more of these; however, R ^x1 ~ At least one of R ^x4 , R ^y1 to R ^y2 and R ^z1 to R ^z4 has an acid anion structure; in the formula (b1), R ^b1 is a monovalent hydrocarbon group with a carbon number of 17 to 50 having a steroid skeleton; Y ^b1 It is a divalent linking group or a single bond containing a heteroatom; V ^b1 is an alkylene group, a fluorinated alkylene group or a single bond; ^Rfa and ^Rfb are independently hydrogen atoms, fluorine atoms, or carbon atoms with 1 to 5 carbon atoms Fluorinated alkyl; Z ^b1 is an acid radical anion structure. The radiation-sensitive resin composition according to claim 1 or claim 2, wherein X in the formula ( ¹ ) is represented by the following formula (s1) or formula (s2),

In the formula (s1), Cy is an aliphatic ring group formed together with a carbon atom; Ra ⁰¹ to Ra ⁰³ are each independently a hydrogen atom, a substituted or unsubstituted monovalent chain with 1 to 10 carbon atoms A saturated hydrocarbon group or a substituted or unsubstituted monovalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbons, or an aliphatic ring structure formed by combining two or more of these, wherein the The aliphatic ring structure will not form a crosslinked structure; in the formula (s2), Cy has the same meaning as the formula (s1); Ra ⁰⁴ is a substituted or unsubstituted aromatic hydrocarbon group; in the formula , * all represent the bond with the oxygen atom. The radiation-sensitive resin composition according to Claim 1 or Claim 2, wherein the resin further includes a structural unit having a phenolic hydroxyl group. The radiation-sensitive resin composition according to Claim 1 or Claim 2, wherein the resin further comprises at least A structural unit. The radiation-sensitive resin composition according to Claim 1 or Claim 2 further includes a high-fluorine-content resin having a mass content of fluorine atoms greater than that of the resin. A pattern forming method, comprising: A step of directly or indirectly coating the radiation-sensitive resin composition described in any one of claim 1 to claim 7 on a substrate to form a resist film; exposing the resist film to light; and and developing the exposed resist film with a developer. The pattern forming method according to claim 8, wherein the exposure is performed using extreme ultraviolet rays or electron beams.