TW202229368A - Radiation-sensitive resin composition, pattern formation method, and water repellency-improving agent - Google Patents

Abstract

Provided are: a radiation-sensitive resin composition which exhibits good sensitivity and can form a resist pattern having high water repellency and few defects; and a resist pattern formation method and a water repellency-improving agent using same. This radiation-sensitive resin composition contains a resin A having a first structural unit containing a partial structure represented by formula (1). In formula (1), X is a divalent linking group. R1 and R2 are each independently a monovalent chain-like hydrocarbon group having 1-40 carbon atoms, a monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, a monovalent aromatic hydrocarbon group having 6-12 carbon atoms, or a monovalent fluorinated hydrocarbon group having 1-40 carbon atoms, or R1 and R2 bond to each other to form a 3 to 20-membered ring structure (a) together with the carbon atom to which these are bonded. R3 is a fluorinated chain-like hydrocarbon group having 1-4 carbon atoms. ∗ denotes a position of linking to a polymer main chain. The radiation-sensitive resin composition also contains: resin B containing a structural unit having an acid-dissociable group; a radiation-sensitive acid generator; and a solvent.

Description

Radiation-sensitive resin composition, pattern forming method, and water repellency improver

The present invention relates to a radiation-sensitive resin composition, a method for forming a resist pattern using the same, a water repellency improving agent, and the like.

With the miniaturization of the structures of various electronic elements such as semiconductor elements and liquid crystal elements, further miniaturization of the resist pattern in the lithography step is required, and therefore, various radiation-sensitive resin compositions have been studied. Such a radiation-sensitive resin composition is irradiated with extreme ultraviolet rays such as ArF excimer lasers, and radiation such as electron beams to generate an acid in the exposed portion, and the exposed portion and the unexposed portion are made to interact with each other by the catalytic action of the acid. The dissolution rate of the developer is poor, and a resist pattern is formed on the substrate.

In such a radiation-sensitive resin composition, for example, a liquid immersion exposure method (liquid immersion lithography) is used as a method of forming a finer resist pattern with a line width of about 45 nm. In this method, the exposure optical path space (between the lens and the resist film) is filled with a liquid immersion medium whose refractive index (n) is greater than that of air or inert gas, such as pure water, fluorine-based inert liquid, etc. state for exposure. Therefore, even when the numerical aperture (NA) of the lens is increased, the depth of focus is difficult to decrease, and high resolution can be obtained.

In the resin composition used in the liquid immersion exposure method, in order to suppress the elution of acid generators and the like from the formed resist film to the liquid immersion medium, to prevent the performance of the resist film from being lowered or the contamination of devices such as lenses, and The water repellency of the resist film surface is good, the watermark can be prevented from remaining, and high-speed scanning can be performed. Therefore, for the purpose of improving the hydrophobicity of the resist film surface, a water repellent containing a fluorine atom-containing polymer can be used. Polymer additives (for example, refer to Patent Document 1). However, if the hydrophobicity of the resist film surface is increased, the surface wettability with respect to the developer solution or the rinse solution is lowered, so that there are cases in which the development residue deposited on the unexposed portion of the resist film surface during development becomes The removal becomes insufficient, and defects such as blob defects are generated in the resist pattern. For the purpose of suppressing the occurrence of such defects, a fluorine atom-containing polymer which is hydrophobic during liquid immersion exposure but exhibits hydrophilicity during alkali development, specifically a fluoroalkyl ester structure into which a carboxylic acid is introduced, has been proposed. (for example, refer to Patent Document 2), it is considered that the generation of defects can be suppressed by using such a polymer as a water-repellent polymer additive. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2007/116664 [Patent Document 2] Japanese Patent Laid-Open No. 2010-32994

[The problem to be solved by the invention]

However, as the miniaturization of the resist pattern progresses to the level of the line width of 45 nm or less, the required level of the defect suppression property is further increased. In addition, the water-repellent polymer additive is also required to obtain a high-precision pattern with a high yield by improving the sensitivity performance of the radiation-sensitive resin composition containing the water-repellent polymer additive. However, in the above-mentioned conventional radiation-sensitive resin compositions, these requirements cannot be satisfied.

An object of the present invention is to provide a radiation-sensitive resin composition capable of forming a resist pattern with good sensitivity, high water repellency and few defects, a resist pattern forming method, a water repellency improving agent, and the like using the same. [Means of Solving Problems]

The inventors of the present invention have made repeated efforts to solve this problem, and as a result, they have found that the object can be achieved by adopting the following configuration, and have completed the present invention.

（式（1）中， X為二價連結基； R ¹及R ²分別獨立地為碳數1～40的一價鏈狀烴基、碳數3～20的一價脂環式烴基、碳數6～12的一價芳香族烴基、碳數1～40的一價氟化烴基、或者R ¹及R ²相互結合並與該些所鍵結的碳原子一起構成的環員數3～20的環結構（a）； R ³為碳數1～4的氟化鏈狀烴基； *表示與聚合物主鏈部分的連結部位） 含有具有酸解離性基的結構單元的樹脂B、 感放射線性酸產生劑、及 溶劑。 That is, in one embodiment, the present invention relates to a radiation-sensitive resin composition comprising resin A having a first structural unit containing a partial structure represented by the following formula (1), [Chem. 1]

(In formula (1), X is a divalent linking group; R ¹ and R ² are each independently a monovalent chain hydrocarbon group having 1 to 40 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, A monovalent aromatic hydrocarbon group of 6 to 12, a monovalent fluorinated hydrocarbon group of 1 to 40 carbon atoms, or a group of 3 to 20 ring members composed of R ¹ and R ² combined with each other and these bonded carbon atoms Ring structure (a); R ³ is a fluorinated chain hydrocarbon group having 1 to 4 carbon atoms; * represents a linking site with the main chain portion of the polymer) Resin B containing a structural unit having an acid-dissociable group, radiation-sensitive acid generator, and solvent.

Since the radiation-sensitive resin composition of the present invention contains the resin A, it is possible to form a resist pattern with good sensitivity, high water repellency, and few defects. The resin A is mainly -C(=O)OCR ¹ R ² R ³ and exhibits excellent water repellency and stability to water, so it is presumed that it will affect the high water repellency and defect suppression of the resist pattern. Furthermore, the scope of the right of the present invention is not necessarily limited by speculating on the mechanism of action.

In the present invention, examples of the organic group include a monovalent hydrocarbon group, a group containing a divalent heteroatom-containing group between carbon and carbon of the hydrocarbon group, a monovalent heteroatom-containing group substituted for the hydrocarbon group, and A group including a part or all of hydrogen atoms contained in a group containing a divalent heteroatom-containing group, etc.

In the present invention, the "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group unless the element is particularly limited. The "hydrocarbon group" includes both a saturated hydrocarbon group and an unsaturated hydrocarbon group. The "chain hydrocarbon group" refers to a hydrocarbon group that does not contain a cyclic structure but only includes a chain structure, and includes both a straight-chain hydrocarbon group and a branched-chain hydrocarbon group. The "alicyclic hydrocarbon group" refers to a hydrocarbon group including only an alicyclic structure as a ring structure but not an aromatic ring structure, and includes both a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic hydrocarbon group. However, it is not necessary to include only an alicyclic structure, and a chain structure may be included in a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to include only an aromatic ring structure, and a chain structure or an alicyclic structure may be included in a part thereof.

On the other hand, in another embodiment, the present invention relates to a method for forming a resist pattern, which includes: a step of directly or indirectly coating the radiation-sensitive resin composition on a substrate to form a resist film; exposing the resist film by immersion exposure; and A step of developing the exposed resist film.

Since the method for forming a resist pattern of the present invention includes the step of using the radiation-sensitive resin composition, a resist pattern with good sensitivity, high water repellency, and few defects can be obtained.

（式（2）中， X為二價連結基； R為氫原子、氟原子、或者未經取代或經鹵素原子或烷氧基取代的一價烴基； R ¹及R ²分別獨立地為碳數1～40的一價鏈狀烴基、碳數3～20的一價脂環式烴基、碳數6～12的一價芳香族烴基、或者R ¹及R ²相互結合並與該些所鍵結的碳原子一起構成的環員數3～20的環結構（a）； R ³為碳數1～4的氟化鏈狀烴基） On the other hand, in another embodiment, the present invention relates to a water repellency improving agent comprising resin A having a first structural unit represented by the following formula (2). [hua 2]

(In formula (2), X is a divalent linking group; R is a hydrogen atom, a fluorine atom, or a monovalent hydrocarbon group unsubstituted or substituted by a halogen atom or an alkoxy group; R ¹ and R ² are independently carbon A monovalent chain hydrocarbon group having 1 to 40 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, or R ¹ and R ² are bonded to each other and to these A ring structure with 3 to 20 ring members formed by the carbon atoms of the knot together (a); R ³ is a fluorinated chain hydrocarbon group with 1 to 4 carbon atoms)

The water repellency improver of the present invention can easily impart, increase or improve the water repellency of a resist film or the like by including the resin A.

Hereinafter, the 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 (hereinafter, also simply referred to as "composition") of the present embodiment includes predetermined resin A, resin B, a radiation-sensitive acid generator, and a solvent. As long as the effect of this invention is not impaired, this composition may contain other arbitrary components. By containing the predetermined resin A, the radiation-sensitive resin composition can form a resist pattern with good sensitivity, high water repellency, and few defects.

(Resin A) Resin A is resin A which has the 1st structural unit containing the partial structure represented by the said formula (1).

In the above formula (1), the divalent linking group represented by the X includes, for example, a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, and among these groups. One or more carbon atoms are substituted by divalent groups such as -O-, -CO-, -COO-, -CONR'-, -S-, -CS-, -COS, -CSO-, etc. R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

In the above formula (1), as the chain hydrocarbon group having 1 to 40 carbon atoms represented by the above R ¹ and R ² , a linear or branched saturated hydrocarbon group having 1 to 40 carbon atoms, or a carbon A straight or branched chain unsaturated hydrocarbon group of 1 to 40.

In the above formula (1), as the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by the above R ¹ and R ² , each independently includes, for example, cyclopropyl, cyclobutyl, and cyclopentyl. , cyclohexyl, etc.

In the above formula (1), as the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by the above R ¹ and R ² , each independently includes, for example, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. , anthracenyl and other aryl groups; benzyl, phenethyl, naphthylmethyl and other aralkyl groups, etc.

In the above formula (1), as the monovalent fluorinated hydrocarbon group having 1 to 40 carbon atoms represented by the above R ¹ and R ² , each independently includes, for example, a monovalent fluorinated chain having 1 to 40 carbon atoms. A hydrocarbon group, a monovalent fluorinated alicyclic hydrocarbon group having 3 to 40 carbon atoms, and the like.

In the above formula (1), as the ring structure (a) having 3 to 20 ring members in which the above R ¹ and R ² are bonded to each other and constituted together with the carbon atoms to which they are bonded, for example, the carbon atoms described above can be exemplified. Number of alicyclic hydrocarbons or one or more carbon atoms in alicyclic hydrocarbons via -O-, -CO-, -COO-, -CONR'-, -S-, -CS-, -COS, -CSO- A group obtained by removing two hydrogen atoms from the same carbon atom in a structure substituted by an equivalent divalent group, etc.

In the above formula (1), the fluorinated chain hydrocarbon group having 1 to 4 carbon atoms represented by R ³ includes, for example, a monovalent fluorinated chain hydrocarbon group having 1 to 4 carbon atoms, and a fluorinated chain hydrocarbon group having 3 to 4 carbon atoms. Monovalent fluorinated alicyclic hydrocarbon group, etc.

Examples of the monovalent fluorinated chain hydrocarbon group having 1 to 4 carbon atoms include: Trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoro Fluorinated alkyl groups such as propyl and heptafluoro-n-propyl; Fluorinated alkenyl such as trifluorovinyl and pentafluoropropenyl; Fluorinated alkynyl groups such as fluoroethynyl, trifluoropropynyl, and the like.

Examples of the monovalent fluorinated alicyclic hydrocarbon group having 3 to 4 carbon atoms include fluorinated cycloalkyl groups such as fluorocyclobutyl.

In the above formula (1), the * represents a linking site with the main chain portion of the polymer, and is preferably a covalent bond.

（式（2）中， X及R ¹～R ³與式（1）相同； R為氫原子、氟原子、或者未經取代或經鹵素原子或烷氧基取代的一價烴基） The first structural unit (hereinafter, also referred to as "structural unit (1)") is preferably a structural unit represented by the following formula (2). [hua 3]

(In formula (2), X and R ¹ to R ³ are the same as those in formula (1); R is a hydrogen atom, a fluorine atom, or an unsubstituted or substituted monovalent hydrocarbon group with a halogen atom or an alkoxy group)

In the above-mentioned formula (2), the unsubstituted or halogen atom- or alkoxy-substituted monovalent hydrocarbon group represented by the above R is defined from the viewpoint of the copolymerizability of the monomer containing the first structural unit. In other words, a hydrogen atom and a methyl group are preferable, and a methyl group is more preferable.

（式（2-1）中， Z ¹及Z ²分別獨立地為氫原子、氟原子、一價烴基、一價氟化烴基、一價烴基或一價氟化烴基中的一個以上的碳原子經*-O-*、*-CO-*、*-COO-*或*-OCO-*所表示的連結基取代而成的基（其中，所述連結基中的*為與碳原子的鍵結鍵）、或者Z ¹及Z ²相互結合並與該些所鍵結的碳原子一起構成的環員數3～20的環結構； L為單鍵或二價有機基； n為1～5的整數） It is preferable that X in the said 1st structural unit is the group represented by following formula (2-1) in the said formula (2). [hua 4]

(In formula (2-1), Z ¹ and Z ² are each independently one or more carbon atoms selected from a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group, a monovalent fluorinated hydrocarbon group, a monovalent hydrocarbon group, or a monovalent fluorinated hydrocarbon group. A group substituted with a linking group represented by *-O-*, *-CO-*, *-COO-* or *-OCO-* (wherein, * in the linking group is a bond with a carbon atom bond), or Z ¹ and Z ² are combined with each other and form a ring structure with 3-20 ring members together with these bonded carbon atoms; L is a single bond or a divalent organic group; n is 1-5 integer)

In the above formula (2-1), examples of the monovalent hydrocarbon groups represented by Z ¹ and Z ² each independently include, for example, a methyl group, an ethyl group, and the like.

In the above formula (2-1), examples of the monovalent fluorinated hydrocarbon groups represented by Z ¹ and Z ² each independently include, for example, monovalent fluorinated hydrocarbon groups having 1 to 10 carbon atoms.

In the above formula (2-1), examples of the monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms represented by the above Z ¹ and Z ² include, for example, a monovalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms, A monovalent fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms, etc.

Examples of the monovalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms include: Trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl, 1,1,1,3,3,3-hexafluoro Fluorinated alkyl groups such as propyl and heptafluoro-n-propyl; Fluorinated alkenyl such as trifluorovinyl and pentafluoropropenyl; Fluorinated alkynyl groups such as fluoroethynyl, trifluoropropynyl, and the like.

Examples of the monovalent fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms include: Fluorocyclopentyl, difluorocyclopentyl, nonafluorocyclopentyl, fluorocyclohexyl, difluorocyclohexyl, undecafluorocyclohexylmethyl, fluoronorbornyl, fluoroadamantyl, fluorobornyl, fluoroiso Fluorinated cycloalkyl groups such as bornyl; Fluorinated cycloalkenyl such as fluorocyclopentenyl, nonafluorocyclohexenyl, etc.

The fluorinated hydrocarbon group is preferably the monovalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms, more preferably a monovalent fluorinated alkyl group having 1 to 8 carbon atoms, and still more preferably a monovalent fluorinated alkyl group having 1 to 6 carbon atoms. The perfluoroalkyl group is particularly preferably a linear perfluoroalkyl group having 1 to 6 carbon atoms.

In the above formula (2-1), as groups in which one or more carbon atoms in the monovalent fluorinated hydrocarbon groups represented by Z ¹ and Z ² are substituted with a linking group represented by *-O-*, each independently Examples include methoxymethyl and the like.

In the above formula (2-1), as a group in which one or more carbon atoms in the monovalent fluorinated hydrocarbon groups represented by Z ¹ and Z ² are substituted with a linking group represented by *-CO-*, each independently For example, acetyl group and the like can be mentioned.

In the above formula (2-1), as a group in which one or more carbon atoms in the monovalent fluorinated hydrocarbon groups represented by Z ¹ and Z ² are substituted by a linking group represented by *-COO-*, each independently Examples include methoxycarbonyl, ethoxycarbonyl and the like.

In the above formula (2-1), as groups in which one or more carbon atoms in the monovalent fluorinated hydrocarbon groups represented by Z ¹ and Z ² are substituted with a linking group represented by *-OCO-*, each independently Examples include methyl carbonate and the like.

In the above formula (2-1), as the ring structure (b) with 3 to 20 ring members formed by the bonding of the Z ¹ and Z ² to each other and the carbon atoms to which these bonded carbon atoms are formed, for example, if it is a self- The group obtained by removing two hydrogen atoms from the same carbon atom of the carbocyclic ring of the hydrocarbon having the above-mentioned number of carbon atoms is not particularly limited.

In the above formula (2-1), the divalent organic group represented by L includes, for example, a substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms, and a carbon-carbon bond between the hydrocarbon group. Divalent groups having -O-, -S-, -CO-, -COO-, -NR ²⁰ -, -CONR ²⁰ -, etc. (R ²⁰ is a hydrogen atom or a monovalent hydrocarbon group; the same applies hereinafter), divalent heterocycles Base et al.

In the above formula (2-1), n is an integer of 1 to 5, preferably 2 to 3.

Examples of the first structural unit include structural units represented by the following formulae (F-1) to (F-34) (hereinafter, also referred to as “structural units (1-1) to structural units (1-34). )")Wait.

[hua 5]

The content ratio of the first structural unit in the resin A is, for example, preferably 10 mol % or more, more preferably 20 mol % or more, with respect to all the structural units constituting the resin A. In addition, it may be 100 mol %, preferably 90 mol % or less, more preferably 80 mol % or less.

（式（3）中， R ⁴為氫原子、氟原子、甲基或三氟甲基； R ⁵為碳數1～20的一價烴基； R ⁶及R ⁷分別獨立地為碳數1～10的一價鏈狀烴基或碳數3～20的一價脂環式烴基、或者R ⁶及R ⁷相互結合並與該些所鍵結的碳原子一起構成的碳數3～20的二價脂環式基） The resin A may further have a second structural unit represented by the following formula (3) (hereinafter, also referred to as "structural unit (2)"). [hua 6]

(In formula (3), R ⁴ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R ⁵ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; R ⁶ and R ⁷ are each independently a carbon number of 1 to 20. A monovalent chain hydrocarbon group of 10 or a monovalent alicyclic hydrocarbon group of 3 to 20 carbon atoms, or a divalent carbon number of 3 to 20 composed of R ⁶ and R ⁷ combined with each other and these bonded carbon atoms alicyclic base)

In the above formula (3), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁵ include a methyl group, an ethyl group, and the like.

In the above formula (3), examples of the monovalent chain hydrocarbon group having 1 to 10 carbon atoms represented by R ⁶ and R ⁷ each independently include, for example, a methyl group, an ethyl group, and the like.

In the above formula (3), examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ⁶ and R ⁷ each independently include, for example, a cyclopentyl group, a cyclohexyl group, and the like.

In the above formula (3), as a bivalent alicyclic group having 3 to 20 carbon atoms in which R ⁶ and R ⁷ are bonded to each other and constituted together with these bonded carbon atoms, if it is self-constituting the above carbon atoms The group obtained by removing two hydrogen atoms from the same carbon atom of the carbocyclic ring of the hydrocarbon is not particularly limited.

Examples of the second structural unit include structural units represented by the following formulae (2-1) to (2-6) (hereinafter, also referred to as “structural units (2-1) to structural units (2-6). )")Wait.

[hua 7]

In the above formulas (2-1) to (2-6), R ⁴ to R ⁷ have the same meanings as in the above formula (2). i and j are each independently an integer of 0 to 16. k is 0-1.

As i and j, 1 is preferable. As R ⁵ , methyl, ethyl or isopropyl is preferred.

The resin A may contain one kind or two or more kinds of structural units (2) in combination.

With respect to all the structural units constituting the resin A, the content ratio of the second structural unit in the resin A when the second structural unit is included is, for example, preferably 1 mol % or more, more preferably 5 mol % or more. . In addition, it is preferably 70 mol % or less, more preferably 60 mol % or less.

(Synthesis method of resin A) The resin A can be synthesized by, for example, polymerizing a monomer providing each structural unit in an appropriate solvent using a radical polymerization initiator or the like.

Examples of the radical polymerization initiator include: azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) , 2,2'-azobis(2-cyclopropylpropanenitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyric acid Azo radical initiators such as dimethyl ester; peroxide radical initiators such as benzyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc. Among these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferable, and AIBN is more preferable. These radical initiators may be used alone or in combination of two or more.

Examples of the solvent used in the polymerization include: n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other alkanes; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylene dibromide, and chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate; Acetone, methyl ethyl ketone, 4-methyl-2-pentanone, 2-heptanone and other ketones; Ethers such as tetrahydrofuran, dimethoxyethane, and diethoxyethane; Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol, etc. These solvents used for the polymerization may be used alone or in combination of two or more.

The reaction temperature in the polymerization is usually 40°C to 150°C, preferably 50°C to 120°C. The reaction time is usually 1 hour to 48 hours, preferably 1 hour to 24 hours.

The molecular weight of the resin A is not particularly limited, and the polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) is preferably 1,000 or more and 50,000 or less, more preferably 2,000 or more and 30,000 or less, more preferably 3,000 or more and 15,000 or less, and particularly preferably 4,000 or more and 12,000 or less. If the Mw of the base resin is less than the lower limit, the heat resistance of the obtained resist film may decrease. When Mw of a base resin exceeds the said upper limit, the developability of a resist film may fall.

The ratio (Mw/Mn) of Mw of the resin A to the polystyrene conversion 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 1 or more and 2 or less.

The Mw and Mn of the resin A are values measured using gel permeation chromatography (GPC) under the following conditions.

GPC columns: 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (the above are manufactured by Tosoh Corporation) Column temperature: 40℃ Dissolution solvent: tetrahydrofuran Flow rate: 1.0 mL/min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Detector: Differential Refractometer Standard material: monodisperse polystyrene

The content of resin A is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and particularly preferably 1.5 part by mass or more with respect to 100 parts by mass of the following base resin. Moreover, 15 mass parts or less are preferable, 12 mass parts or less are more preferable, 10 mass parts or less are still more preferable, and 8 mass parts or less are especially preferable.

(Resin B) The resin B is a resin containing a structural unit having an acid dissociable group (hereinafter, this resin is also referred to as a "base resin"). Resin B is an aggregate of polymers having a structural unit containing an acid dissociable group (hereinafter, also referred to as "structural unit (I)"). The "acid-dissociable group" refers to a group that substitutes a hydrogen atom contained in a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a sulfo group, and the like, and is a group that is dissociated by the action of an acid. This radiation-sensitive resin composition is excellent in pattern formability because the resin has the structural unit (I).

The base resin preferably has, in addition to the structural unit (I), a structural unit (II) including at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure, which will be described later, You may have other structural units other than the structural unit (I) and the structural unit (II). Hereinafter, each structural unit will be described.

[Structural unit (I)] The structural unit (I) is a structural unit containing an acid dissociable group. The structural unit (I) is not particularly limited as long as it contains an acid dissociable group, and examples thereof include a structural unit having a tertiary alkyl ester moiety, and a structure in which a hydrogen atom having a phenolic hydroxyl group is substituted with a tertiary alkyl group. A structural unit, a structural unit having an acetal bond, or the like, is preferably a structural unit represented by the following formula (4) (hereinafter, also referred to as the "Structural Unit (I-1)").

（式（4）中， R ⁸為氫原子、氟原子、甲基或三氟甲基； R ⁹為碳數1～20的一價烴基； R ¹⁰及R ¹¹分別獨立地為碳數1～10的一價鏈狀烴基或碳數3～20的一價脂環式烴基、或者R ¹⁰及R ¹¹相互結合並與該些所鍵結的碳原子一起構成的碳數3～20的二價脂環式基） [hua 8]

(In the formula (4), R ⁸ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R ⁹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; R ¹⁰ and R ¹¹ are independently each of which has a carbon number of 1 to 20. A monovalent chain hydrocarbon group of 10 or a monovalent alicyclic hydrocarbon group of 3 to 20 carbon atoms, or a divalent carbon number of 3 to 20 in which R ¹⁰ and R ¹¹ are bonded to each other and together with these bonded carbon atoms alicyclic base)

In the above formula (4), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ include a methyl group, an ethyl group, and the like.

In the above formula (4), examples of the monovalent chain hydrocarbon group having 1 to 10 carbon atoms represented by R ¹⁰ and R ¹¹ each independently include, for example, a methyl group, an ethyl group, and the like.

In the above formula (4), examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ¹⁰ and R ¹¹ each independently include, for example, a cyclopentyl group, a cyclohexyl group, and the like.

In the above formula (4), as a bivalent alicyclic group having 3 to 20 carbon atoms in which R ¹⁰ and R ¹¹ are bonded to each other and constituted together with these bonded carbon atoms, if they are self-constituting the above carbon atoms The group obtained by removing two hydrogen atoms from the same carbon atom of the carbocyclic ring of the hydrocarbon is not particularly limited.

As the structural unit (I-1), for example, structural units represented by the following formulae (4-1) to (4-6) (hereinafter, also referred to as “structural unit (I-1-1) to unit (I-1-6)”), etc.

[Chemical 9]

In the above formulas (4-1) to (4-6), R ⁸ to R ¹¹ have the same meanings as in the above formula (4). i' and j' are each independently an integer of 0-16. k' is 0-1.

As i' and j', 1 is preferable. As R ⁹ , methyl, ethyl or isopropyl is preferred.

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

With respect to all the structural units constituting the base resin, the content ratio of the structural unit (I) (in the case of including a plurality of types, the total content ratio) is preferably 10 mol % or more, more preferably 20 mol % or more, and further Preferably, it is 30 mol % or more, and particularly preferably 35 mol % or more. In addition, it is preferably 80 mol % or less, more preferably 75 mol % or less, still more preferably 70 mol % or less, and particularly preferably 65 mol % or less. By making the content ratio of a structural unit (I) into the said range, the pattern formability of this radiation sensitive resin composition can be improved further.

[Structural unit (II)] The structural unit (II) is a structural unit containing 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 (II), the base resin can adjust the solubility with respect to the developing solution, and as a result, can improve the lithography performance such as the analytical properties of the radiation-sensitive resin composition. Moreover, the adhesiveness of the resist pattern formed with the base resin and a board|substrate can be improved.

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

[Chemical 10]

In the 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 carbon atoms, 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 divalent alicyclic group having 3 to 8 carbon atoms which are 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.

Examples of the divalent alicyclic group having 3 to 8 carbon atoms in which the R ^L4 and R ^L5 are bonded to each other and constituted together with the bonded carbon atoms include R ¹ and R in the formula (1) above. The chain hydrocarbon group or alicyclic hydrocarbon group represented by ² is a group having 3 to 8 carbon atoms among the divalent alicyclic groups having 3 to 20 carbon atoms in which the chain hydrocarbon group or the alicyclic hydrocarbon group is bonded to each other and constituted together with the bonded carbon atoms. One or more hydrogen atoms on the alicyclic group may be substituted with a hydroxyl group.

Examples of the divalent linking group represented by L ² include a divalent linear or branched hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms. One or more of these hydrocarbon groups and at least one group of -CO-, -O-, -NH- and -S-, etc.

As the structural unit (II), among these, a structural unit containing a lactone structure is preferable, a structural unit containing a norbornane lactone structure is more preferable, and a norbornane lactone derived (meth)acrylate is further preferable. - Structural unit of base ester.

The content ratio of the structural unit (II) is preferably 20 mol % or more, more preferably 25 mol % or more, and still more preferably 30 mol % or more with respect to all the structural units constituting the base resin. In addition, it is preferably 80 mol % or less, more preferably 75 mol % or less, still more preferably 70 mol % or less. By making the content ratio of a structural unit (II) into the said range, lithography performance, such as the analytical property of this radiation sensitive resin composition, and the adhesiveness of the formed resist pattern and a board|substrate can be improved further.

[Structural unit (III)] The base resin optionally has other structural units in addition to the structural unit (I) and the structural unit (II). As said other structural unit, the structural unit (III) containing a polar group etc. are mentioned, for example (however, the thing corresponding to a structural unit (II) is excluded). By further having the structural unit (III), the base resin can adjust the solubility with respect to the developing solution, and as a result, can improve the lithography performance such as the analytical properties of the radiation-sensitive resin composition. As said polar group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a sulfonamido 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 (III), the structural unit etc. which are represented by the following formula are mentioned, for example.

[Chemical 11]

In the formula, ^RA is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

When the base resin contains the structural unit (III) having a polar group, the content of the structural unit (III) is preferably 5 mol % or more relative to all the structural units constituting the base resin, More preferably, it is 8 mol % or more, and still more preferably 10 mol % or more. In addition, it is preferably 40 mol % or less, more preferably 35 mol % or less, still more preferably 30 mol % or less. By setting the content ratio of the structural unit (III) to the above-mentioned range, the lithography performance such as the resolution of the radiation-sensitive resin composition can be further improved.

[Structural Unit (IV)] As other structural units, in addition to the structural unit (III) having a polar group, the base resin optionally has a structural unit derived from hydroxystyrene or a structural unit having a phenolic hydroxyl group (hereinafter, both are also referred to together). "Structural Unit (IV)"). The structural unit (IV) contributes to the improvement of etching resistance and the improvement of the difference in developer solubility (dissolution contrast) between the exposed part and the unexposed part. In particular, it can be preferably applied to pattern formation using exposure with radiation having a wavelength of 50 nm or less, such as electron beams or EUV. In this case, it is preferable that resin has a structural unit (IV) and a structural unit (I) together.

In this case, it is preferable to carry out the polymerization in a state in which the phenolic hydroxyl group is protected by a protecting group such as an alkali dissociable group during the polymerization, and then hydrolyze and deprotect, whereby the structural unit (IV) is obtained. The structural unit which provides the structural unit (IV) by hydrolysis is preferably represented by the following formula (6-1) and formula (6-2).

[Chemical 12]

In the formula (6-1) and formula (6-2), R ¹³ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ¹⁴ is a monovalent hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹⁴ include the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ⁸ in the structural unit (I). As an alkoxy group, a methoxy group, an ethoxy group, a 3rd butoxy group, etc. are mentioned, for example.

As the R ¹⁴ , an alkyl group and an alkoxy group are preferable, and among them, a methyl group and a tertiary butoxy group are more preferable.

In the case of a resin for exposure by radiation with a wavelength of 50 nm or less, the content ratio of the structural unit (IV) is preferably 10 mol % or more, more preferably 20 mol % with respect to all the structural units constituting the resin. %above. In addition, it is preferably 70 mol % or less, more preferably 60 mol % or less.

(Synthesis method of resin B) The resin B can be synthesized by, for example, polymerizing a monomer providing each structural unit in an appropriate solvent using a radical polymerization initiator or the like.

As the radical polymerization initiator, azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), ,2'-azobis(2-cyclopropylpropanenitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyric acid dimethyl Azo-based radical initiators such as esters; peroxide-based radical initiators such as benzyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc. Among these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferable, and AIBN is more preferable. These radical initiators may be used alone or in combination of two or more.

Examples of the solvent used in the polymerization include: n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other alkanes; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylene dibromide, and chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate; Acetone, methyl ethyl ketone, 4-methyl-2-pentanone, 2-heptanone and other ketones; Ethers such as tetrahydrofuran, dimethoxyethane, and diethoxyethane; Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol, etc. These solvents used for the polymerization may be used alone or in combination of two or more.

The reaction temperature in the polymerization is usually 40°C to 150°C, preferably 50°C to 120°C. The reaction time is usually 1 hour to 48 hours, preferably 1 hour to 24 hours.

The molecular weight of the base resin is not particularly limited, and the polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) is preferably 1,000 or more and 50,000 or less, more preferably 2,000 or more and 30,000 or less, More preferably, it is 3,000 or more and 15,000 or less, and particularly preferably 4,000 or more and 12,000 or less. If the Mw of the base resin is less than the lower limit, the heat resistance of the obtained resist film may decrease. When Mw of a base resin exceeds the said upper limit, the developability of a resist film may fall.

The ratio (Mw/Mn) of Mw of 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 1 or more. , 2 or less.

The Mw and Mn of the base resin are values measured by gel permeation chromatography (GPC) in the same manner as in the case of the resin A described above.

The content of the base resin is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more with respect to the total solid content of the radiation-sensitive resin composition.

(other resins) The radiation-sensitive resin composition of the present embodiment may contain a resin having a larger mass content of fluorine atoms than the base resin (hereinafter, also referred to as "high fluorine content resin") as another resin different from the resin A. resin. When the radiation-sensitive resin composition contains a resin with a high fluorine content, it can be biased to exist in the surface layer of the resist film relative to the base resin, and as a result, the resistance of the resist film at the time of liquid immersion exposure can be improved. Water repellency of the surface.

The high fluorine content resin preferably has, for example, a structural unit represented by the following formula (7) (hereinafter, also referred to as "structural unit (V)"), and may have a structural unit in the base resin as necessary (I) or structural unit (II).

[Chemical 13]

In the formula (7), R ¹⁵ is a hydrogen atom, a methyl group or a trifluoromethyl group. GL is a single bond, an oxygen atom, a sulfur atom, -COO-, -SO ₂ ^ONH- , -CONH- or -OCONH-. R ¹⁶ is a monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms.

As said ^R15 , ^a hydrogen atom and a methyl group are preferable from a viewpoint of the copolymerizability of the monomer which provides a structural unit (V), and a methyl group is more preferable.

As said GL, a single bond and -COO- are preferable from a viewpoint of providing the copolymerizability of the monomer of a structural unit (V), and ^-COO- is more preferable.

Examples of the monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms represented by R ^{1 6} include a part or all of the hydrogen atoms contained in the straight-chain or branched alkyl group having 1 to 20 carbon atoms that have undergone fluorine atoms. replaced by.

As the monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ^{1 6} , a part or all of the hydrogen atoms contained in the monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms are fluorinated. Atom replacement.

The R ¹⁶ is preferably a fluorinated chain hydrocarbon group, more preferably a fluorinated alkyl group, and still more preferably 2,2,2-trifluoroethyl, 1,1,1,3,3,3-hexa Fluoropropyl and 5,5,5-trifluoro-1,1-diethylpentyl.

When the high fluorine content resin has a structural unit (V), the content ratio of the structural unit (V) is preferably 30 mol % or more, more preferably 40 mol % with respect to all the structural units constituting the high fluorine content resin % or more, more preferably 45 mol % or more, and particularly preferably 50 mol % or more. In addition, it is preferably 95 mol % or less, more preferably 90 mol % or less, and still more preferably 85 mol % or less. By setting the content ratio of the structural unit (V) to the above-mentioned range, the mass content ratio of fluorine atoms in the resin with high fluorine content can be adjusted more appropriately, and the biased existence in the surface layer of the resist film can be further promoted, as a result. , the water repellency of the resist film during liquid immersion exposure can be further improved.

The high fluorine content resin may have a fluorine atom-containing structural unit (hereinafter, also referred to as a structural unit (VI) represented by the following formula (f-2) together with the structural unit (V) or in place of the structural unit (V). )). Since the high fluorine content resin has the structural unit (f-2), the solubility to an alkaline developer can be improved, and the occurrence of development defects can be suppressed.

[Chemical 14]

The structural unit (VI) is roughly classified into those having (x) an alkali-soluble group, and those having (y) a group that is dissociated by the action of an alkali and has an increased solubility in an alkaline developer (hereinafter, also abbreviated as "alkali"). dissociative base") in both cases. Both (x) and (y) are common, and in the formula (f-2), R ^C is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ^D is a single bond, a (s+1)-valent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, -NR ^dd -, a carbonyl group, and -COO- are bonded to the terminal on the R ^E side of the hydrocarbon group. or -CONH-, or a structure in which a part of the hydrogen atoms contained in the hydrocarbon group is substituted with an organic group having a heteroatom. R ^dd is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. s is an integer of 1-3.

When the structural unit (VI) has (x) an alkali-soluble group, R ^F is a hydrogen atom, and A ¹ is an oxygen atom, -COO-* or -SO ₂ O-*. * ^Indicates the site bound to RF. W ¹ is a single bond, a hydrocarbon group having 1 to 20 carbon atoms or a divalent fluorinated hydrocarbon group. When A ¹ is an oxygen atom, W ¹ is a fluorinated hydrocarbon group having a fluorine atom or a fluoroalkyl group on the carbon atom to which A ¹ is bonded. R ^E is a single bond or a divalent organic group having 1 to 20 carbon atoms. When s is 2 or 3, a plurality of RE, ^{W 1} , ^{A 1} and RF may be the same or different, respectively. When the structural unit (VI) has (x) an alkali-soluble group, the affinity for an alkaline developer can be improved, and development defects can be suppressed. The structural unit (VI) having (x) an alkali-soluble group is particularly preferably one in which A ¹ is an oxygen atom and W ¹ is 1,1,1,3,3,3-hexafluoro-2,2-methanediyl. Happening.

When the structural unit (VI) has (y) a base dissociable group, R ^F is a monovalent organic group having 1 to 30 carbon atoms, and A ¹ is an oxygen atom, -NR ^aa -, -COO-* or -SO ₂ O-*. R ^aa is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. * ^Indicates the site bound to RF. W ¹ is a single bond or a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. R ^E is a single bond or a divalent organic group having 1 to 20 carbon atoms. When A ¹ is -COO-* or -SO ₂ O-*, W ¹ or R ^F has a fluorine atom on a carbon atom bonded to A ¹ or a carbon atom adjacent thereto. When A ¹ is an oxygen atom, W ¹ and R ^E are a single bond, R ^D is a structure in which a carbonyl group is bonded to the terminal on the R ^E side of a hydrocarbon group having 1 to 20 carbon atoms, and R ^F is a structure having fluorine. The organic radical of an atom. When s is 2 or 3, a plurality of RE, ^{W 1} , ^{A 1} and RF may be the same or different, respectively. Since the structural unit (VI) has (y) an alkali dissociable group, in the alkali development step, the surface of the resist film is changed from hydrophobicity to hydrophilicity. As a result, the affinity for the developer can be greatly improved, and development defects can be suppressed more efficiently. As a structural unit (VI) which has a base dissociable group (y), A ¹ is -COO-*, and it is especially preferable that R ^F or W ¹ or both have a fluorine atom.

As R ^C , a hydrogen atom and a methyl group are preferable, and a methyl group is more preferable from the viewpoint of the copolymerizability of the monomer which provides the structural unit (VI).

When ^RE is a divalent organic group, it is preferably a group having a lactone structure, more preferably a group having a polycyclic lactone structure, and still more preferably a group having a norbornane lactone structure.

When the high fluorine content resin has a structural unit (VI), the content ratio of the structural unit (VI) is preferably 50 mol % or more, more preferably 60 mol % with respect to all the structural units constituting the high fluorine content resin % or more, more preferably 70 mol % or more. In addition, it is preferably 95 mol % or less, more preferably 90 mol % or less, and still more preferably 85 mol % or less. By setting the content ratio of the structural unit (VI) to the above range, the water repellency of the resist film at the time of liquid immersion exposure can be further improved.

（所述式（8）中，R ^1α為氫原子、氟原子、甲基或三氟甲基；R ^2α為碳數3～20的一價脂環式烴基） [Other Structural Units] The high fluorine content resin may contain, as structural units other than the structural units listed above, a structural unit having an alicyclic structure represented by the following formula (8). [Chemical 15]

(In the above formula (8), R ^1α is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R ^2α is a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms)

In the above formula (8), examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ^2α include a part of hydrogen atoms contained in a monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms, or All groups substituted with fluorine atoms.

When the high fluorine content resin contains the structural unit having an alicyclic structure, the content ratio of the structural unit having an alicyclic structure is preferably 10 mol % with respect to all the structural units constituting the high fluorine content resin Above, more preferably 20 mol % or more, still more preferably 30 mol % or more. In addition, it is preferably 70 mol % or less, more preferably 60 mol % or less, and still more preferably 50 mol % or less.

As a lower limit of Mw of a high fluorine content resin, 1,000 is preferable, 2,000 is more preferable, 3,000 is still more preferable, and 5,000 is especially preferable. The upper limit of the Mw is preferably 50,000, more preferably 30,000, still more preferably 20,000, and particularly preferably 15,000.

The lower limit of Mw/Mn of the high fluorine content resin is usually 1, and more preferably 1.1. The upper limit of the Mw/Mn is usually 5, preferably 3, more preferably 2, still more preferably 1.9.

The content of the high fluorine content resin is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and particularly preferably 1.5 part by mass or more, relative to 100 parts by mass of the base resin. Moreover, 15 mass parts or less are preferable, 12 mass parts or less are more preferable, 10 mass parts or less are still more preferable, and 8 mass parts or less are especially preferable.

The radiation-sensitive resin composition may contain one kind or two or more kinds of high fluorine content resins.

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

(radiosensitive acid generator) The radiation-sensitive resin composition of the present embodiment further includes a radiation-sensitive acid generator that generates an acid by irradiation (exposure) with radiation. In the case where the base resin having the structural unit (I) and the resin A includes the structural unit (2), the acid generated by the radiation-sensitive acid generator by exposure can make the structural unit (I) and the structure The acid-dissociable group of the unit (2) is dissociated to generate a carboxyl group or the like.

When the radiation-sensitive resin composition contains the radiation-sensitive acid generator, the polarity of the resin in the exposed portion increases, and when the resin in the exposed portion is developed in an alkaline aqueous solution, it becomes soluble in the developing solution, and the other is On the other hand, in the case of developing with an organic solvent, it becomes poorly soluble with respect to a developing solution.

As a radiation-sensitive acid generator, an onium salt compound, a sulfonimide compound, a halogen-containing compound, a diazoketone compound, etc. are mentioned, for example. As an onium salt compound, a pernium salt, a tetrahydrothiophenium salt, an iodonium salt, a phosphonium salt, a diazonium salt, a pyridinium salt, etc. are mentioned, for example. Among these, pericynium salts and iodonium salts are preferred.

As an acid generated by exposure, a sulfonic acid is generated by exposure. Examples of such an acid include compounds in which one or more fluorine atoms or fluorinated hydrocarbon groups are substituted on the carbon atoms adjacent to the sulfo group. Among them, as the radiation-sensitive acid generator, those having a cyclic structure are particularly preferred.

These radiation-sensitive acid generators may be used alone or in combination of two or more. With respect to 100 parts by mass of the base resin, the content of the radiation-sensitive acid generator (when a plurality of types of radiation-sensitive acid generators are used in combination, the sum of these) is preferably 0.1 part by mass or more, more preferably 1 part by mass part or more, more preferably 5 parts by mass or more. Moreover, 40 mass parts or less are preferable with respect to 100 mass parts of said resins, 35 mass parts or less are more preferable, 30 mass parts or less are further more preferable, and 20 mass parts or less are especially preferable. Thereby, excellent sensitivity, LWR performance, and CDU performance can be exhibited when forming a resist pattern.

(acid diffusion control agent) The radiation-sensitive resin composition may contain an acid diffusion control agent as needed. The acid diffusion control agent has the effect of controlling the diffusion phenomenon in the resist film of the acid generated by the radiation-sensitive acid generator by exposure, and suppressing the undesired chemical reaction in the non-exposed area. In addition, the storage stability of the obtained radiation-sensitive resin composition is improved. Furthermore, the resolution of the resist pattern is further improved, and the variation in the line width of the resist pattern caused by the fluctuation of the standing time from exposure to development can be suppressed, so that radiation sensitivity excellent in process stability can be obtained. resin composition.

Examples of the acid diffusion control agent include a compound represented by the following formula (5) (hereinafter, also referred to as "nitrogen-containing compound (I)") and a compound having two nitrogen atoms in the same molecule (hereinafter, "nitrogen-containing compound (I)") Also referred to as "nitrogen-containing compound (II)"), compounds having three nitrogen atoms (hereinafter, also referred to as "nitrogen-containing compound (III)"), amide group-containing compounds, urea compounds, nitrogen-containing heterocycles compounds, etc.

[Chemical 16]

In the formula (5), R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or substituted or unsubstituted aralkyl.

Examples of the nitrogen-containing compound (I) include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; and aromatic amines such as aniline. class etc.

As nitrogen-containing compound (II), ethylenediamine, N,N,N',N'- tetramethylethylenediamine, etc. are mentioned, for example.

Examples of the nitrogen-containing compound (III) include polyamine compounds such as polyethyleneimine and polyallylamine; polymers such as dimethylaminoethylacrylamide and the like.

Examples of the amide group-containing compound include carboxamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N - Dimethylacetamide, propionamide, benzylamide, pyrrolidone, N-methylpyrrolidone, etc.

As a urea compound, urea, methyl urea, 1, 1- dimethyl urea, 1, 3- dimethyl urea, 1, 1, 3, 3- tetramethyl urea, 1, 3- di- Phenyl urea, tributyl thiourea, etc.

Examples of nitrogen-containing heterocyclic compounds include pyridines such as pyridine and 2-picoline; morpholines such as N-propylmorpholine and N-(undecylcarbonyloxyethyl)morpholine; pyridines oxazine, pyrazole, etc.

Moreover, as said nitrogen-containing organic compound, the compound which has an acid dissociable group can also be used. Examples of the nitrogen-containing organic compound having such an acid dissociable group include N-tert-butoxycarbonylpiperidine, N-tert-butoxycarbonylimidazole, and N-tert-butoxycarbonylbenzimidazole. , N-tertiary butoxycarbonyl-2-phenylbenzimidazole, N-(tertiary butoxycarbonyl) di-n-octylamine, N-(tertiary butoxycarbonyl) diethanolamine, N-( tertiary butoxycarbonyl) dicyclohexylamine, N-(tertiary butoxycarbonyl) diphenylamine, N-tertiary butoxycarbonyl-4-hydroxypiperidine, N-tertiary pentoxycarbonyl -4-Hydroxypiperidine etc.

Moreover, as an acid diffusion control agent, the photodegradable base which produces|generates a weak acid by exposure can also be used suitably. Examples of the photodegradable base include compounds containing a radiosensitive onium cation decomposed by exposure and an anion of a weak acid. Since the photodegradable base generates a weak acid in the exposed portion by the proton generated by the decomposition of the radiosensitive onium cation and the anion of the weak acid, the acid diffusion controllability is lowered.

As a photodegradable base, the periconium salt compound represented by following formula (6-1), the iodonium salt compound represented by following formula (6-2), etc. are mentioned, for example.

[Chemical 17]

In the above formulas (6-1) and (6-2), J ⁺ is a perionium cation, and U ⁺ is an iodonium cation. As pericium cations represented by J ⁺ , in addition to the pericium cations represented by the following formulas (1-1-a) and (1-1-b), those represented by the following formula (X-1) may also be mentioned. As the iodonium cation represented by U ⁺ , in addition to the iodonium cation represented by the above formula (1-1-c), the iodonium cation represented by the following formula (X-2) can be exemplified. E ^- and Q ^- are each independently an anion represented by OH ^- , Rα-COO ^- , and Rα-SO ₃ ^- . Rα is an alkyl group, an aryl group or an aralkyl group. The hydrogen atom of the aromatic ring of the aryl group or aralkyl group represented by Rα may be substituted with a hydroxyl group, a fluorine atom-substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[Chemical 18]

[Chemical 19]

In the formula (X-1), R ^c1 , R ^c2 and R ^c3 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted alkyl group A substituted aromatic hydrocarbon group having 6 to 12 carbon atoms.

In the formula (X-2), R ^e1 and R ^e2 are each independently a halogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted alkyl group. A substituted aromatic hydrocarbon group having 6 to 12 carbon atoms. k8 and k9 are each independently an integer of 0-4.

Examples of substituents that can substitute the hydrogen atoms of the above groups include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, and alkyl groups ( In the case of substituting a hydrogen atom of a cycloalkyl group or an aromatic hydrocarbon group), aryl group (in the case of substituting a hydrogen atom of an alkyl group), alkoxy group, alkoxycarbonyl group, alkoxycarbonyloxy group, acyl group , oxyalkyl, etc. Among these, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an acyl group, and an acyloxy group are preferable, and an alkoxy group or an alkoxycarbonyl group is more preferable.

As said photodegradable base, the compound etc. which are represented by the following formula are mentioned, for example.

[hua 20]

Among these, the photodegradable base is preferably a perylene salt, more preferably a triaryl perylene salt, and still more preferably a triphenyl perylene salicylate and a triphenyl perylene 10-camphorsulfonate.

The lower limit of the content of the acid diffusion control agent is preferably 3 parts by mass, more preferably 4 parts by mass, and still more preferably 5 parts by mass with respect to 100 parts by mass of the radiation-sensitive acid generator in total. The upper limit of the content is preferably 150 parts by mass, more preferably 120 parts by mass, and still more preferably 110 parts by mass.

By setting the content of the acid diffusion control agent to the above-mentioned range, the lithography performance of the radiation-sensitive resin composition can be further improved. The radiation-sensitive resin composition may contain one or two or more acid diffusion control agents.

(solvent) The radiation-sensitive resin composition of the present embodiment contains a solvent. The solvent is not particularly limited as long as it can dissolve or disperse at least the resin A, the resin B, the radiation-sensitive acid generator, and the like.

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

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 monohydric alcohol solvents with carbon number of 1 to 18; Ethylene glycol, 1,2-propylene glycol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc. carbon number 2 ~18 polyol-based solvents; A polyhydric alcohol partial ether type solvent etc. which etherify a part of the hydroxyl group which the said polyhydric alcohol type solvent has.

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

Examples of the ketone-based solvent include chain ketone-based solvents such as acetone, methyl ethyl ketone, and methyl-isobutyl ketone; Cyclic ketone solvents such as cyclopentanone, cyclohexanone, methyl cyclohexanone; 2,4-pentanedione, acetone acetone, acetophenone, etc.

Examples of the amide-based solvent 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 solvents such as amide and N-methylpropionamide, 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 polyhydric alcohol partial ether acetate solvents; Lactone solvents such as γ-butyrolactone and valerolactone; Carbonate-based solvents such as diethyl carbonate, ethylene carbonate, and propyl carbonate; Polycarboxylic acid diester-based solvents such as propylene glycol diacetate, methoxytriethylene glycol acetate, diethyl oxalate, ethyl acetate, ethyl lactate, and diethyl phthalate.

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

Among these, ester-based solvents and ketone-based solvents are preferred, polyol partial ether acetate-based solvents, cyclic ketone-based solvents, and lactone-based solvents are more preferred, and propylene glycol monomethyl ether acetate, Cyclohexanone, gamma-butyrolactone. The radiation-sensitive resin composition may contain one or two or more kinds of solvents.

(any other ingredients) The radiation-sensitive resin composition may contain other arbitrary components in addition to the above-mentioned components. Examples of the other optional components include a crosslinking agent, a biasing accelerator, a surfactant, an alicyclic skeleton-containing compound, a sensitizer, and the like. These other optional components may be used alone or in combination of two or more.

(crosslinking agent) The crosslinking agent is a compound having two or more functional groups, and in the baking step after the general exposure step, a crosslinking reaction is induced in the resin component by an acid catalyst reaction, and the molecular weight of the resin component is increased. By increasing, the solubility of the pattern exposure portion with respect to the developing solution is decreased. As said functional group, a (meth)acryloyl group, a hydroxymethyl group, an alkoxymethyl group, an epoxy group, a vinyl ether group, etc. are mentioned, for example.

(biased towards existential accelerators) The localization accelerator has the effect of making the high fluorine content resin more efficiently localized on the surface of the resist film. By making the radiation-sensitive resin composition contain the biased existence accelerator, the addition amount of the high-fluorine-content resin can be reduced compared with the conventional method. Therefore, while maintaining the lithography performance of the radiation-sensitive resin composition, the elution of components from the resist film to the liquid immersion medium can be further suppressed, or the liquid immersion exposure can be performed at a higher speed by high-speed scanning. As a result, It is possible to improve the hydrophobicity of the surface of the resist film which suppresses defects derived from liquid immersion such as watermark defects. As a thing which can be used as such a biasing accelerator, for example, a low molecular weight compound whose relative dielectric constant is 30 or more and 200 or less and whose boiling point under one atmospheric pressure is 100 degreeC or more is mentioned. As such a compound, a lactone compound, a carbonate compound, a nitrile compound, a polyhydric alcohol etc. are mentioned specifically,.

As said lactone compound, gamma-butyrolactone, valerolactone, mevalonic lactone, norbornane lactone etc. are mentioned, for example.

As said carbonate compound, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, etc. are mentioned, for example.

As said nitrile compound, succinonitrile etc. are mentioned, for example.

As said polyhydric alcohol, glycerol etc. are mentioned, for example.

With respect to 100 parts by mass of the total amount of resin in the radiation-sensitive resin composition, the content of the biasing accelerator is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more, Particularly preferred is 25 parts by mass or more. Moreover, 300 mass parts or less are preferable, 200 mass parts or less are more preferable, 100 mass parts or less are still more preferable, and 80 mass parts or less are especially preferable. The radiation-sensitive resin composition may also contain one or two or more kinds of biased existence accelerators.

(surfactant) The surfactant has the effect of improving coatability, striation, developability, and the like. As the surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyoxyethylene Nonionic surfactants such as ethylene glycol dilaurate and polyethylene glycol distearate; commercially available products include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75. Polyflow No.95 (the above are manufactured by Gongrongsha Chemical), Eftop EF301, Eftop EF303, Eftop EF352 (the above are Taokai) Tohchem Products), Megafac F171, Megafac F173 (the above are manufactured by DIC), Fluorad FC430, Fluorad FC431 (above Made for Sumitomo 3M), Asahi Guard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon ) SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (the above are manufactured by Asahi Glass Industry), etc. The content of the surfactant in the radiation-sensitive resin composition is usually 2 parts by mass or less with respect to 100 parts by mass of the resin.

(compounds containing alicyclic skeleton) The compound containing an alicyclic skeleton has the effect of improving dry etching resistance, pattern shape, adhesion to a substrate, and the like.

Examples of compounds containing an alicyclic skeleton include: Adamantane derivatives such as 1-adamantane carboxylic acid, 2-adamantanone, 1-adamantane carboxylic acid tert-butyl ester; Deoxycholate esters such as 3-butyl deoxycholate, 3-butoxycarbonyl deoxycholate, and 2-ethoxyethyl deoxycholate; Lithocholic acid 3-butyl ester, lithocholic acid 3-butoxycarbonyl methyl ester, lithocholic acid 2-ethoxyethyl ester and other lithocholic acid esters; 3-[2-Hydroxy-2,2-bis(trifluoromethyl)ethyl]tetracyclo[4.4.0.1(2,5).1(7,10)]dodecane, 2-hydroxy-9- Methoxycarbonyl-5-oxo-4-oxa-tricyclo[4.2.1.0(3,7)]nonane, etc. The content of the alicyclic skeleton-containing compound in the radiation-sensitive resin composition is usually 5 parts by mass or less with respect to 100 parts by mass of the resin.

(sensitizer) The sensitizer has the effect of increasing the amount of acid generated from the radiation-sensitive acid generator or the like, and has the effect of improving the "apparent sensitivity" of the radiation-sensitive resin composition.

Examples of sensitizers include: carbazoles, acetophenones, benzophenones, naphthalenes, phenols, diacetyl, eosin, rose Bengal, pyrenes, anthracenes, phenothiazine class etc. These sensitizers may be used alone or in combination of two or more. The content of the sensitizer in the radiation-sensitive resin composition is usually 2 parts by mass or less with respect to 100 parts by mass of the resin.

<Preparation method of radiation-sensitive resin composition> The radiation-sensitive resin composition can be prepared, for example, by mixing the resin A, the resin B, the radiation-sensitive acid generator, optionally a high fluorine-content resin, etc., and a solvent 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 after mixing. The solid content concentration of the radiation-sensitive resin composition is usually 0.1 to 50 mass %, preferably 0.5 to 30 mass %, and more preferably 1 to 20 mass %.

<Method for forming a resist pattern> A method for forming a resist pattern according to an embodiment of the present invention includes: A step of directly or indirectly coating the radiation-sensitive resin composition on a substrate to form a resist film (hereinafter, also referred to as "resist film forming step"); a step of exposing the resist film by immersion exposure (hereinafter, also referred to as an "exposure step"); and A step of developing the exposed resist film (hereinafter, also referred to as a "development step").

According to the method for forming a resist pattern, since the radiation-sensitive resin composition containing the resin A is used, a resist pattern with good sensitivity, high water repellency, and few defects can be formed. Hereinafter, each step will be described.

[Resist film formation step] In this step (resist film forming step), a resist film is formed using the radiation-sensitive resin composition. As a substrate on which the resist film is formed, for example, conventionally known ones such as silicon wafers, silicon dioxide, and aluminum-coated wafers can be mentioned. In addition, an organic or inorganic antireflection film disclosed in, for example, Japanese Patent Laid-Open No. 6-12452, Japanese Patent Laid-Open No. 59-93448, etc. may be formed on the substrate. As a coating method, spin coating (spin coating), casting coating, roll coating, etc. are mentioned, for example. After coating, prebake (PB) may be performed as necessary 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 thickness of the resist film to be formed is preferably 10 nm to 1,000 nm, and more preferably 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, in order to avoid direct contact between the liquid immersion liquid and the resist film For the purpose of immersion, a liquid immersion protective film which is insoluble to the liquid immersion liquid may be provided on the formed resist film. As the liquid immersion protective film, a film formed by the water repellency improving agent can also be used. As the protective film for liquid immersion, a solvent peeling type protective film that is peeled off with a solvent before the development step (for example, refer to Japanese Patent Laid-Open No. 2006-227632), and a developer peeling type that is peeled off simultaneously with the development of the developing step can also be used Any of the protective films (for example, refer to WO2005-069076 A and WO2006-035790). Among them, from the viewpoint of yield, it is preferable to use a developing solution peeling-type liquid immersion protective film.

In addition, when performing the exposure step as the next step with radiation having a wavelength of 50 nm or less, it is preferable to use a resin having the structural unit (I) and the structural unit (IV) as a base in the composition resin.

[Exposure step] In this step (the exposure step), the resist film formed in the resist film forming step is exposed to radiation by irradiating the resist film formed in the resist film forming step through a photomask (via a liquid immersion medium such as water as appropriate). 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, and charged particle beams such as electron beams and α rays, depending on the line width of the target pattern. . Among them, far-ultraviolet rays, electron beams, EUV are preferred, ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), electron beams, EUV are more preferred, and further preferred are positioned as Electron beam and EUV with wavelengths below 50 nm for next-generation exposure technology.

When exposure is performed by liquid immersion exposure, as a liquid immersion liquid to be used, water, a fluorine-type inert liquid, etc. are mentioned, for example. The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a temperature coefficient of refractive index as small as possible to minimize the distortion of the optical image projected on the film, especially when the exposure light source is an ArF excimer laser. In the case of irradiated light (wavelength of 193 nm), it is preferable to use water from the viewpoints of easiness of acquisition, easiness of handling, and the like. In the case of using water, an additive which reduces the surface tension of water and increases the interfacial active force may be added at a slight ratio. The additive preferably does not dissolve the resist film on the wafer and has a negligible effect on the optical coating on the lower surface of the lens. As the water to be used, distilled water is preferred.

Preferably, a post exposure bake (PEB) is performed after the exposure, and in the exposed portion of the resist film, the acid generated by the self-inductive radiation acid generator by exposure is used to promote the resin Dissociation of acid dissociable groups, etc. Due to this PEB, the difference in solubility with respect to the developer occurs between the exposed portion and the unexposed portion. 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 step] In this step (the development step), the resist film exposed in the exposure step is developed. Thereby, a predetermined resist pattern can be formed. Generally, it wash|cleans with the rinse liquid, such as water or alcohol, after image development, and it is dried.

As the developing solution 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 amine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethyl ammonium hydroxide (TMAH), Bases such as pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene Alkaline aqueous solution of at least one kind of 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 developing with an organic solvent, organic solvents such as hydrocarbon-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, and alcohol-based solvents, or solvents containing organic solvents can be exemplified. As the organic solvent, for example, one or two or more of the solvents listed as the solvent of the radiation-sensitive resin composition may be mentioned. Among these, ether-based solvents, ester-based solvents, and ketone-based solvents are preferred. The ether-based solvent is preferably a glycol ether-based solvent, and more preferably ethylene glycol monomethyl ether and propylene glycol monomethyl ether. As the ester-based solvent, an acetate-based solvent is preferable, and n-butyl acetate and amyl acetate are more preferable. The ketone-based solvent is preferably a chain ketone, more preferably 2-heptanone. The content of the organic solvent in the developer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 99% by mass or more. As a component other than the organic solvent in a developer, water, a silicone oil, etc. are mentioned, for example.

As described above, as the developer, either an alkaline developer or an organic solvent developer may be used.

Examples of the developing method include: a method of immersing a substrate in a tank filled with a developing solution for a fixed period of time (dipping method); a method of developing by depositing a developing solution on the surface of the substrate by utilizing surface tension and standing still for a fixed period of time (overlay method) liquid (puddle) method); the method of spraying the developer on the surface of the substrate (spray method); the method of continuously applying the developer on the substrate rotating at a fixed speed while scanning the nozzle for the developer at a fixed speed (dynamic distribution method) etc.

＜Water repellency improver＞ The water repellency improving agent of one Embodiment of this invention contains the said resin A. As long as the effect of this invention is not impaired, this water repellency improver may contain other arbitrary components. By containing the predetermined resin A, the water repellency improving agent can easily impart, increase or improve the water repellency of a resist film or the like.

Resin A is resin A which has the 1st structural unit containing the partial structure represented by the said formula (1). As the resin A, the resin described in the section of the radiation-sensitive resin composition can be suitably used in the same manner.

As said arbitrary component, a solvent etc. are mentioned, for example. The solvent described in the section of the radiation-sensitive resin composition can be suitably used in the same manner.

In the case of performing liquid immersion exposure based on, for example, ArF excimer laser light or the like using the radiation-sensitive resin composition containing the water repellency improving agent of the present invention, the elution of the composition into the liquid immersion liquid can be prevented or reduced, In addition, contamination of the lens of the exposure light source can be prevented or reduced.

In addition, when exposure by, for example, EUV (Extreme Ultraviolet) is performed using the radiation-sensitive resin composition containing the water repellency improving agent of the present invention, it is possible to suppress or reduce the occurrence of rinsing treatment with fresh water after development. Droplet residual defect.

In addition, the immersion upper layer film-forming composition containing the water repellency improving agent and the solvent of the present invention can be used to form an immersion upper layer film on a resist film. [Example]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. The measurement methods of various physical property values are shown below. In addition, in the following synthesis examples and the like, unless otherwise specified, the parts by mass refer to the value when the total mass of the monomers used is 100 parts by mass, and the mole % refers to the amount of the monomers used. The total number of moles of the measuring body is the value when 100 mole % is used.

[Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn)] The adjusted Mw and Mn of the polymer were determined by gel permeation chromatography (GPC) using GPC columns (two "G2000HXL", one "G3000HXL" and one "G4000HXL" manufactured by Tosoh Corporation). root), and measured under the following conditions. In addition, the degree of dispersion (Mw/Mn) was calculated from the measurement results of Mw and Mn. Dissolution medium: tetrahydrofuran Flow: 1.0 mL/min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Column temperature: 40℃ Detector: Differential Refractometer Standard material: monodisperse polystyrene

[ ¹³ C-Nuclear Magnetic Resonance (NMR) Analysis] The ¹³ C-NMR analysis of the polymer was performed using a nuclear magnetic resonance apparatus (“JNM-Delta400” manufactured by Nippon Electronics Co., Ltd.).

<Synthesis of [F] compound (monomer)> The monomers used in the synthesis of the [E] polymer in each Example and examples of the synthesis method thereof are shown below.

[Synthesis Example 1] (Synthesis of Compound (F-1)) 20.0 mmol of acetone, 30.0 mmol of (trifluoromethyl)trimethylsilane, 0.20 mmol of tetrabutylammonium fluoride and 50 g of tetrahydrofuran were added to the reaction vessel, and the mixture was stirred at room temperature for 1 hour. Then, after adding water for dilution, ethyl acetate was added for extraction, and the organic layer was separated. The obtained organic layer was washed with a saturated aqueous sodium chloride solution and water in this order. After drying with sodium sulfate, the solvent was distilled off and purified by atmospheric distillation, whereby a fluorinated alcohol body was obtained in good yield.

20.0 mmol of bromoacetyl bromide, 30.0 mmol of triethylamine and 50 g of tetrahydrofuran were added to the fluorinated alcohol, and the mixture was stirred at room temperature for 2 hours. Then, after adding water for dilution, ethyl acetate was added for extraction, and the organic layer was separated. The obtained organic layer was washed with a saturated aqueous ammonium chloride solution and water in this order. After drying with sodium sulfate, the solvent was distilled off and purified by column chromatography, whereby a bromine body was obtained in good yield.

To the bromine body were added 30.0 mmol of potassium carbonate, 30.0 mmol of methacrylic acid and 50 g of dimethylformamide, and the mixture was stirred at 50° C. for 4 hours. Then, the reaction solution was cooled to 30° C. or lower, diluted with water, and then extracted with ethyl acetate, and the organic layer was separated. The obtained organic layer was washed with a saturated aqueous sodium chloride solution and water in this order. After drying with sodium sulfate, the solvent was distilled off and purified by column chromatography, whereby a compound represented by the following formula (F-1) (hereinafter, sometimes described as "" Compound (F-1)” or “Monomer (F-1)”). The synthesis scheme of compound (F-1) is shown below.

[Chemical 21]

[Synthesis Example 2 to Synthesis Example 5] (Synthesis of Monomer (F-2) to Monomer (F-5)) Compounds represented by the following formulae (F-2) to (F-5) were synthesized in the same manner as in Synthesis Example 1 except that the raw materials and precursors were appropriately changed (hereinafter, the formulae (F-2) to ( The compounds represented by F-5) are described as "compound (F-2)" to "compound (F-5)" or "monomer (F-2)" to "monomeric (F-5)", respectively ).

[Chemical 22]

[Synthesis Example 6] (Synthesis of Compound (F-6)) To the bromine body obtained in Synthesis Example 1 were added 25.0 mmol of zinc powder, 2.00 mmol of chlorotrimethylsilane and 50 g of tetrahydrofuran, followed by stirring at room temperature for 1 hour. Then, 20.0 mmol of acetone was added to the reaction solution, followed by stirring at room temperature for 6 hours. Then, after adding a saturated aqueous ammonium chloride solution to the reaction solution to complete the reaction, ethyl acetate was added for extraction, and the organic layer was separated. The obtained organic layer was washed with a saturated aqueous sodium chloride solution and water in this order. After drying with sodium sulfate, the solvent was distilled off, and the alcohol body was obtained in good yield by purification by column chromatography.

To the alcohol body were added 30.0 mmol of triethylamine, 30.0 mmol of methacryloyl chloride, and 50 g of tetrahydrofuran, and the mixture was stirred at 80° C. for 1 hour. After that, the reaction solution was cooled to 30° C. or lower, a saturated aqueous ammonium chloride solution was added to complete the reaction, and ethyl acetate was added for extraction, and the organic layer was separated. The obtained organic layer was washed with a saturated aqueous sodium chloride solution and water in this order. After drying with sodium sulfate, the solvent was distilled off and purified by column chromatography, whereby a compound represented by the following formula (F-6) (hereinafter, sometimes described as "" Compound (F-6)" or "monomer (F-6)"). The synthesis scheme of compound (F-6) is shown below.

[Chemical 23]

[Synthesis Example 7 to Synthesis Example 16] (Synthesis of Monomer (F-7) to Monomer (F-16)) The compounds represented by the following formulae (F-7) to (F-16) (hereinafter, the formulae (F-7) to ( The compounds represented by F-16) are described as "compound (F-7)" to "compound (F-16)" or "monomeric (F-7)" to "monomeric (F-16)", respectively ).

[Chemical 24]

<Synthesis of [A] Polymer and [E] Polymer> The monomers used in the synthesis of each polymer in each Example and each Comparative Example are shown below.

[Chemical 25]

[Synthesis Example 17] (Synthesis of Polymer (A-1)) Monomer (M-1), Monomer (M-2) and Monomer (M-13) were dissolved in 2-butanone at a molar ratio of 40/15/45 (mol%) (200 parts by mass), azobisisobutyronitrile (AIBN) as a starting agent (3 mol % with respect to the total 100 mol % of the monomers used) was added to prepare a monomer solution . 2-Butanone (100 parts by mass) was placed in the reaction container, and after 30 minutes of nitrogen flushing, the inside of the reaction container was set to 80° C., and the monomer solution was added dropwise over 3 hours while stirring. The start of dropwise addition was set as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours.

After the completion of the polymerization reaction, the polymerization solution was cooled to 30°C or lower by water-cooling. The cooled polymerization solution was put into methanol (2,000 parts by mass), and the precipitated white powder was separated by filtration. After the white powder separated by filtration was washed twice with methanol, it was separated by filtration, and dried at 50° C. for 10 hours to obtain a white powdery polymer (A-1) (yield: 82%). The Mw of the polymer (A-1) was 8,800, and the Mw/Mn was 1.50. In addition, as a result of ¹³ C-NMR analysis, the content ratios of the respective structural units derived from (M-1), (M-2) and (M-13) were 41.3 mol %, 13.8 mol % and 44.9 mol %, respectively. Ear%.

[Synthesis Example 18 to Synthesis Example 27] (Synthesis of Polymer (A-2) to Polymer (A-11)) Polymers (A-2) to (A-11) were synthesized in the same manner as in Synthesis Example 17, except that the monomers of the types and compounding ratios shown in the following Table 1 were used. The content ratio (mol %), yield (%), and physical property values (Mw and Mw/Mn) of each structural unit of the obtained polymer are collectively shown in Table 1 below. In addition, "-" in the following Table 1 means that the corresponding monomer was not used.

[Table 1] [A] Polymer Monomers that provide structural units (I) Monomers that provide structural unit (II) Monomers that provide structural unit (III) Mw Mw/Mn type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) Synthesis Example 17 A-1 M-1 40 41.3 M-13 45 44.9 - - - 8800 1.50 M-2 15 13.8 Synthesis Example 18 A-2 M-1 30 31.4 M-6 60 60.6 - - - 9000 1.44 M-2 10 8.0 Synthesis Example 19 A-3 M-1 30 31.9 M-5 60 61.7 - - - 8900 1.39 M-3 10 6.4 Synthesis Example 20 A-4 M-1 35 32.3 M-12 45 49.6 - - - 8000 1.56 M-3 20 18.1 Synthesis Example 21 A-5 M-1 40 41.1 M-10 45 45.7 - - - 8700 1.44 M-4 15 13.2 Synthesis Example 22 A-6 M-1 40 40.2 M-11 45 47.8 - - - 7000 1.49 M-4 15 12.0 Synthesis Example 23 A-7 M-1 40 42.4 M-10 45 39.5 M-14 15 18.1 7800 1.59 Synthesis Example 24 A-8 M-1 40 41.1 M-7 40 35.7 M-15 20 23.2 8500 1.61 Synthesis Example 25 A-9 M-1 50 51.0 M-8 50 49.0 - - - 7800 1.55 Synthesis Example 26 A-10 M-1 40 44.4 M-9 60 55.6 - - - 7900 1.59 Synthesis Example 27 A-11 M-1 40 42.8 M-6 60 57.2 - - - 8000 1.43

[Synthesis Example 28] (Synthesis of Polymer (A-12)) Monomer (M-1) and Monomer (M-18) were dissolved in 1-methoxy-2-propanol (200 parts by mass) at a molar ratio of 50/50 (mol %). , AIBN (5 mol %) was added as a starting agent to prepare a single volume solution. 1-Methoxy-2-propanol (100 parts by mass) was placed in the reaction vessel, and after 30 minutes of nitrogen flushing, the inside of the reaction vessel was set to 80°C, and the monomer was added dropwise over 3 hours while stirring. solution. The start of dropwise addition was set as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours.

After the completion of the polymerization reaction, the polymerization solution was cooled to 30°C or lower by water-cooling. The cooled polymerization solution was put into hexane (2,000 parts by mass), and the precipitated white powder was separated by filtration. After the white powder separated by filtration was washed twice with hexane, it was separated by filtration and dissolved in 1-methoxy-2-propanol (300 parts by mass). Next, methanol (500 parts by mass), triethylamine (50 parts by mass), and ultrapure water (10 parts by mass) were added, and a hydrolysis reaction was performed at 70° C. for 6 hours while stirring. After the completion of the reaction, the residual solvent was distilled off, the obtained solid was dissolved in acetone (100 parts by mass), and added dropwise to water (500 parts by mass) to solidify the resin. The obtained solid was separated by filtration and dried at 50° C. for 13 hours to obtain a white powdery polymer (A-12) (yield: 80%). The Mw of the polymer (A-12) was 5,200, and the Mw/Mn was 1.60. In addition, as a result of ¹³ C-NMR analysis, the content ratios of the respective structural units derived from (M-1) and (M-18) were 51.3 mol % and 48.7 mol %, respectively.

[Synthesis Example 29 to Synthesis Example 31] (Synthesis of Polymer (A-13) to Polymer (A-15)) Polymers (A-13) to (A-15) were synthesized in the same manner as in Synthesis Example 28, except that the monomers of the types and compounding ratios shown in the following Table 2 were used. The content ratio (mol %), yield (%), and physical property values (Mw and Mw/Mn) of each structural unit of the obtained polymer are collectively shown in Table 2 below.

[Table 2] [A] Polymer Monomers that provide structural units (I) Monomers that provide structural unit (II) Monomers that provide structural unit (III) Mw Mw/Mn type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) Synthesis Example 28 A-12 M-1 50 51.3 - - - M-18 50 48.7 5200 1.60 Synthesis Example 29 A-13 M-3 50 46.6 M-14 10 11.1 M-19 40 42.3 5600 1.55 Synthesis Example 30 A-14 M-2 50 48.1 M-17 20 21.3 M-18 30 30.6 5100 1.59 Synthesis Example 31 A-15 M-1 55 55.7 M-17 15 15.1 M-19 30 29.2 6100 1.50

[Synthesis Example 32] (Synthesis of Polymer (E-1)) Monomer (F-1) and Monomer (M-2) were dissolved in 2-butanone (200 parts by mass) at a molar ratio of 80/20 (mol %), and added as a starting point A single dose of AIBN (5 mol%) was used to prepare a single volume solution. 2-Butanone (100 parts by mass) was placed in the reaction container, and after 30 minutes of nitrogen flushing, the inside of the reaction container was set to 80° C., and the monomer solution was added dropwise over 3 hours while stirring. The start of dropwise addition was set as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours.

After the completion of the polymerization reaction, the polymerization solution was cooled to 30°C or lower by water-cooling. After replacing the solvent with acetonitrile (400 parts by mass), hexane (100 parts by mass) was added and stirred, and the acetonitrile layer was recovered, and the operation was repeated three times. By replacing the solvent with propylene glycol monomethyl ether acetate, a solution of the polymer (E-1) was obtained (yield: 70%). The Mw of the polymer (E-1) was 5,100, and the Mw/Mn was 1.55. In addition, as a result of ¹³ C-NMR analysis, the content ratios of the respective structural units derived from (F-1) and (M-2) were 80.3 mol % and 19.7 mol %, respectively.

[Synthesis Example 33 to Synthesis Example 53] (Synthesis of Polymer (E-2) to Polymer (E-22)) A polymer (E-2) to a polymer (E-22) were synthesized in the same manner as in Synthesis Example 32, except that the monomers of the types and compounding ratios shown in the following Table 3 were used. The content ratio (mol %), yield (%), and physical property values (Mw and Mw/Mn) of each structural unit of the obtained polymer are shown in Table 3 below.

[table 3] [E] Polymer Monomers that provide building blocks (F) Monomers that provide structural units (I) Monomers that provide structural unit (II) Monomers that provide structural unit (III) Mw Mw/Mn type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) Synthesis Example 32 E-1 F-1 80 80.3 M-2 20 19.7 - - - - - - 5100 1.55 Synthesis Example 33 E-2 F-2 80 80.5 M-20 20 19.5 - - - - - - 6000 1.60 Synthesis Example 34 E-3 F-3 100 100 - - - - - - - - - 5500 1.61 Synthesis Example 35 E-4 F-1 80 78.3 - - - M-14 20 21.7 - - - 5900 1.54 Synthesis Example 36 E-5 F-2 80 80.1 - - - - - - M-21 20 19.9 4900 1.61 Synthesis Example 37 E-6 F-3 60 58.9 M-20 20 19.7 - - - M-23 20 21.4 5100 1.62 Synthesis Example 38 E-7 F-1 60 61.1 M-3 20 19.3 - - - M-24 20 19.6 5000 1.56 Synthesis Example 39 E-8 F-2 60 60.0 M-4 20 19.1 - - - M-27 20 20.9 5400 1.56 Synthesis Example 40 E-9 F-3 60 59.3 M-3 20 19.6 M-14 10 11.2 M-25 10 9.9 6000 1.58 Synthesis Example 41 E-10 F-4 80 81.0 M-1 20 19.0 - - - - - - 5600 1.49 Synthesis Example 42 E-11 F-5 60 61.0 M-20 30 28.7 - - - M-22 10 10.3 5500 1.60 Synthesis Example 43 E-12 F-6 90 90.4 - - - - - - M-22 10 9.6 5600 1.50 Synthesis Example 44 E-13 F-7 80 78.1 M-4 10 8.7 M-14 10 13.2 - - - 5100 1.51 Synthesis Example 45 E-14 F-8 70 71.6 M-2 30 28.4 - - - - - - 4800 1.55 Synthesis Example 46 E-15 F-9 70 69.8 M-1 15 15.0 M-17 15 15.2 - - - 5200 1.56 Synthesis Example 47 E-16 F-10 40 38.3 M-20 40 39.2 M-17 10 11.2 M-25 10 11.3 5100 1.65 Synthesis Example 48 E-17 F-11 50 49.4 M-1 30 31.0 M-17 10 10.3 M-22 10 9.3 4900 1.54 Synthesis Example 49 E-18 F-12 60 59.3 M-1 40 40.7 - - - - - - 5100 1.61 Synthesis Example 50 E-19 F-13 60 58.9 M-20 20 19.4 M-17 10 10.7 M-22 10 11.0 5400 1.49 Synthesis Example 51 E-20 F-14 60 59.0 M-2 30 29.7 M-15 10 11.3 - - - 5700 1.60 Synthesis Example 52 E-21 F-15 80 78.3 - - - M-10 20 21.7 - - - 5300 1.50 Synthesis Example 53 E-22 F-16 60 61.5 M-3 20 19.5 M-13 10 11.5 M-26 10 7.5 5200 1.55

[Comparative Synthesis Example 54 to Comparative Synthesis Example 70] (Synthesis of Polymer (E-23) to Polymer (E-39)) Polymers (E-23) to (E-39) were synthesized in the same manner as in Synthesis Example 32, except that the monomers of the types and compounding ratios shown in the following Table 4 were used. The content ratio (mol %), yield (%), and physical property values (Mw and Mw/Mn) of each structural unit of the obtained polymer are shown in Table 4 below.

[Table 4] [E] Polymer Monomers that provide structural units (I) Monomers that provide structural unit (II) Monomers that provide structural unit (III) Mw Mw/Mn type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) type Allocation ratio (mol%) Structural unit content (mol%) Synthesis Example 54 E-23 M-1 20 20.3 - - - M-21 80 79.7 5000 1.60 Synthesis Example 55 E-24 M-2 20 19.2 - - - M-21 80 80.8 5200 1.56 Synthesis Example 56 E-25 M-20 20 19.3 - - - M-21 80 80.7 5500 1.54 Synthesis Example 57 E-26 - - - - - - M-21 100 100.0 6100 1.55 Synthesis Example 58 E-27 - - - - - - M-21 90 91.0 5200 1.61 M-22 10 9.0 Synthesis Example 59 E-28 - - - M-14 20 20.6 M-21 80 79.4 5600 1.50 Synthesis Example 60 E-29 M-3 20 18.9 - - - M-24 80 81.1 5200 1.54 Synthesis Example 61 E-30 M-3 20 19.3 - - - M-26 80 80.7 5000 1.55 Synthesis Example 62 E-31 M-4 20 18.7 - - - M-27 80 81.3 5400 1.55 Synthesis Example 63 E-32 M-20 20 19.3 - - - M-23 80 80.7 6000 1.64 Synthesis Example 64 E-33 M-20 20 19.4 - - - M-26 80 80.6 5600 1.61 Synthesis Example 65 E-34 M-20 40 39.1 - - - M-25 60 60.9 6100 1.56 Synthesis Example 66 E-35 M-1 40 40.1 - - - M-27 60 59.9 5200 1.65 Synthesis Example 67 E-36 M-3 20 19.3 M-14 10 11.2 M-25 70 69.5 5500 1.54 Synthesis Example 68 E-37 M-4 10 9.7 M-14 10 10.9 M-21 80 79.4 5800 1.61 Synthesis Example 69 E-38 M-1 15 15.6 M-17 15 15.9 M-23 70 68.5 5300 1.59 Synthesis Example 70 E-39 - - - M-10 20 20.6 M-23 80 79.4 5500 1.54

<Preparation of radiation-sensitive resin composition> Components other than the [A] polymer and the [E] polymer used in the preparation of each radiation-sensitive resin composition are shown below.

[[B] Acid generator] B-1 to B-5: Compounds represented by the following formulae (B-1) to (B-5)

[Chemical 26]

[[C] Acid Diffusion Control Agent] C-1 to C-5: Compounds represented by the following formulae (C-1) to (C-5)

[Chemical 27]

[[D]solvent] D-1: Propylene glycol monomethyl ether acetate D-2: Propylene Glycol Monomethyl Ether D-3: γ-Butyrolactone D-4: Ethyl lactate

[Preparation of positive radiation-sensitive resin composition for ArF exposure] [Example 1] 100 parts by mass of (A-1) as [A] polymer, 14.0 parts by mass of (B-1) as [B] acid generator, and 5.0 parts by mass of (C-1) as [C] acid diffusion control agent part, (E-1) 3.0 parts by mass (solid content) as [E] polymer, and (D-1)/(D-2)/(D-3)=70/29 as [D] solvent /1 (mass ratio) of 3,230 parts by mass of a mixed solvent, and filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive resin composition (J-1).

[Example 2 to Example 48 and Comparative Example 1 to Comparative Example 17] A radiation-sensitive resin composition (J-2) to a radiation-sensitive resin composition (J-48) and a radiation-sensitive resin composition (J-48) and a radiation-sensitive resin composition were prepared in the same manner as in Example 1, except that each component of the type and content shown in the following Table 5 was used. Radiation-sensitive resin composition (CJ-1) to radiation-sensitive resin composition (CJ-17).

[table 5] Radiation sensitive resin composition [A] Polymer [B] Acid generator [C] Acid diffusion control agent [E] Polymer [D] Organic solvent type Content (mass parts) type Content (mass parts) type Content (mass parts) type Content (mass parts) type Content (mass parts) Example 1 J-1 A-1 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 2 J-2 A-1 100 B-1 14.0 C-1 5.0 E-2 3.0 D-1/D-2/D-3 2240/960/30 Example 3 J-3 A-1 100 B-1 14.0 C-1 5.0 E-3 3.0 D-1/D-2/D-3 2240/960/30 Example 4 J-4 A-1 100 B-1 14.0 C-1 5.0 E-4 3.0 D-1/D-2/D-3 2240/960/30 Example 5 J-5 A-1 100 B-1 14.0 C-1 5.0 E-5 3.0 D-1/D-2/D-3 2240/960/30 Example 6 J-6 A-1 100 B-1 14.0 C-1 5.0 E-6 3.0 D-1/D-2/D-3 2240/960/30 Example 7 J-7 A-1 100 B-1 14.0 C-1 5.0 E-7 3.0 D-1/D-2/D-3 2240/960/30 Example 8 J-8 A-1 100 B-1 14.0 C-1 5.0 E-8 3.0 D-1/D-2/D-3 2240/960/30 Example 9 J-9 A-1 100 B-1 14.0 C-1 5.0 E-9 3.0 D-1/D-2/D-3 2240/960/30 Example 10 J-10 A-1 100 B-1 14.0 C-1 5.0 E-10 3.0 D-1/D-2/D-3 2240/960/30 Example 11 J-11 A-1 100 B-1 14.0 C-1 5.0 E-11 3.0 D-1/D-2/D-3 2240/960/30 Example 12 J-12 A-1 100 B-1 14.0 C-1 5.0 E-12 3.0 D-1/D-2/D-3 2240/960/30 Example 13 J-13 A-1 100 B-1 14.0 C-1 5.0 E-13 3.0 D-1/D-2/D-3 2240/960/30 Example 14 J-14 A-1 100 B-1 14.0 C-1 5.0 E-14 3.0 D-1/D-2/D-3 2240/960/30 Example 15 J-15 A-1 100 B-1 14.0 C-1 5.0 E-15 3.0 D-1/D-2/D-3 2240/960/30 Example 16 J-16 A-1 100 B-1 14.0 C-1 5.0 E-16 3.0 D-1/D-2/D-3 2240/960/30 Example 17 J-17 A-1 100 B-1 14.0 C-1 5.0 E-17 3.0 D-1/D-2/D-3 2240/960/30 Example 18 J-18 A-1 100 B-1 14.0 C-1 5.0 E-18 3.0 D-1/D-2/D-3 2240/960/30 Example 19 J-19 A-1 100 B-1 14.0 C-1 5.0 E-19 3.0 D-1/D-2/D-3 2240/960/30 Example 20 J-20 A-1 100 B-1 14.0 C-1 5.0 E-20 3.0 D-1/D-2/D-3 2240/960/30 Example 21 J-21 A-1 100 B-1 14.0 C-1 5.0 E-21 3.0 D-1/D-2/D-3 2240/960/30 Example 22 J-22 A-1 100 B-1 14.0 C-1 5.0 E-22 3.0 D-1/D-2/D-3 2240/960/30 Example 23 J-23 A-2 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 24 J-24 A-3 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 25 J-25 A-4 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 26 J-26 A-5 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 27 J-27 A-6 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 28 J-28 A-7 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 29 J-29 A-8 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 30 J-30 A-9 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 31 J-31 A-10 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 32 J-32 A-1l 100 B-1 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 33 J-33 A-1 100 B-2 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 34 J-34 A-1 100 B-3 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 35 J-35 A-1 100 B-4 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 36 J-36 A-1 100 B-5 14.0 C-1 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 37 J-37 A-1 100 B-1 14.0 C-2 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 38 J-38 A-1 100 B-1 14.0 C-3 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 39 J-39 A-1 100 B-1 14.0 C-4 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 40 J-40 A-1 100 B-1 14.0 C-5 5.0 E-1 3.0 D-1/D-2/D-3 2240/960/30 Example 41 J-41 A-1 100 B-1 14.0 C-1 5.0 E-1 0.3 D-1/D-2/D-3 2240/960/30 Example 42 J-42 A-1 100 B-1 14.0 C-1 5.0 E-1 1.5 D-1/D-2/D-3 2240/960/30 Example 43 J-43 A-1 100 B-1 14.0 C-1 5.0 E-1 6.0 D-1/D-2/D-3 2240/960/30 Example 44 J-44 A-1 100 B-1 14.0 C-1 5.0 E-1 10.0 D-1/D-2/D-3 2240/960/30 Example 45 J-45 A-1 100 B-1 14.0 C-1 5.0 E-1 25.0 D-1/D-2/D-3 2240/960/30 Example 46 J-46 A-1 100 B-1 14.0 C-1 5.0 E-1/E-23 0.2/2.8 D-1/D-2/D-3 2240/960/30 Example 47 J-47 A-1 100 B-1 14.0 C-1 5.0 E-1/E-23 1.5/1.5 D-1/D-2/D-3 2240/960/30 Example 48 J-48 A-1 100 B-1 14.0 C-1 5.0 E-1/E-23 2.8/0.2 D-1/D-2/D-3 2240/960/30 Comparative Example 1 CJ-1 A-1 100 B-1 14.0 C-1 5.0 E-23 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 2 CJ-2 A-1 100 B-1 14.0 C-1 5.0 E-24 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 3 CJ-3 A-1 100 B-1 14.0 C-1 5.0 E-25 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 4 CJ-4 A-1 100 B-1 14.0 C-1 5.0 E-26 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 5 CJ-5 A-1 100 B-1 14.0 C-1 5.0 E-27 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 6 CJ-6 A-1 100 B-1 14.0 C-1 5.0 E-28 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 7 CJ-7 A-1 100 B-1 14.0 C-1 5.0 E-29 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 8 CJ-8 A-1 100 B-1 14.0 C-1 5.0 E-30 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 9 CJ-9 A-1 100 B-1 14.0 C-1 5.0 E-31 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 10 CJ-10 A-1 100 B-1 14.0 C-1 5.0 E-32 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 11 CJ-11 A-1 100 B-1 14.0 C-1 5.0 E-33 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 12 CJ-12 A-1 100 B-1 14.0 C-1 5.0 E-34 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 13 CJ-13 A-1 100 B-1 14.0 C-1 5.0 E-35 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 14 CJ-14 A-1 100 B-1 14.0 C-1 5.0 E-36 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 15 CJ-15 A-1 100 B-1 14.0 C-1 5.0 E-37 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 16 CJ-16 A-1 100 B-1 14.0 C-1 5.0 E-38 3.0 D-1/D-2/D-3 2240/960/30 Comparative Example 17 CJ-17 A-1 100 B-1 14.0 C-1 5.0 E-39 3.0 D-1/D-2/D-3 2240/960/30

<Formation of resist pattern using positive radiation-sensitive resin composition for ArF exposure> Using a spin coater (“CLEAN TRACK ACT12” manufactured by Tokyo Electron Co., Ltd.), the composition for forming a lower layer antireflection film (“ARC66” manufactured by Brewer Science Co., Ltd.) was applied After being placed on a 12-inch silicon wafer, it was heated at 205° C. for 60 seconds to form a lower anti-reflection film with an average thickness of 100 nm. The prepared positive-type radiation-sensitive resin composition for ArF exposure was coated on the lower antireflection film using the spin coater, and prebaked (PB) at 100° C. for 60 seconds. Then, it cooled at 23 degreeC for 30 second, and formed the resist film with an average thickness of 90 nm. Next, using an ArF excimer laser immersion exposure device (“TWINSCAN XT-1900i” from ASML), under the optical conditions of NA=1.35, Dipole (σ=0.9/0.7), a line of 40 nm is separated. With a mask pattern of spaces, the resist film is exposed to light. After exposure, a post-exposure bake (PEB) was performed at 100°C for 60 seconds. Then, using 2.38 mass % TMAH aqueous solution as an alkaline developing solution, the resist film was subjected to alkaline development, washed with water after development, and dried to form a positive-type resist pattern (40 nm line and space pattern).

＜Evaluation＞ With respect to the resist pattern formed using the radiation-sensitive resin composition for ArF exposure, the sensitivity and the number of defects after development were evaluated according to the following methods. In addition, with respect to the resist film before ArF exposure, the receding contact angle was evaluated according to the following method. These results are shown in Table 6 below. In addition, for the length measurement of the resist pattern, a scanning electron microscope (“CG-5000” manufactured by Hitachi High-Technologies Co., Ltd.) was used.

[Sensitivity] In the formation of the resist pattern using the radiation-sensitive resin composition for ArF exposure, the exposure amount for forming a 40 nm line and space pattern was set as the optimum exposure amount, and the optimum exposure amount was set as the optimum exposure amount. is the sensitivity (mJ/cm ² ). Regarding the sensitivity, the case of 25 mJ/cm ² or less was evaluated as "good", and the case of more than 25 mJ/cm ² was evaluated as "poor".

[Receding contact angle after SB] For the resist film before ArF exposure in the method for forming the resist pattern, DSA-10 manufactured by KRUS was used in an environment of room temperature 23° C., relative humidity 40%, and normal pressure, and the following procedures were used. procedure to determine the receding contact angle.

After water was discharged from the needle of DSA-10 to form 25 μL of water droplets on the resist film, the water droplets were sucked by the needle at a speed of 10 μL/min for 90 seconds, and the contact angle per second was measured (90 times in total). In this measurement, the average value was calculated for the contact angles at a total of 20 points from the point at which the contact angle stabilized, and it was set as the receding contact angle (°) after SB. When the receding contact angle after SB was 70° or more, it was evaluated as "good", and when it was less than 70°, it was evaluated as "poor".

[Number of development defects] The resist film was exposed at the optimum exposure amount to form a line-and-space pattern with a line width of 40 nm, and a wafer for defect inspection was produced. The number of defects on the wafer for defect inspection was measured using a defect inspection apparatus (“KLA2810” manufactured by KLA-Tencor Corporation). Then, the measured defects were classified into defects determined to be derived from the resist film and foreign substances derived from the outside, and the number of defects determined to be derived from the resist film was calculated. Regarding the number of defects after development, the case where the number of defects determined to be derived from the resist film was 15 or less was evaluated as "good", and the case where it exceeded 15 was evaluated as "poor".

[Table 6] Radiation sensitive resin composition Sensitivity (mJ/cm ² ) Receding contact angle / after PB (°) Number of developing defects (pieces) Example 1 J-1 twenty three 80 1 Example 2 J-2 twenty four 81 2 Example 3 J-3 twenty four 82 5 Example 4 J-4 twenty three 80 1 Example 5 J-5 twenty three 81 2 Example 6 J-6 twenty three 78 8 Example 7 J-7 twenty four 85 1 Example 8 J-8 twenty two 86 7 Example 9 J-9 twenty two 81 7 Example 10 J-10 twenty four 78 2 Example 11 J-11 twenty four 79 8 Example 12 J-12 twenty three 77 1 Example 13 J-13 twenty two 81 9 Example 14 J-14 twenty three 78 3 Example 15 J-15 twenty two 85 9 Example 16 J-16 twenty four 86 10 Example 17 J-17 twenty one 81 2 Example 18 J-18 twenty four 78 2 Example 19 J-19 twenty four 79 1 Example 20 J-20 twenty four 77 1 Example 21 J-21 twenty three 78 0 Example 22 J-22 twenty three 83 5 Example 23 J-23 twenty three 81 2 Example 24 J-24 twenty four 78 3 Example 25 J-25 twenty two 80 1 Example 26 J-26 twenty two 81 2 Example 27 J-27 twenty two 82 1 Example 28 J-28 twenty four 80 2 Example 29 J-29 twenty three 81 3 Example 30 J-30 twenty two 80 1 Example 31 J-31 twenty two 79 1 Example 32 J-32 twenty three 80 1 Example 33 J-33 twenty three 80 3 Example 34 J-34 twenty four 80 2 Example 35 J-35 twenty two 81 3 Example 36 J-36 twenty two 80 1 Example 37 J-37 twenty two 79 2 Example 38 J-38 twenty four 81 1 Example 39 J-39 twenty two 81 2 Example 40 J-40 twenty three 80 3 Example 41 J-41 twenty two 77 9 Example 42 J-42 twenty one 79 4 Example 43 J-43 twenty two 81 4 Example 44 J-44 twenty two 80 8 Example 45 J-45 twenty three 78 12 Example 46 J-46 twenty two 77 12 Example 47 J-47 twenty one 78 10 Example 48 J-48 twenty two 80 4 Comparative Example 1 CJ-1 27 63 189 Comparative Example 2 CJ-2 28 66 222 Comparative Example 3 CJ-3 27 67 210 Comparative Example 4 CJ-4 27 62 160 Comparative Example 5 CJ-5 28 65 216 Comparative Example 6 CJ-6 29 67 471 Comparative Example 7 CJ-7 27 66 428 Comparative Example 8 CJ-8 30 65 267 Comparative Example 9 CJ-9 27 67 98 Comparative Example 10 CJ-10 28 67 329 Comparative Example 11 CJ-11 29 65 318 Comparative Example 12 CJ-12 28 68 161 Comparative Example 13 CJ-13 27 67 106 Comparative Example 14 CJ-14 27 62 520 Comparative Example 15 CJ-15 29 66 89 Comparative Example 16 CJ-16 29 65 78 Comparative Example 17 CJ-17 27 61 67

As is clear from the results in Table 6, when the radiation-sensitive resin compositions of Examples were used for ArF exposure, the sensitivity, the receding contact angle performance after SB, and the defect performance after development were good. In the example, each characteristic is inferior to that of the example. Therefore, when the radiation-sensitive resin composition of the Example is used for ArF exposure, a resist pattern with high sensitivity, high water repellency, and few defects can be formed.

[Preparation of radiation-sensitive resin composition for extreme ultraviolet (EUV) exposure] [Example 49] 100 parts by mass of (A-12) as [A] polymer, 15.0 parts by mass of (B-1) as [B] acid generator, and 10.0 parts by mass of (C-2) as [C] acid diffusion control agent parts, 4.0 parts by mass of (E-1) as [E] polymer, and 6,110 parts by mass of a mixed solvent of (D-1)/(D-4)=70/30 (mass ratio) as [D] solvent , and filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive resin composition (J-49).

[Example 50 to Example 72 and Comparative Example 18 to Comparative Example 24] A radiation-sensitive resin composition (J-50) to a radiation-sensitive resin composition (J-72) and a radiation-sensitive resin composition (J-72) and a radiation-sensitive resin composition were prepared in the same manner as in Example 49, except that each component of the type and content shown in the following Table 7 was used. Radiation-sensitive resin composition (CJ-18) to radiation-sensitive resin composition (CJ-24).

[Table 7] Radiation sensitive resin composition [A] Polymer [B] Acid generator [C] Acid diffusion control agent [E] Polymer [D] Organic solvent type Content (mass parts) type Content (mass parts) type Content (mass parts) type Content (mass parts) type Content (mass parts) Example 49 J-49 A-12 100 B-1 15.0 C-2 10.0 E-1 4.0 D-1/D-4 4280/1830 Example 50 J-50 A-12 100 B-1 15.0 C-2 10.0 E-2 4.0 D-1/D-4 4280/1830 Example 51 J-51 A-12 100 B-1 15.0 C-2 10.0 E-3 4.0 D-1/D-4 4280/1830 Example 52 J-52 A-12 100 B-1 15.0 C-2 10.0 E-12 4.0 D-1/D-4 4280/1830 Example 53 J-53 A-12 100 B-1 15.0 C-2 10.0 E-14 4.0 D-1/D-4 4280/1830 Example 54 J-54 A-12 100 B-1 15.0 C-2 10.0 E-17 4.0 D-1/D-4 4280/1830 Example 55 J-55 A-12 100 B-1 15.0 C-2 10.0 E-18 4.0 D-1/D-4 4280/1830 Example 56 J-56 A-12 100 B-1 15.0 C-2 10.0 E-19 4.0 D-1/D-4 4280/1830 Example 57 J-57 A-12 100 B-1 15.0 C-2 10.0 E-21 4.0 D-1/D-4 4280/1830 Example 58 J-58 A-13 100 B-1 15.0 C-2 10.0 E-1 4.0 D-1/D-4 4280/1830 Example 59 J-59 A-14 100 B-1 15.0 C-2 10.0 E-1 4.0 D-1/D-4 4280/1830 Example 60 J-60 A-15 100 B-1 15.0 C-2 10.0 E-1 4.0 D-1/D-4 4280/1830 Example 61 J-61 A-12 100 B-2 15.0 C-2 10.0 E-1 4.0 D-1/D-4 4280/1830 Example 62 J-62 A-12 100 B-3 15.0 C-2 10.0 E-1 4.0 D-1/D-4 4280/1830 Example 63 J-63 A-12 100 B-4 15.0 C-2 10.0 E-1 4.0 D-1/D-4 4280/1830 Example 64 J-64 A-12 100 B-5 15.0 C-2 10.0 E-1 4.0 D-1/D-4 4280/1830 Example 65 J-65 A-12 100 B-1 15.0 C-2 10.0 E-1 0.3 D-1/D-4 4280/1830 Example 66 J-66 A-12 100 B-1 15.0 C-2 10.0 E-1 1.5 D-1/D-4 4280/1830 Example 67 J-67 A-12 100 B-1 15.0 C-2 10.0 E-1 6.0 D-1/D-4 4280/1830 Example 68 J-68 A-12 100 B-1 15.0 C-2 10.0 E-1 10.0 D-1/D-4 4280/1830 Example 69 J-69 A-12 100 B-1 15.0 C-2 10.0 E-1 25.0 D-1/D-4 4280/1830 Example 70 J-70 A-12 100 B-1 15.0 C-2 10.0 E-1/E-24 0.2/3.8 D-1/D-4 4280/1830 Example 71 J-71 A-12 100 B-1 15.0 C-2 10.0 E-1/E-24 2.0/2.0 D-1/D-4 4280/1830 Example 72 J-72 A-12 100 B-1 15.0 C-2 10.0 E-1/E-24 3.8/0.2 D-1/D-4 4280/1830 Comparative Example 18 CJ-18 A-12 100 B-1 15.0 C-2 10.0 E-24 4.0 D-1/D-4 4280/1830 Comparative Example 19 CJ-19 A-12 100 B-1 15.0 C-2 10.0 E-25 4.0 D-1/D-4 4280/1830 Comparative Example 20 CJ-20 A-12 100 B-1 15.0 C-2 10.0 E-26 4.0 D-1/D-4 4280/1830 Comparative Example 21 CJ-21 A-12 100 B-1 15.0 C-2 10.0 E-27 4.0 D-1/D-4 4280/1830 Comparative Example 22 CJ-22 A-12 100 B-1 15.0 C-2 10.0 E-35 4.0 D-1/D-4 4280/1830 Comparative Example 23 CJ-23 A-12 100 B-1 15.0 C-2 10.0 E-38 4.0 D-1/D-4 4280/1830 Comparative Example 24 CJ-24 A-12 100 B-1 15.0 C-2 10.0 E-39 4.0 D-1/D-4 4280/1830

<Formation of resist pattern using radiation-sensitive resin composition for EUV exposure> Using a spin coater (“CLEAN TRACK ACT12” manufactured by Tokyo Electron Co., Ltd.), the composition for forming a lower layer antireflection film (“ARC66” manufactured by Brewer Science Co., Ltd.) was applied After being placed on a 12-inch silicon wafer, it was heated at 205° C. for 60 seconds to form a lower anti-reflection film with an average thickness of 105 nm. The prepared radiation-sensitive resin composition for EUV exposure was coated on the lower antireflection film using the spin coater, and PB was performed at 130° C. for 60 seconds. Then, it cooled at 23 degreeC for 30 second, and formed the resist film with an average thickness of 55 nm. Next, using an EUV exposure apparatus (“NXE3300” manufactured by ASML), the resist film was exposed at NA=0.33, illumination condition: Conventional s=0.89, and mask: imecDEFECT32FFR02. After exposure, PEB was performed at 120°C for 60 seconds. Then, using 2.38 mass % TMAH aqueous solution as an alkaline developer, the resist film was subjected to alkaline development, washed with water after development, and dried to form a positive-type resist pattern (32 nm line and space pattern).

＜Evaluation＞ With respect to the resist pattern formed using the radiation-sensitive resin composition for EUV exposure, the sensitivity and LWR performance were evaluated according to the following methods. The results are shown in Table 8 below. In addition, for the length measurement of the resist pattern, a scanning electron microscope (“CG-5000” manufactured by Hitachi High-Technologies Co., Ltd.) was used.

[Sensitivity] In the formation of the resist pattern using the radiation-sensitive resin composition for EUV exposure, the exposure amount for forming the 32 nm line and space pattern was set as the optimum exposure amount, and the optimum exposure amount was set as the optimum exposure amount. is the sensitivity (mJ/cm ² ). Regarding the sensitivity, the case of 25 mJ/cm ² or less was evaluated as "good", and the case of more than 25 mJ/cm ² was evaluated as "poor".

[Number of development defects] The resist film was exposed at the optimum exposure amount to form a line and space pattern with a line width of 32 nm, and a wafer for defect inspection was produced. The number of defects on the wafer for defect inspection was measured using a defect inspection apparatus (“KLA2810” manufactured by KLA-Tencor Corporation). Then, the measured defects were classified into defects determined to be derived from the resist film and foreign substances derived from the outside, and the number of defects determined to be derived from the resist film was calculated. Regarding the number of defects after development, the case where the number of defects determined to be derived from the resist film was 15 or less was evaluated as "good", and the case where it exceeded 15 was evaluated as "poor".

[Table 8] Radiation sensitive resin composition Sensitivity (mJ/cm ² ) Number of developing defects (pieces) Example 49 J-49 twenty two 5 Example 50 J-50 twenty three 6 Example 51 J-51 twenty four 10 Example 52 J-52 twenty two 3 Example 53 J-53 twenty three 4 Example 54 J-54 twenty two 1 Example 55 J-55 twenty three 4 Example 56 J-56 twenty one 8 Example 57 J-57 twenty three 9 Example 58 J-58 twenty one 4 Example 59 J-59 twenty two 5 Example 60 J-60 twenty two 3 Example 61 J-61 twenty two 7 Example 62 J-62 twenty three 5 Example 63 J-63 twenty four 6 Example 64 J-64 twenty one 4 Example 65 J-65 twenty two 11 Example 66 J-66 twenty two 9 Example 67 J-67 twenty one 8 Example 68 J-68 twenty two 10 Example 69 J-69 twenty two 12 Example 70 J-70 twenty two 13 Example 71 J-71 twenty four 8 Example 72 J-72 twenty two 7 Comparative Example 18 CJ-18 29 261 Comparative Example 19 CJ-19 30 218 Comparative Example 20 CJ-20 28 319 Comparative Example 21 CJ-21 29 161 Comparative Example 22 CJ-22 29 194 Comparative Example 23 CJ-23 27 173 Comparative Example 24 CJ-24 28 185

As is clear from the results in Table 8, when the radiation-sensitive resin compositions of Examples were used for EUV exposure, the sensitivity and post-development defect performance were good. On the other hand, in the comparative example, each characteristic is inferior to the Example. Therefore, when the radiation-sensitive resin composition of the Example is used for EUV exposure, a resist pattern with high sensitivity and few defects can be formed.

[Preparation of Negative Radiation Sensitive Resin Composition for ArF Exposure, Formation and Evaluation of Resist Pattern Using the Composition] [Example 82] 100 parts by mass of (A-1) as [A] polymer, 10.0 parts by mass of (B-4) as [B] acid generator, and 5.0 parts by mass of (C-3) as [C] acid diffusion control agent part, (E-1) 3.0 parts by mass (solid content) as [E] polymer, and (D-1)/(D-2)/(D-3)=70/29 as [D] solvent /1 (mass ratio) of 3,230 parts by mass of a mixed solvent, and filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive resin composition (J-73).

In the formation of the resist pattern using the positive-type radiation-sensitive resin composition for ArF exposure, the negative-type radiation-sensitive resin composition for ArF exposure (J-73) prepared as described above was used as the radiation-sensitive resin. Other than the composition, a resist film was formed in the same manner, ArF exposure was performed, and PEB was performed. Then, using n-butyl acetate as an organic solvent developer, the resist film was developed with an organic solvent and dried to form a negative resist pattern (40 nm line and space pattern).

For the resist pattern using the negative radiation-sensitive resin composition for ArF exposure and the resist film before ArF exposure, and the resist pattern using the positive radiation-sensitive resin composition for ArF exposure The evaluation was performed in the same way. As a result, the radiation-sensitive resin composition of Example 73 was excellent in sensitivity, receding contact angle performance after PB, and defect performance after development even when a negative resist pattern was formed by ArF exposure. [Industrial Availability]

According to the radiation-sensitive resin composition of the present invention, a resist pattern forming method using the same, a water repellency improving agent, and the like, a resist pattern having good sensitivity to exposure light, high water repellency, and few defects can be formed. The polymer of the present invention can be preferably used as the polymer of the radiation-sensitive resin composition. The compound of the present invention can be preferably used as a monomer of the polymer. Therefore, these can be preferably used in the processing and the like of semiconductor devices which are expected to be further miniaturized in the future.

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Claims (9)

A radiation-sensitive resin composition comprising a resin A having a first structural unit having a partial structure represented by the following formula (1), [Chem. 1]

(In formula (1), X is a divalent linking group; R ¹ and R ² are each independently a monovalent chain hydrocarbon group having 1 to 40 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, A monovalent aromatic hydrocarbon group of 6 to 12, a monovalent fluorinated hydrocarbon group of 1 to 40 carbon atoms, or a group of 3 to 20 ring members composed of R ¹ and R ² combined with each other and these bonded carbon atoms Ring structure (a); R ³ is a fluorinated chain hydrocarbon group having 1 to 4 carbon atoms; * represents a linking site with the main chain portion of the polymer) Resin B containing a structural unit having an acid-dissociable group, radiation-sensitive acid generator, and solvent. The radiation-sensitive resin composition according to claim 1, wherein the first structural unit is a structural unit represented by the following formula (2);

(In formula (2), X and R ¹ to R ³ are the same as those in formula (1); R is a hydrogen atom, a fluorine atom, or an unsubstituted or halogen atom- or alkoxy-substituted monovalent hydrocarbon group). The radiation-sensitive resin composition according to claim 2, wherein, in the first structural unit, X in the formula (2) is a group represented by the following formula (2-1); ]

(In formula (2-1), Z ¹ and Z ² are each independently one or more carbon atoms selected from a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group, a monovalent fluorinated hydrocarbon group, a monovalent hydrocarbon group, or a monovalent fluorinated hydrocarbon group. A group substituted with a linking group represented by *-O-*, *-CO-*, *-COO-* or *-OCO-* (wherein, * in the linking group is a bond with a carbon atom bond), or Z ¹ and Z ² are combined with each other and form a ring structure with 3-20 ring members together with these bonded carbon atoms; L is a single bond or a divalent organic group; n is 1-5 an integer). The radiation-sensitive resin composition according to any one of claim 1 to claim 3, wherein the resin A further has a second structural unit represented by the following formula (3);

(In formula (3), R ⁴ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R ⁵ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; R ⁶ and R ⁷ are each independently a carbon number of 1 to 20. A monovalent chain hydrocarbon group of 10 or a monovalent alicyclic hydrocarbon group with a carbon number of 3 to 20, or a divalent carbon number of 3 to 20 composed of R ⁶ and R ⁷ combined with each other and these bonded carbon atoms alicyclic base). The radiation-sensitive resin composition according to any one of claim 1 to claim 4, wherein the resin B further comprises a compound selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure A structural unit of at least one of the group. The radiation-sensitive resin composition according to any one of claim 1 to claim 5, wherein the structural unit having an acid dissociable group in the resin B is represented by the following formula (4); ]

(In formula (4), R ⁸ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R ⁹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; R ¹⁰ and R ¹¹ are each independently a carbon number of 1 to 20. A monovalent chain hydrocarbon group of 10 or a monovalent alicyclic hydrocarbon group of 3 to 20 carbon atoms, or a divalent carbon number of 3 to 20 in which R ¹⁰ and R ¹¹ are bonded to each other and together with these bonded carbon atoms alicyclic base). A method for forming a resist pattern, comprising: The step of directly or indirectly coating the radiation-sensitive resin composition according to any one of claim 1 to claim 6 on a substrate to form a resist film; exposing the resist film by immersion exposure; and A step of developing the exposed resist film. The method for forming a resist pattern according to claim 7, wherein the radiation used in the exposing step is ArF excimer laser light, extreme ultraviolet (EUV), X-ray or electron beam (EB). A water repellency improving agent, comprising resin A having a first structural unit represented by the following formula (2);

(In formula (2), X is a divalent linking group; R is a hydrogen atom, a fluorine atom, or a monovalent hydrocarbon group unsubstituted or substituted with a halogen atom or an alkoxy group; R ¹ and R ² are independently carbon A monovalent chain hydrocarbon group having 1 to 40 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, or R ¹ and R ² are bonded to each other and to these A ring structure (a) with 3 to 20 ring members formed by the bonded carbon atoms together; R ³ is a fluorinated chain hydrocarbon group with 1 to 4 carbon atoms).