TW201809867A - Method for forming pattern, process for producing electronic device, actinic-ray-sensitive or radiation-sensitive resin composition, and resist film - Google Patents

Abstract

Provided are: a method for forming a pattern using a film of an actinic-ray-sensitive or radiation-sensitive resin composition having excellent water conformability and excellent developability; a process for producing an electronic device; an actinic-ray-sensitive or radiation-sensitive resin composition; and a resist film. The method for forming a pattern comprises: a resist film formation step in which an actinic-ray-sensitive or radiation-sensitive resin composition is used to form, on a substrate, a film of the actinic-ray-sensitive or radiation-sensitive resin composition; an exposure step; and a development step. The actinic-ray-sensitive or radiation-sensitive resin composition comprises resin A, which increases in solubility in alkaline developing solutions by the action of an acid, compound B, which generates an acid upon irradiation with actinic rays or radiation, and resin C and/or a combination of resin C1 with resin C2.

Description

Pattern forming method, method for manufacturing electronic component, photosensitized radioactive or radiation-sensitive resin composition, and resist film

The present invention relates to a method for forming a pattern, a method for manufacturing an electronic component, a photosensitive radiation- or radiation-sensitive resin composition, and a resist film.

With the miniaturization of the structure of various electronic components such as semiconductor devices and liquid crystal devices, liquid immersion exposure may be used in order to form finer resist patterns. In the liquid immersion exposure, when ArF excimer laser is used as the light source, pure water is used as the liquid immersion liquid from the aspects of higher operational safety, higher light transmittance at 193 nm, and higher refractive index at 193 nm. More often.

In addition, when forming a fine resist pattern, a chemical amplification is sometimes used as a resist pattern forming method. A positive resist pattern formation method using chemical amplification is given as an example. This method of forming a resist pattern is a method in which an acid generator is first decomposed in an exposed portion to generate an acid. Next, in the post-exposure baking (PEB: PostExposureBake), the generated acid is used as a reaction catalyst, and the alkali-insoluble group contained in the resin in the resist film is changed to an alkali-soluble group. The alkali developed to remove the exposed portion.

It is known that if a liquid immersion exposure is applied to a resist film using chemical amplification, the resist film comes into contact with the liquid immersion liquid during exposure, and thus the resist film may be deteriorated and / or the constituent components of the resist film may be changed from The resist film leaks into the liquid immersion liquid.

In addition, in the liquid immersion exposure, when a scanning type liquid immersion exposure machine is used for exposure, it is required to follow the high speed movement of the lens of the liquid immersion exposure machine, and the liquid immersion liquid also moves at high speed. As described above, when the liquid immersion liquid is water, it is known that the resist film is preferably hydrophobic. Patent Document 1 describes a method for treating a photoresist composition, which includes the following: a light containing two or more substances containing one or more resins, photoactive components, and substantially non-miscible with respect to one or more resins The resist composition is applied to a substrate; and the photoresist layer is immersed and exposed to photosensitizing radiation for the resist composition, wherein two or more substantially non-mixing substances include (i) a surface layer substance and (ii) an intermediate Substances, and surface substances and intermediate substances have different surface energies. [Prior Art Literature] [Patent Literature]

[Patent Document 1]: Japanese Patent Laid-Open No. 2009-199058

The inventors have applied the photoresist composition described in Patent Document 1 to a liquid immersion exposure process and a development process, and found that a resist film formed from the photoresist composition has a certain level of followability to water (water Followability), but the developability during alkali development (hereinafter referred to as "development") does not meet the previously required level. In this specification, the water followability refers to a value that can be measured by the method described in the examples, and indicates whether the liquid immersion liquid can follow the high speed of the exposure device on the resist film during the liquid immersion exposure. Indicator of movement.

Then, an object of the present invention is to provide a photoresistive or radiation-sensitive resin composition film (hereinafter, also referred to as a “resist film”) using an excellent water followability and excellent developability. ) Pattern formation method. Another object of the present invention is to provide a method for manufacturing an electronic component, a case of a photosensitized or radiation-sensitive resin composition, and a resist film. In addition, the excellent developability in this specification means the developability of a resist film that can be measured by a method described in Examples described later, that is, pattern collapse and line edge roughness (LER: line edge). Whether the evaluation of roughness), scum and development defects have reached the actual application level.

As a result of intensive research in order to achieve the above-mentioned problems, the present inventors have found a pattern forming method including a resist film formation process, an exposure process, and a development process to be described later, in which a photosensitized or radiation-sensitive resin composition contains The resin A, the compound B, and the combination of the resin C1 and the resin C2 and at least one of the resin C, which will be described later, can solve the above-mentioned problems and have completed the present invention. That is, it was found that the above-mentioned problem can be achieved by the following configuration.

[1] A pattern forming method, comprising: a resist film forming process, using a photosensitive radiation- or radiation-sensitive resin composition to form a photosensitive radiation- or radiation-sensitive resin composition film on a substrate; an exposure process, Irradiating actinic radiation or radiation to a photoresistive or radiation-sensitive resin composition film; and a development process using an alkali developer to perform actinic radiation or radiation-sensitive resin composition films to which actinic radiation or radiation has been irradiated; Development, in which the actinic radiation- or radiation-sensitive resin composition contains: resin A whose solubility in an alkali developing solution increases due to the action of acid; resin B which generates an acid by irradiation with actinic radiation or radiation; and A combination of the resin C1 and the resin C2 and at least one of the resin C. Wherein, the resin C1 contains at least one selected from the group consisting of a repeating unit represented by the formula X1, a group represented by the formula X2, and a group represented by the formula X3, and the resin C2 contains a member selected from the group represented by the formula Y1. At least one of the group consisting of a group represented by the formula Y3 and a repeating unit represented by the formula Y2, and the resin C contains: a group selected from the repeating unit represented by the formula X1 and the group represented by the formula X2 And at least one of the group consisting of a group represented by formula X3; and a member selected from the group consisting of a group represented by formula Y1, a group represented by formula Y3, and a repeating unit represented by formula Y2 at least one. [2] The pattern forming method according to [1], wherein the photosensitized or radiation-sensitive resin composition includes one or two or more selected from the group consisting of resin C1, resin C2, and resin C. In the case of a specific resin, all the specific resins include a repeating unit derived from a monomer that satisfies at least one formula selected from the group consisting of formulas 3 to 5. [3] The pattern forming method according to [2], wherein at least one of the specific resins includes a repeating unit derived from a monomer satisfying Formula 4 and Formula 6, or Formula 5 and Formula 6. [4] The pattern forming method according to any one of [1] to [3], wherein R ₁ in the repeating unit represented by Formula X1 and R ₂ in the group represented by Formula X2 are three or more Fluorine atom substituted alkyl. [5] The pattern forming method according to any one of [1] to [4], wherein R in the repeating unit represented by the formula Y2, the group represented by the formula Y1, and the group represented by the formula Y3 R is a hydrogen atom. [6] The pattern forming method according to any one of [1] to [4], wherein R in the repeating unit represented by Formula Y2, the group represented by Formula Y1, and the group represented by Formula Y3 R is an alkyl, aryl or alkylamino group containing a substituent. [7] The pattern forming method according to [6], wherein R in the repeating unit represented by the formula Y2, R in the group represented by the formula Y1, and R in the group represented by the formula Y3 are under basic conditions. Leaving alkyl or aryl. [8] The pattern forming method according to any one of [1] to [7], wherein the resin C and the resin C2 contain a repeating unit, and the repeating unit contains two or more groups selected from the group represented by formula Y1 And at least one group in the group consisting of the group represented by formula Y3. [9] The pattern forming method according to any one of [1] to [8], wherein the resin C, the resin C1, and the resin C2 are selected from the group consisting of a (meth) acrylate derivative, a styrene derivative, and an olefin-containing compound. At least one polymer in the group consisting of propyl compounds. [10] The pattern forming method according to any one of [1] to [9], wherein at least one resin selected from the group consisting of resin C1, resin C2, and resin C contains an aromatic ring. [11] The pattern forming method according to any one of [1] to [10], wherein the resin C1 and the resin C contain a repeating unit represented by Formula 7. [12] The pattern forming method according to any one of [1] to [11], wherein the photosensitive radiation- or radiation-sensitive resin composition contains: resin C, and selected from the group consisting of resin C1 and resin C2 At least one of the groups. [13] The pattern forming method according to any one of [1] to [12], wherein the resin A contains a repeating unit, and the repeating unit contains a lactone structure. [14] The pattern forming method according to any one of [1] to [13], wherein the photosensitized radiation- or radiation-sensitive resin composition further contains a solvent D. [15] The pattern forming method according to any one of [1] to [14], wherein the film thickness of the photosensitive radiation- or radiation-sensitive resin composition film is 80 nm or less. [16] The pattern forming method according to any one of [1] to [15], wherein the exposure process is a liquid immersion exposure process. [17] A method for manufacturing an electronic component, comprising the pattern forming method according to any one of [1] to [16]. [18] A photosensitized or radiation-sensitive resin composition containing: resin A that has an increased solubility in an alkali developing solution due to the action of an acid; resin B that generates an acid by irradiation with actinic rays or radiation And at least one of the combination of resin C1 and resin C2 and resin C; The resin C1 contains at least one selected from the group consisting of a repeating unit represented by the formula X1, a group represented by the formula X2, and a group represented by the formula X3, and the resin C2 contains a member selected from the group consisting of At least one of the group consisting of a group represented by the formula Y3 and a repeating unit represented by the formula Y2, and the resin C contains: a group selected from the repeating unit represented by the formula X1 and the group represented by the formula X2 And at least one of the group consisting of a group represented by formula X3; and a member selected from the group consisting of a group represented by formula Y1, a group represented by formula Y3, and a repeating unit represented by formula Y2 at least one. [19] The photosensitized or radiation-sensitive resin composition according to [18], which contains one or two or more specific resins selected from the group consisting of resin C1, resin C2, and resin C, and all The specific resin contains a repeating unit derived from a monomer that satisfies at least one formula selected from the group consisting of Formulas 3 to 5. [20] The actinic radiation- or radiation-sensitive resin composition according to [19], wherein at least one of the specific resins contains a repeating unit derived from a monomer satisfying Formula 4 and Formula 6 or Formula 5 and Formula 6 . [21] The photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [20], wherein R ₁ in the repeating unit represented by the formula X1 and the group represented by the formula X2 R ₂ in the above is an alkyl group substituted with three or more fluorine atoms. [22] The photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [21], wherein R in the repeating unit represented by Formula Y2, the group represented by Formula Y1, and R in the group represented by the formula Y3 is a hydrogen atom. [23] The photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [21], wherein R in the repeating unit represented by Formula Y2, the group represented by Formula Y1, and R in the group represented by the formula Y3 is an alkyl group, an aryl group, or an alkylamino group containing a substituent. [24] The photosensitive radiation- or radiation-sensitive resin composition according to [23], wherein R in the repeating unit represented by the formula Y2, the group represented by the formula Y1, and the group represented by the formula Y3 R is an alkyl or aryl group which is removed under basic conditions. [25] The photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [24], wherein the resin C and the resin C2 contain a repeating unit, and the repeating unit contains two or more selected from the group consisting of At least one group in the group consisting of a group represented by the formula Y1 and a group represented by the formula Y3. [26] The photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [25], wherein the resin C, the resin C1, and the resin C2 are selected from (meth) acrylate derivatives At least one polymer in the group consisting of styrene derivatives and allyl-containing compounds. [27] The photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [26], wherein at least one resin is selected from the group consisting of resin C1, resin C2, and resin C Contains aromatic rings. [28] The photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [27], wherein the resin C1 and the resin C contain a repeating unit represented by Formula 7. [29] The photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [28], comprising: resin C, and at least one selected from the group consisting of resin C1 and resin C2 One. [30] The photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [29], wherein the resin A contains a repeating unit, and the repeating unit contains a lactone structure. [31] The photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [30], further comprising a solvent D. [32] A resist film formed using the photosensitive radiation- or radiation-sensitive resin composition according to any one of [18] to [31]. [Inventive effect]

According to the present invention, it is possible to provide a pattern forming method using a resist film having excellent water followability and excellent developability. Furthermore, the present invention can also provide a method for manufacturing an electronic component, a photosensitized or radiation-sensitive resin composition, and a resist film.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. In addition, in this specification, a numerical range indicated by "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In addition, the "actinic rays" or "radiation" in this specification refers to, for example, a bright line spectrum of a mercury lamp, an excimer laser light, and extreme ultraviolet (EUV: Extreme ultraviolet), X-ray, and electrons. Beam etc. Furthermore, in this specification, "light" means actinic radiation or radiation. Unless otherwise specified, "exposure" in this manual includes not only exposure based on far-ultraviolet rays, X-rays, and EUV light typified by mercury lamps and excimer laser light, but also electron beam and ion beam based exposure. Particle beam depiction. In addition, in this specification, "(meth) acrylate" means an acrylate and a methacrylate. In the present specification, "(meth) acrylic acid" means acrylic acid and methacrylic acid. In the present specification, "(meth) acrylfluorenyl" means acrylfluorenyl and methacrylfluorenyl. In addition, in this specification, "(meth) acrylamide" means acrylamide and methacrylamide. In this specification, the definition of "monomer" is the same as "monomer". The monomer is a compound which is classified into an oligomer and a polymer and has a weight average molecular weight of 2,000 or less. In the present specification, the "polymerizable compound" means a compound having a polymerizable group, and it may be a monomer or a polymer. "Polymerizable group" means a group that participates in a polymerization reaction.

Hereinafter, first, the photosensitized radioactive or radiation-sensitive resin composition used in the pattern forming method according to the embodiment of the present invention will be described, and then the pattern forming method will be described for each process.

[Photosensitized radioactive or radiation-sensitive resin composition] The above photosensitized radioactive or radiation-sensitive resin composition (hereinafter, also referred to as "resist composition") contains the following (1) to (3) . (1) Resin A whose solubility in an alkaline developer is increased by the action of an acid. (2) Resin B that generates acid by irradiation with actinic rays or radiation. (3) A combination of the resin C1 and the resin C2 and at least one of the resin C.

Among them, the resin C1 and the resin C2 include the following (i) and (ii), respectively. Resin C1: (i) At least one selected from the group consisting of a repeating unit represented by Formula X1, a group represented by Formula X2, and a group represented by Formula X3. Resin C2: (ii) At least one selected from the group consisting of a group represented by Formula Y1, a group represented by Formula Y3, and a repeating unit represented by Formula Y2. Moreover, the said resin C contains both of said (i) and (ii).

The above-mentioned resist composition is used for positive-type development (development where an unexposed portion remains as a pattern and the exposed portion is removed). That is, development is performed using an alkali developing solution. It is known that when a liquid immersion exposure is applied to a resist film using chemical amplification, the resist film is more hydrophobic. The reason is considered to be that when the liquid immersion liquid is water, the water easily follows the high-speed movement (scanning movement) of the exposure device. According to the study by the present inventors, it has been found that a conventional resist film having relatively high hydrophobicity has a problem in terms of developability during alkali development. The inventors believe that the reason is that the resist film is hydrophobic, so that the alkali developing solution cannot sufficiently penetrate into the resist film.

One of the features of the resist composition is that it contains at least one of a combination of resin C1 and resin C2 and resin C. The combination of resin C1 and resin C2 and resin C contain: (i) at least one selected from the group consisting of a repeating unit represented by formula X1, a group represented by formula X2, and a group represented by formula X3, and (Ii) At least one selected from the group consisting of a group represented by Formula Y1, a group represented by Formula Y3, and a repeating unit represented by Formula Y2. Here, (i) its structure contains fluorine atoms or silicon atoms, so these are biased to the surface of the resist film, the surface hydrophobicity tends to be high, and it is beneficial to the improvement of water followability. In addition, (ii) contains a hydrophilic group in its structure. The hydrophilic group has the effect of easily dissolving the resist film in the alkali developing solution, and is advantageous for improving the developability. It is presumed that the above-mentioned resist composition is obtained by the phase containing (i) and (ii) by containing the resin containing (i) and (ii) or a combination of the resin containing (i) and (ii). Multiply the effect and obtain the effect of the present invention. In addition, the above is speculation, and the scope of the present invention is not limited to the range in which the effect is obtained by the above-mentioned action mechanism.

Hereinafter, each aspect of the above-mentioned resist composition will be described.

[Resin A with increased solubility in alkaline developer due to the action of acid] Resin A is a resin with increased solubility in alkaline developer due to the action of acid, and is the main chain or side chain of the resin, or the main Both the chain and the side chain have a resin that is decomposed by the action of an acid and generates an alkali-soluble group (hereinafter, also referred to as an "acid-decomposable group").

Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfoamido group, a sulfoimino group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (Alkylsulfonyl) (alkylcarbonyl) fluorenimine, bis (alkylcarbonyl) methylene, bis (alkylcarbonyl) fluorenimine, bis (alkylsulfonyl) methylene, Bis (alkylsulfonyl) fluorenimine, tris (alkylcarbonyl) methylene and tris (alkylsulfonyl) methylene.

Examples of the group to be removed by the acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), and the like. In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ to R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, or the like.

The resin A preferably has a repeating unit, and the repeating unit has an acid-decomposable group. As the repeating unit having an acid-decomposable group, a repeating unit represented by the following formula (AI) is preferable. [Chemical Formula 1]

In the formula (AI), Xa ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a methylol group. T represents a single bond or a divalent linking group. Rx ₁ to Rx ₃ each independently represent an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). At least two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Formula (A1) will be described in more detail. Examples of the divalent linking group of T include an alkylene group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the aforementioned cycloalkyl group and / or at least one of Rx ₁ to Rx ₃ is the aforementioned cycloalkyl group. The -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) group, which is an acid-decomposable group in the formula (AI), may have a group represented by at least _one- (L) _n1 -P as a substituent. Among them, L represents a divalent linking group, n ₁ represents 0 or 1, and P represents a polar group.

Examples of the divalent linking group of L include linear or branched alkylene, cycloalkylene, and the like. The number of atoms of the divalent linking group of L is preferably 20 or less, and more preferably 15 or less. good. The linear or branched alkylene and cycloalkylene groups preferably have a carbon number of 8 or less. The linear or branched alkylene and cycloalkylene may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, and an alkoxy group (having 1 carbon atoms). ～ 4), carboxyl group, alkoxycarbonyl group (carbon number is 2 to 6), etc.

Examples of the polar group of P include a group containing a hetero atom such as a hydroxyl group, a keto group, a cyano group, an amidino group, an alkylamidoamine group, a sulfonamido group, a lower ester group, and a lower sulfonic acid ester group. group. Among them, "lower" is preferably a group having 2 to 3 carbon atoms. The preferred polar group is a hydroxyl group, a cyano group, an amido group, and more preferably a hydroxyl group.

Among the groups represented _by- (L) _n1 -P, when n1 = 1, for example, a linear or branched alkyl group having a hydroxyl group, a cyano group, an amidino group, an alkylamidoamino group, or a sulfonamido group may be mentioned. Group (preferably having 1 to 10 carbons), cycloalkyl (preferably having 3 to 15 carbons), preferably an alkyl group having a hydroxyl group (preferably having 1 to 5 carbons, more preferably The carbon number is 1 to 3.).

Among them, P is a hydroxyl group, n1 is 0 or 1, and L is a linear or branched alkylene group (preferably having 1 to 5 carbon atoms) is preferred. It is preferred that the group represented by -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) in formula (AI) has 1 to 3 groups represented _by- (L) _n1 -P, and has 1 or 2 One is better, and one is best. The repeating unit represented by the formula (AI) is preferably a repeating unit represented by the following formula (1-1). [Chemical Formula 2]

In formula (1-1), R ₃ is the same as Xa ₁ in formula (AI). R ₄ and R ₅ are the same as Rx ₁ and Rx _{2 in} Formula 1. The group represented _by- (L) _n1 -P is the same as the group represented _by- (L) _n1 -P in formula (A1). P represents an integer of 1 to 3. p is preferably 1 or 2, and more preferably 1.

The monomer corresponding to the repeating unit of the formula (A1) can be synthesized, for example, by a method described in Japanese Patent Application Laid-Open No. 2006-16379.

The content of the repeating unit having an acid-decomposable group is preferably 20 to 50 mol%, and more preferably 25 to 45 mol% relative to the total repeating unit in the resin (A).

As a preferable aspect of the acid-decomposable group, repeating units described in paragraphs 0049 to 0054 of Japanese Patent Application Laid-Open No. 2010-44358 (hereinafter referred to as "Document A") are listed, and the above contents are incorporated in In this manual.

It is preferable that the resin A further has a repeating unit having at least one group selected from the group consisting of a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group, and having a lactone group (lactone structure) The repeating unit is more preferable.

The repeating unit having a lactone structure that can be contained in the resin A will be described. As the lactone structure, any structure can be used, preferably a 5- to 7-membered cyclic lactone structure, and a 5- to 7-membered cyclic lactone structure to form a bicyclic structure and a spiro ring structure in which other ring structures are fused is more preferred. good. It is more preferable to have a repeating unit having a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-17). Moreover, the lactone structure can be directly bonded to the main chain. The preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17) Moreover, by using a specific lactone structure, line edge roughness and development defects become better. [Chemical Formula 3]

The lactone structure may or may not have a substituent (Rb ₂ ). Examples of the preferable substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms (in the alkyl group, a hydrogen atom may be substituted with a fluorine atom), a cycloalkyl group having 4 to 7 carbon atoms, and a carbon number Examples thereof include an alkoxy group having 1 to 8 carbon atoms, an alkoxy carboxy group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n2 represents an integer from 0 to 4. When n2 is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

Examples of the repeating unit having a lactone structure represented by any one of the formulae (LC1-1) to (LC1-17) include a repeating unit represented by the following formula (AII). [Chemical Formula 4]

In Formula (AII), Ab ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Preferred substituents which the alkyl group of Ab ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Ab ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As Ab ₀ , a hydrogen atom, a methyl group, a methylol group, and a trifluoromethyl group are preferred, and a hydrogen atom and a methyl group are particularly preferred.

A represents a -COO- group or a -CONH- group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether bond, an ester bond, a carbonyl group, a amide bond, an amine ester bond, or a urea bond or a combination of 2 Valent linking group. A single bond is preferably a divalent linking group represented by -Ab ₁ -CO _2- .

Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylidene group, a cyclohexyl group, an adamantyl group, or a norbornyl group. n represents an integer of 1 to 5. n is preferably 1 or 2, more preferably 1.

V represents a group having a structure represented by any one of the formulae (LC1-1) to (LC1-17).

Specific examples of the repeating unit containing a lactone structure include, for example, repeating units described in paragraphs 0064 to 0066 of Document A, and the above contents are incorporated into this specification.

It is preferable that the resin A contains a repeating unit which contains a lactone structure represented by the following formula (3). [Chemical Formula 5]

In formula (3), A represents an ester bond (-COO-) or an amido bond (-CONH-). When R ₀ is plural, each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

When Z is plural, they each independently represent an ether bond, an ester bond, a carboxyl group, a amine bond, an amine ester bond, or a urea bond.

R ₈ represents a monovalent organic group having a lactone structure.

n is the repeating number of the structure represented by -R ₀ -Z- in the repeating unit represented by formula (3), and represents an integer of 1 to 5. n is preferably 1 or 2, more preferably 1.

R ₇ represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent.

The alkylene group and cycloalkylene group of R ₀ may have a substituent. Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

As a repeating unit containing a lactone structure represented by the said Formula (3), the repeating unit described in the paragraph 0079 of the document A is mentioned, and the said content is incorporated into this specification.

As the repeating unit having a lactone structure, a repeating unit represented by the following formula (3-1) is more preferable. [Chemical Formula 6]

In the formula (3-1), the definitions of R ₇ , A, R ₀ , Z, and n are the same as those in the formula (3). When a plurality of R ₉ are present, they each independently represent an alkyl group, a cycloalkyl group, an alkoxycarboxyl group, a cyano group, a hydroxyl group, or an alkoxy group, and when a plurality of R ₉ are present, two R ₉ groups may be bonded to form a ring. .

X represents an alkylene group, an oxygen atom, or a sulfur atom. m is the number of substituents and represents an integer of 0 to 5. It is preferable that m is 0 or 1. When m = 1, the substitution of R ₉ at the α-position or β-position of the carbonyl group of the lactone is preferred, and especially the α-position is preferred. The alkyl group of R ₉ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group, and most preferably a methyl group. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxycarboxyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a tert-butoxycarbonyl group. Examples of the substituent include an alkoxy group such as a hydroxyl group, a methoxy group, and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom. R ₉ is more preferably methyl, cyano or alkoxycarbonyl, and cyano is more preferred. Examples of the alkylene group of X include a methylene group and an ethylene group. X is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

Specific examples of the repeating unit containing a lactone structure represented by formula (3-1) include the repeating units described in paragraphs 0083 to 0084 of Document A, and the above contents are incorporated into this specification.

Optical isomers usually exist in the repeating unit having a lactone group, but any optical isomer may be used. Furthermore, one optical isomer may be used alone, or a plurality of optical isomers may be used in combination. When one optical isomer is mainly used, the optical purity (ee) is preferably 90 or more, and more preferably 95 or more.

The content of the repeating unit having a lactone group is preferably 15 to 60 mol%, more preferably 20 to 50 mol%, and still more preferably 30 to 50 mol% relative to the total repeating unit in the resin.

The resin A preferably has a repeating unit not included in the formula (AI) or (AII) and having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. As the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, adamantyl, diadamantyl, norbornyl is preferable. As a preferable alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, a partial structure represented by the following formulae (VIIa) to (VIId) is preferable. [Chemical Formula 7]

In formulae (VIIa) to (VIIc), R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. It is preferred that one or two of R ₂ c to R ₄ c be a hydroxyl group and the remainder be a hydrogen atom. In formula (VIIa), _two of R ₂ c to R ₄ c are more preferably a hydroxyl group, and the remainder is a hydrogen atom.

Examples of the repeating unit having a partial structure represented by the formulae (VIIa) to (VIId) include repeating units described in paragraphs 0090 to 0091 of Document A, and the above contents are incorporated into the present specification.

The content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, and still more preferably 10 to 25 mol% relative to the total repeating unit in the resin A.

Examples of the repeating unit having a hydroxyl group or a cyano group include the repeating unit described in paragraph 0093 of Document A, and the above-mentioned contents are incorporated into this specification.

The resin A preferably has a repeating unit, and the repeating unit has an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfoamido group, a sulfoamido group imino group, a bissulfoamido group imino group, and an aliphatic alcohol (such as hexafluoroisopropanol) substituted with an electron-withdrawing group at the α position It is more preferable to have a repeating unit, and the repeating unit has a carboxyl group. By including a repeating unit having an alkali-soluble group, the resolution in a contact pore application is increased. Repeating units having an alkali-soluble group, such as repeating units based on acrylic acid and methacrylic acid, are directly bonded to the main chain of the resin, or repeating units having an alkali-soluble group are bonded to the main chain of the resin via a linking group. Either the repeating unit having an alkali-soluble group and the use of a polymerization initiator and / or a chain transfer agent having an alkali-soluble group to introduce the alkali-soluble group to the end of the polymer chain during polymerization are preferred. The linking group may also have a monocyclic or polycyclic cyclic hydrocarbon structure. Particularly preferred are repeating units based on acrylic acid and methacrylic acid.

The resin A preferably contains a repeating unit represented by the formula (I) which does not have any of a hydroxyl group and a cyano group. [Chemical Formula 8]

In the formula (I), R ₅ represents a hydrocarbon group having at least one cyclic structure and not having any of a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or a fluorenyl group. Examples of Ra include a hydrogen atom, a methyl group, a trifluoromethyl group, and a methylol group. * Indicates the bonding position.

In the resin A, in order to adjust the dry etching resistance of the resist and / or the adaptability of a standard developing solution, the substrate adhesion, and the contour of the resist, furthermore, as the resolution, heat resistance, and sensitivity of the general performance of the resist, The molar ratio of each repeating structural unit is appropriately set. When the photosensitized or radiation-sensitive resin composition of the present invention is used for ArF exposure, it is preferable that the resin A does not have an aromatic group in terms of transparency with respect to ArF light.

It is preferable that the resin A does not contain a fluorine atom and a silicon atom.

The resin A can be synthesized by a conventional method (for example, radical polymerization). For example, as a general synthesis method, a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and then heated to perform polymerization, and a solution of the monomer species and the initiator for 1 hour to 10 may be mentioned. A dropwise polymerization method, etc., which is added to a heating solvent by dripping for an hour, is more preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; Solvents such as dimethylformamide and dimethylacetamide, and solvents such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone that dissolve the composition of the present invention described below . More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic radiation-sensitive or radiation-sensitive resin composition of the present invention. This can suppress generation of particles during storage.

The weight average molecular weight of the resin A is a polystyrene conversion value measured by a GPC (Gel Permeation Chromatography) method, and is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and even more preferably 3,000 to 15,000. , Especially preferred is 5,000 to 13,000. By setting the weight-average molecular weight to 1,000 to 200,000, it is possible to prevent deterioration in heat resistance and / or dry etching resistance, and to prevent deterioration in developability or deterioration in film forming property due to increased viscosity.

In the actinic radiation- or radiation-sensitive resin composition of the present invention, the compounding ratio in the entire composition of the resin A is preferably 50 to 99% by mass of the total solid content, and more preferably 70 to 98% by mass. In addition, in the present invention, the resin A may be used singly or in combination.

[Compound B that generates acid by irradiation with actinic radiation or radiation] The above-mentioned photosensitive radiation or radiation-sensitive resin composition contains a compound that generates acid by irradiation with actinic radiation or radiation (hereinafter, also referred to as "Acid generator").

As the acid generator, a photoinitiator used in photocationic polymerization, a photoinitiator for photoradical polymerization, a pigment-based photodecolorant, a photochromic agent, or a microresist can be appropriately selected and used. Irradiation of actinic rays or radiation produces known compounds of acids and mixtures thereof.

For example, a diazonium salt, a sulfonium salt, a sulfonium salt, a sulfonium salt, a sulfonium imine sulfonate, an oxime sulfonate, a diazonium, a dihydrazone, and an o-nitrobenzyl sulfonate are mentioned.

Furthermore, it is also possible to use compounds described in US Pat. No. 3,779,778, European Patent No. 126,712, etc., which generate an acid by light. As a preferable compound in an acid generator, the compound represented by following formula (ZI), (ZII), (ZIII) is mentioned. [Chemical Formula 9]

In the formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is usually 1 to 30, preferably 1 to 20. In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and an oxygen atom, a sulfur atom, an ester bond, a amide bond, and a carbonyl group may be contained in the ring. Examples of the group formed by the two bonds of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butylene group and a butyl group). Z ^- represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion of Z ^- include a sulfonate anion, a carboxylate anion, a sulfofluorenimide anion, a bis (alkylsulfonyl) sulfonimide anion, and a tri (alkylsulfonyl) anion. Methyl anion, etc.

A "non-nucleophilic anion" is an anion with a significantly lower ability to initiate a nucleophilic reaction, and is an anion capable of inhibiting the decomposition over time based on a nucleophilic reaction within a molecule. This improves the stability of the resist over time.

As a more preferable (ZI) component, the compound (ZI-1), (ZI-2), and (ZI-3) demonstrated below are mentioned. The compound (ZI-1) is an arylfluorene compound in which at least one of R ₂₀₁ to R ₂₀₃ of the formula (ZI) is an aryl group, that is, a compound in which arylfluorene is used as a cation.

Next, the compound (ZI-2) will be described. The compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represents an organic group having no aromatic ring. Among them, the "aromatic ring" also includes an aromatic ring containing a hetero atom.

The compound (ZI-3) is a compound represented by the following formula (ZI-3) and is a compound containing a benzamidine methylsulfonium salt structure. [Chemical Formula 10]

In formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _5c , R _6c and R _7c, and R _x and R _y may be respectively bonded to form a ring structure, and the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, and an amidine bond. _Examples of the group formed by the bonding of any two or more of R _1c to R _5c , R _6c and R _7c, and R _x and R _y include butylene and pentenyl. Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ⁻ in the formula (ZI).

In the formulae (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group, or a cycloalkyl group. The aryl groups as R ₂₀₄ to R ₂₀₇ are preferably phenyl and naphthyl, and more preferably phenyl. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group containing a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, and the like. Examples of the aryl group containing a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole), a furan residue (a group formed by losing one hydrogen atom from furan), and a thiophene residue ( A group formed by losing a hydrogen atom from thiophene), an indole residue (a group formed by losing a hydrogen atom from indole), a benzofuran residue (a group formed by losing a hydrogen atom from benzofuran) Group), benzothiophene residues (groups formed by the loss of a hydrogen atom from benzothiophene), etc.

Z ^- represents a non-nucleophilic anion, and the same as Z ^- non-nucleophilic anion in formula (ZI) can be mentioned. Examples of the acid generator include compounds represented by the following formulae (ZIV), (ZV), and (ZVI). [Chemical Formula 11]

In the formulae (ZIV) to (ZVI), Ar ₃ and Ar ₄ each independently represent an aryl group. R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group. A represents an alkylene, an alkenyl or an arylene.

Among the acid generators, compounds represented by the formulae (ZI) to (ZIII) are more preferred. In addition, as the acid generator, a compound that generates an acid containing one sulfonic acid group or a sulfonylimino group is preferable, a compound that generates a perfluoroalkanesulfonic acid, and a group containing a fluorine atom or a fluorine atom are more preferable. Substituted compounds that generate aromatic sulfonic acids or compounds that generate fluorenimine substituted with a group containing a fluorine atom or a fluorine atom, more preferably fluorine-substituted alkanesulfonic acid, fluorine-substituted benzenesulfonic acid, and fluorine-substituted fluorene A phosphonium salt of imine or fluorine-substituted methylated acid. The acid generator that can be used is particularly preferably a fluorine-substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, or a fluorine-substituted sulfamic acid having a pKa of pKa = -1 or less, and the sensitivity is improved. Among the acid generators, particularly preferred examples are listed below. [Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

The acid generator can be used singly or in combination of two or more kinds. Based on the total solids content of the composition, the content of the acid generator in the photosensitized or radiation-sensitive resin composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and more preferably It is preferably 1 to 7 mass%.

[Resin C1, Resin C2, and Resin C] The above-mentioned actinic radiation- or radiation-sensitive resin composition contains at least one of a combination of resin C1 and resin C2 and resin C.

<Resin C1> The resin C1 is a resin containing the following (i). (I) At least one selected from the group consisting of a repeating unit represented by Formula X1, a group represented by Formula X2, and a group represented by Formula X3. As resin C1, it is preferable to contain the following (ib). (Ib) At least one repeating unit X selected from the group consisting of a repeating unit represented by formula X1, a repeating unit containing a group represented by formula X2, and a repeating unit consisting of a group represented by formula X3.

[Chemical Formula 17]

In the repeating unit represented by the formula X1, in the group represented by the formula X2, and in the group represented by the formula X3, L represents a single bond or a linking group. The linking group is not particularly limited. In Formula X1, a (n1 + 1) -valent linking group is sufficient. In Formula X2, a divalent linking group is sufficient. In Formula X3, (n3 + 1) A valence linking group is sufficient. In addition, n1 and n3 each independently represent an integer of 1 or more. The divalent linking group is not particularly limited. Specific examples include a divalent linking group selected from a divalent aliphatic hydrocarbon group such as an alkylene group and a cycloalkylene group, an aryl group such as an phenylene group, an ether group, a thioether group, A group or a combination thereof in the group consisting of a carbonyl group, an ester group, an amido group, an amine ester group, and a urea group. As the (n1 + 1) -valent linking group (when n1 + 1 is 2, the same as the above) and (n3 + 1) -valent linking group (when n3 + 1 is 2, the same as the above), there is no special Examples of the limitation include a group represented by any one of the following formulae (A) to (D) or a group obtained by combining them. [Chemical Formula 18]

In the formulae (A) to (D), L ⁴ represents a trivalent group. T ³ represents a single bond or a divalent linking group, and T ^{3 in which three are present} may be the same as or different from each other. L ⁵ represents a tetravalent group. T ⁴ represents a single bond or a divalent linking group, and T ^{4 in which four are present} may be the same as or different from each other. L ⁶ represents a pentavalent group. T ⁵ represents a single bond or a divalent linking group, and T ^{5 in which 5 is present} may be the same as or different from each other. L ⁷ represents a hexavalent group. T ⁶ represents a single bond or a divalent linking group, and T ^{6 in} which there are ⁶ may be the same as or different from each other. The definition of the divalent linking group represented by T ³ , T ⁴ , T ⁵ and T ⁶ is the same as the definition of the divalent linking group represented by L described above.

In addition, the (n1 + 1) -valent linking group and the (n3 + 1) -valent linking group may be a group represented by the following formulae (K) to (O) or a combination of these. In the formula, * represents a bonding position. [Chemical Formula 19]

In the repeating unit represented by the formula X1, R ₁ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is replaced with a fluorine atom. In the group represented by formula X2, R ₂ represents a fluorine atom, an alkyl group in which at least one hydrogen atom is replaced with a fluorine atom, or -Si (R ₁₀ ) ₃ . The alkyl group substituted with a fluorine atom is not particularly limited, and examples thereof include a group in which at least one hydrogen atom in the alkyl group having 1 to 30 carbon atoms is substituted with a fluorine atom. Among them, an alkyl group substituted with three or more fluorine atoms is preferred. R ₁₀ represents an alkyl group, and the number of carbon atoms in R ₁₀ is not particularly limited, but 1 to 8 is preferred, and 1 to 4 is more preferred. In the group represented by the formula X3, R ₁₀ represents an alkyl group, and the aspect is the same as described above.

Ar represents an aromatic hydrocarbon ring group. The aromatic hydrocarbon ring group preferably has 6 to 10 carbon atoms, and may be a monocyclic ring or a polycyclic ring, and may further include a substituent. The aromatic hydrocarbon ring group is not particularly limited, and examples thereof include a benzene ring group and a naphthalene ring group.

n1, n2, and n3 represent integers of 1 or more. The upper limit values of n1, n2, and n3 are not particularly limited, but usually it is preferably 3 or less. In the above formula, * represents a bonding position.

In the repeating unit represented by the formula X1, R _A represents a hydrogen atom or a monovalent substituent. The monovalent substituent is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a halogenated alkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, Nitro, carboxyl, aryloxy, siloxy, heterocyclooxy, carbamoyloxy, amine (including alkylamino and aniline), fluorenyl, aminocarbonylamino, alkoxy Carbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkyl or arylsulfonylamino, mercapto, alkylthio, arylthio, heterocyclicthio, aminesulfonyl, sulfo Radical, alkyl or arylsulfinyl, alkyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarboxyl, aminoformyl, aryl or heterocyclic azo, fluorenyl Imino, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, silyl, adamantyl, and groups obtained by combining two or more of them. As R _A , a hydrogen atom or a halogenated alkyl group is preferable, an alkyl group in which at least one hydrogen atom in the hydrogen atom or the alkyl group is replaced with a fluorine atom is more preferable, and a hydrogen atom or a trifluoromethyl group is more preferable.

Specific examples of the repeating unit represented by Formula X1 are shown below. However, the repeating unit is not limited to the following specific examples.

[Chemical Formula 20]

Specific examples of the group represented by Formula X2 are shown below. However, the above-mentioned groups are not limited to the following specific examples. In the following formula, "Me" represents a methyl group, and * represents a bonding position. [Chemical Formula 21]

Specific examples of the group represented by Formula X3 are shown below. However, the above-mentioned groups are not limited to the following specific examples. In the following formula, * represents a bonding position. [Chemical Formula 22]

The resin C1 preferably contains the above-mentioned repeating unit X. The repeating unit containing a group represented by formula X2 is preferably based on a repeating unit of a monomer containing a group represented by formula X2, and the above-mentioned monomer preferably contains a polymerizable group. In addition, the repeating unit containing a group represented by Formula X3 is preferably based on a repeating unit of a monomer containing a group represented by Formula X3, and the above-mentioned monomer preferably contains a polymerizable group. The polymerizable group contained in the monomer is not particularly limited, and a group having an ethylenically unsaturated bond such as a (meth) acrylfluorenyl group and a vinyl group is preferred.

Specific examples of the repeating unit containing a group represented by Formula X2 include the following repeating units. The repeating unit is not limited to the following specific examples. [Chemical Formula 23]

Specific examples of the repeating unit containing a group represented by Formula X3 include the following repeating units. The repeating unit is not limited to the following specific examples. [Chemical Formula 24]

It is preferable that the resin C1 and the resin C mentioned later contain a repeating unit represented by the following formula 7. [Chemical Formula 25]

In the formula, R represents at least one selected from the group consisting of a trialkylsilyl group, a fluorinated alkyl group having a carbon number of 2 or more, and a tertiary alkyl group, R _A represents a hydrogen atom or a monovalent substituent, and n Represents an integer of 2 or more. Further, the repeating unit represented by the formula 7, R _A and R _A of the formula X1 of the same group described.

The content of the repeating unit X in the resin C1 is not particularly limited, but is preferably 30 to 100 mol%, and more preferably 50 to 100 mol% relative to the total repeating unit in the resin C1. The resin C1 may contain one kind of the repeating unit X, or may contain two or more kinds. When the resin C1 contains two or more kinds of repeating units X, the total content is preferably within the above range. When the content of the repeating unit X in the resin C1 is 50 mol% or more, a resist film formed using the above-mentioned photosensitive radiation- or radiation-sensitive resin composition has more excellent developability.

(Repeating Unit Z) The resin C1 may contain a repeating unit Z other than the repeating unit X and a repeating unit Y described later. Examples of the repeating unit Z include a repeating unit containing a group represented by the following formula K1 or a group represented by K2. In the following formula, * represents a bonding position. [Chemical Formula 26]

In the group represented by formula K1 and the group represented by formula K2, L represents a single bond or a linking group. The form of L in formula K1 is the same as that of L in formula X1, and the form of L in formula K2 It is the same as L in Formula X2. Ar represents an aromatic hydrocarbon ring group, and the state of the aromatic hydrocarbon ring group is the same as that of Ar in Formula X2. R _X represents a straight-chain, cyclic, or branched-chain alkyl group in which neither a fluorine atom nor a silicon atom is substituted. A plurality of R _X may be the same or different. The carbon number of the alkyl group is not particularly limited, and 4 or more is preferable. n4 and n5 represent integers of 1 or more, and a plurality of R _X may be bonded to each other to form a ring.

A specific example of the repeating unit Z is shown below. However, the repeating unit Z that the resin C1 may contain is not limited to the following specific examples. [Chemical Formula 27]

The repeating unit Z may have the following structure. [Chemical Formula 28]

The content of the repeating unit Z in the resin C1 is not particularly limited, but is preferably 0 to 70 mol%, and more preferably 5 to 50 mol% relative to the total repeating unit in the resin C1. The resin C1 may contain one kind of the repeating unit Z, or may contain two or more kinds. When the resin C1 contains two or more kinds of repeating units Z, the total content is preferably within the above range.

The weight average molecular weight of the resin C1 is not particularly limited. As a polystyrene conversion value measured by GPC (Gel Permeation Chromatography) method, 6000 to 50,000 is preferable, and 7,000 to 50,000 is more preferable. 7500 to 40,000 is further preferred, and 8000 to 30,000 is particularly preferred. When the weight average molecular weight of the resin C1 is 7,000 or more, a resist film formed using the above-mentioned photosensitized or radiation-sensitive resin composition has more excellent water followability. For example, in the GPC measurement apparatus: "Alliance GPC2000 (Waters Corporation, Ltd.)," _{Column: TSKgel GMH 6 -HT × 2 +} TSKgel GMH 6 -HTL × 2 ( both 7.5mmI.D. × 30cm, TOSOH CORPORATION Ltd.), Column temperature: 140 ° C, detector: differential refractive index meter, mobile phase: solvent (for example, o-dichlorobenzene, etc.), composition and conditions, and the molecular weight composition can be determined using standard polystyrene.

The content of the resin C1 in the photosensitive radiation- or radiation-sensitive resin composition is not particularly limited, and it is 0.1 to 6% by mass based on the total solid content of the photosensitive radiation- or radiation-sensitive resin composition. Preferably, 0.2 to 3% by mass is more preferable. The resin C1 may be used singly or in combination of two or more kinds. When two or more kinds of resins C1 are used simultaneously, it is preferable that the total content of the resins C1 in the photosensitized or radiation-sensitive resin composition is within the above range.

<Resin C2> The resin C2 is a resin containing the following (ii). (Ii) At least one selected from the group consisting of a group represented by Formula Y1, a group represented by Formula Y3, and a repeating unit represented by Formula Y2. As the resin C2, the following (iib) is preferably contained. (Iib) At least one repeating unit Y selected from the group consisting of a repeating unit containing a group represented by formula Y1, a repeating unit containing a group represented by formula Y3, and a repeating unit represented by formula Y2. As resin C2, the following (iic) is more preferable. (Iic) at least one repeating unit selected from the group consisting of a repeating unit containing two or more groups represented by formula Y1 or a group represented by Y3 and a repeating unit represented by formula Y2. As resin C2, the following (iid) is more preferable. (Iid) A repeating unit containing at least one group selected from the group consisting of a group represented by formula Y1 and a group represented by formula Y3.

[Chemical Formula 29]

In Formula Y1 and Formula Y3, L represents a single bond or a linking group. The aspect of L is the same as that in the above-mentioned formula X2. R ₃ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is replaced with a fluorine atom. R _{3 is} the same as R _{1 in} Formula X1 and R _{2 in} Formula X2. In Formula Y2, R _A represents a hydrogen atom or a monovalent substituent. The definition of the monovalent substituent is the same as the definition of the monovalent substituent represented by R _A in the above formula X1. In the formulae Y1 to Y3, R represents a hydrogen atom or a monovalent substituent. The definition of the monovalent substituent is the same as the definition of the monovalent substituent represented by R _A in the above formula X1. R is preferably a hydrogen atom. In addition, R is preferably an alkyl group, an aryl group, or an alkylamino group containing a substituent. The alkyl group in the substituent-containing alkyl group may be any of linear, branched, and cyclic. The number of carbon atoms contained in the alkyl group is not particularly limited, but 1 to 20 is preferred. The type of the substituent in the alkyl group containing a substituent is not particularly limited, and examples thereof include a halogen atom (preferably a fluorine atom). Among them, as the alkyl group containing a substituent, an alkyl group in which at least one hydrogen atom is replaced with a fluorine atom is preferred.

Moreover, as R, an alkyl group or an aryl group which dissociates under basic conditions is also preferable. "Alkyl group or aryl group dissociated under basic conditions" means a group which dissociates under basic conditions and indicates a hydrophilic group. Preferred examples of the alkyl or aryl group dissociated under basic conditions include groups in which one or more hydrogen atoms at any position are substituted with a halogen atom such as a fluorine atom, and an electron-withdrawing group such as a nitro group or a cyano group. .

When R is a hydrogen atom, L _A represents a single bond. When R is a monovalent substituent, L _A represents a linking group. The aspect of the linking group is the same as that of L in the above formula X2. When R is a monovalent substituent, L _A may be a divalent linking group represented by the following formula (L _Y2 ). [Chemical Formula 30]

In the formula (L _Y2 ), L _B and L _C each independently represent a single bond or a divalent linking group, and V represents a group containing a structure represented by the above formula (LC1-1) to (LC1-17). The divalent group of two hydrogen atoms at any position is removed. When L _B and L _C are a divalent linking group, the state is the same as L as the divalent linking group in Formula X2. Also, * indicates a bonding position. Specific examples of the divalent linking group represented by the formula (L _Y2 ) are shown below. However, the group represented by the above formula (L _Y2 ) is not limited to the following. In the following formula, * represents a bonding position. [Chemical Formula 31]

Specific examples of the group represented by Formula Y1 are shown below. However, the above-mentioned groups are not limited to the following specific examples. In the following formula, * represents a bonding position. [Chemical Formula 32]

Specific examples of the repeating unit represented by Formula Y2 are shown below. However, the repeating unit is not limited to the following specific examples. [Chemical Formula 33]

Specific examples of the group represented by the formula Y3 include -SO ₃ H and the like. However, the above-mentioned groups are not limited to specific examples.

The resin C2 preferably contains a repeating unit Y. The repeating unit containing the group represented by the formula Y1 or the group represented by the formula Y3 is preferably based on the repeating unit of the monomer containing the group represented by the formula Y1 or the monomer containing the group represented by the formula Y3. It is more preferable that the above-mentioned monomer contains a polymerizable group. The aspect of the polymerizable group contained in the monomer is the same as the polymerizable group contained in the repeating unit based on the monomer containing the group represented by the formula X2.

Specific examples of the repeating unit containing a group represented by the formula Y1 include the following repeating units. The repeating unit is not limited to the following specific examples. [Chemical Formula 34]

The content of the repeating unit Y in the resin C2 is not particularly limited, and is preferably 5 to 100 mol%, and more preferably 10 to 100 mol% relative to the total repeating unit in the resin C2. The resin C2 may contain one kind of the repeating unit Y, or may contain two or more kinds. When the resin C2 contains two or more kinds of repeating units Y, the total content is preferably within the above range.

(Repeating Unit Z) The resin C2 may contain a repeating unit Z other than the repeating unit X and the repeating unit Y. The aspect of the repeating unit Z is the same as described above. The content of the repeating unit Z in the resin C2 is not particularly limited, but is preferably 0 to 70 mol%, and more preferably 5 to 70 mol% relative to the total repeating unit in the resin C2. The resin C2 may contain one kind of the repeating unit Z, or may contain two or more kinds. When the resin C2 contains two or more kinds of repeating units Z, the total content is preferably within the above range.

The weight average molecular weight of the resin C2 is not particularly limited. As a polystyrene conversion value measured by GPC (Gel Permeation Chromatography) method, 7,000 to 50,000 is preferable, and 7500 to 40,000 is more preferable. 7800 to 30,000 is more preferable.

The content of the resin C2 in the photosensitive radiation- or radiation-sensitive resin composition is not particularly limited, and it is 0.3 to 8% by mass relative to the total solid content of the photosensitive radiation- or radiation-sensitive resin composition. It is more preferably 0.5 to 5 mass%. Moreover, the resin C2 may be used individually by 1 type, and may use 2 or more types together. When two or more kinds of resins C2 are used simultaneously, it is preferable that the total content of the resins C2 in the photosensitized or radiation-sensitive resin composition is within the above range.

When the photosensitive radiation- or radiation-sensitive resin composition contains resin C1 and resin C2, the total content is 0.4 to 8% by mass relative to the total solid content of the photosensitive radiation- or radiation-sensitive resin composition. More preferably, 0.7 to 7 mass% is more preferable. As the mass ratio of the content of the resin C2 to the content of the resin C1 in the actinic radiation- or radiation-sensitive resin composition (containing mass ratio: content of resin C2 / content of resin C1), 0.6 to 8 is preferable. 0.8 to 5 is more preferable.

<Resin C> The resin C is a resin containing both of the following (i) and (ii). (I) At least one selected from the group consisting of a repeating unit represented by Formula X1, a group represented by Formula X2, and a group represented by Formula X3. (Ii) At least one selected from the group consisting of a group represented by Formula Y1, a group represented by Formula Y3, and a repeating unit represented by Formula Y2. The resin C preferably contains a repeating unit X and a repeating unit Y. The aspect of (i), (ii), repeating unit X, and repeating unit Y is the same as that described above. The resin C may contain a repeating unit Z. The aspect of the repeating unit Z is the same as that described above.

The content of the repeating unit X in the resin C is not particularly limited, but is preferably 0.1 to 99 mol%, and more preferably 1 to 96 mol% with respect to the total repeating unit in the resin C. The content of the repeating unit Y in the resin C is not particularly limited, but is preferably 0.1 to 99 mol%, and more preferably 1 to 96 mol% with respect to the total repeating unit in the resin C. The content of the repeating unit Z in the resin C is not particularly limited, but is preferably 0 to 50 mol%, and more preferably 3 to 50 mol% relative to the total repeating unit in the resin C.

The weight average molecular weight of the resin C is not particularly limited. As a polystyrene conversion value measured by GPC (Gel Permeation Chromatography) method, 6,000 to 50,000 is preferable, and 7,000 to 50,000 is more preferable. 7500 to 40,000 is further preferred, 7800 to 30,000 is particularly preferred, and 8000 to 30,000 is most preferred. If the weight average molecular weight of the resin C is 7000 or more, the resist film obtained from the above photosensitized or radiation-sensitive resin composition has more excellent water followability, and if the weight average molecular weight of the resin C is 7500 As described above, the resist film obtained from the above photosensitized or radiation-sensitive resin composition has more excellent water followability.

The content of the resin C in the photosensitive radiation- or radiation-sensitive resin composition is not particularly limited, and is 0.4 to 8% by mass relative to the total solid content of the photosensitive radiation- or radiation-sensitive resin composition. More preferably, it is 0.6 to 6 mass%. The resin C may be used singly or in combination of two or more kinds. When two or more types of resin C are used simultaneously, it is preferable that the total content of the resin C in the above-mentioned actinic radiation- or radiation-sensitive resin composition is within the above range.

The resin C, resin C1, and resin C2 are preferably at least one polymer selected from the group consisting of (meth) acrylate derivatives, styrene derivatives, and allyl-containing compounds. It is preferable that at least one resin selected from the group consisting of resin C1, resin C2, and resin C contains an aromatic ring.

The said photosensitized or radiation-sensitive resin composition contains at least one of the combination of resin C1 and resin C2, and resin C. Examples of the combination of the resin C1, resin C2, and resin C contained in the photosensitive radiation- or radiation-sensitive resin composition include: resin C; resin C1 and resin C2; resin C and resin C1; resin C and resin C2; Resin C1, Resin C2, Resin C, etc. Moreover, each resin may be used individually by 1 type, and may use 2 or more types together. Among them, as the above-mentioned actinic radiation- or radiation-sensitive resin composition, from the viewpoint of obtaining more excellent effects of the present invention, at least one containing resin C and selected from the group consisting of resin C1 and resin C2 is Better.

When the actinic radiation- or radiation-sensitive resin composition contains one or two or more specific resins selected from the group consisting of resin C1, resin C2, and resin C, all the specific resins contain Repeating units of at least one monomer of the formula in the group consisting of 3 to 5 are preferred. The resist film formed using all the specific resins satisfying the above-mentioned photosensitized or radiation-sensitive resin composition has more excellent developability. The above-mentioned resist film particularly has more excellent developability and water followability. The developability and water followability can be evaluated by the "pattern collapse, LER, scum, development defect, water followability" evaluation method (each evaluation method described in Examples) described later.

P / Mw≥0.03 (3) Q _F × M _F /Mw≥0.35 (4) Q _Si × M _Si /Mw≥0.15 (5)

In Formula 3, P represents a ClogP value of the monomer. The "monomer" refers to a monomer that forms a specific resin by polymerization. Here, the "CLogP value" refers to a computer-calculated value of the logP of the partition coefficient P in water-n-octanol in a common logarithm, and is used as an index indicating the degree of hydrophilicity and hydrophobicity of a substance. The CLogP of each cell can be calculated, for example, by using software from Cambridge Soft, Chem Draw Ultra 8.0. Moreover, Mw represents the molecular weight of the said monomer. Here, "molecular weight" means a molecular weight which can be calculated from the chemical structural formula of each monomer.

In Formula 4, Q _F represents the number of fluorine atoms in each molecule of each monomer, and M _F represents the atomic weight of fluorine atoms. In addition, in Formula 5, Q _Si represents the number of silicon atoms in each molecule of each monomer, and M _Si represents the atomic weight of silicon atoms.

It is more preferable that the specific resin contains a repeating unit derived from a monomer satisfying the above formula (4) and the following formula (6) or the above formula (5) and the following formula (6). A resist film obtained by using a photosensitized radiation- or radiation-sensitive resin composition containing a monomer satisfying the above formula has more excellent developability. The above-mentioned resist film is less likely to cause development residues during development. In addition, the difficulty in generating development residue can be evaluated by the "scum" evaluation method described later.

P / Mw≥0.02 (6) In formula (6), P and Mw are the same as P and Mw in formula (3).

Resin C, Resin C1, and Resin C2 have less impurities such as metals, and the residual monomer and / or oligomer component is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass is more preferable. This makes it possible to obtain a photosensitized radioactive or radiation-sensitive resin composition with time-dependent changes such as foreign matter and / or sensitivity in the liquid. In addition, in terms of resolution, resist shape, side wall of the resist pattern, roughness, etc., the molecular weight distribution (Mw / Mn, also called dispersion) is preferably in a range of 1 to 3, and more preferably 1 to 2, more preferably 1 to 1.8, and most preferably 1 to 1.5.

As the resin C, the resin C1, and the resin C2, commercially available products can be used, and they can be synthesized by a known method, for example, a radical polymerization method. As the above-mentioned synthesis method, for example, the method described in paragraphs 0203 to 0210 of Japanese Patent Application Laid-Open No. 2010-44358 can be used, and the above contents are incorporated into this specification.

Specific examples of the resin C, the resin C1, and the resin C2 include the following resins. The resin is not limited to the following specific examples. In addition, Table 1 shows the molar ratios of the repeating units in each resin (corresponding to the repeating units in order from the left) and the weight average molecular weight (Mw). [Chemical Formula 35]

[Chemical Formula 36]

[Chemical Formula 37] In the formula, * indicates a bonding position.

[Chemical Formula 38] In the formula, * indicates a bonding position.

[Table 1]

[Table 1 (continued)]

[Table 1 (continued)]

In the above table, "-" indicates a monomer that does not contain the column (the same applies hereinafter).

[Optional component] The above-mentioned actinic radiation- or radiation-sensitive resin composition may contain components other than the above. Examples of components other than the above include solvents and basic compounds.

<Solvent D> Examples of solvents that can be used to dissolve the above components and can be used in the preparation of a photosensitized or radiation-sensitive resin composition include, for example, alkylene glycol monoalkyl ether carboxylic acid esters and alkylene diamines. Alcohol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably 4 to 10 carbons), monoketone compounds that may contain rings (preferably 4 to 10 carbons) 10) Organic solvents such as alkylene carbonate, alkyl alkoxyacetate and alkyl pyruvate.

Alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, cyclic lactone, cyclic monoketone compound, alkylene carbonate, alkoxy Specific examples of the alkyl acetate and the alkyl pyruvate are described in paragraphs 0227, 0228, 0229, 0230, 0231, 0232, and 0233 of Document A, respectively, and the above contents are incorporated into this specification. Moreover, as a preferable solvent, the solvent described in paragraph 0234 of the document A is mentioned, and this content is incorporated into this specification.

These solvents may be used singly or in combination of two or more kinds. In addition, as the organic solvent, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure and a solvent containing no hydroxyl group can be used. In addition, as a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group, they are described in paragraphs 0235 and 0236 of Document A, respectively, and the contents are incorporated into this specification.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass of a non-hydroxyl-containing solvent is particularly preferred. The solvent is preferably a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

<Basic Compound> In order to reduce the change in performance over time from exposure to heating, it is preferred that the photosensitized radiation or radiation-sensitive resin composition contains a basic compound. The aspect of the basic compound is described in paragraphs 0238 to 0250 of Document A, and this content is incorporated into this specification.

Although a particularly preferable compound (D) is specifically shown as a basic compound, a basic compound is not limited to this. [Chemical Formula 39]

[Chemical Formula 40]

[Chemical Formula 41]

These basic compounds may be used alone or in combination of two or more.

The amount of the basic compound used is usually 0.001 to 10% by mass, and preferably 0.01 to 5% by mass, based on the solid content of the photosensitized or radiation-sensitive resin composition.

<Surfactant> The photosensitized or radiation-sensitive resin composition preferably further contains a surfactant, and contains fluorine-based and / or silicon-based surfactants (fluorine-based surfactants, silicon-based surfactants, It is more preferable to use any one or two or more of a surfactant including a fluorine atom and a silicon atom.

When the photosensitizing or radiation-sensitive resin composition contains the above-mentioned surfactant, when using an exposure light source of 250 nm or less, especially 220 nm or less, it is possible to provide a pattern with less adhesion and less development defects with good sensitivity and resolution. .

The specific aspect of the surfactant is described in paragraphs 0257 to 0262 of Document A, and this content is incorporated into this specification.

These surfactants can be used alone or in combination. The amount of the surfactant to be used is preferably 0.0001 to 2% by mass, and more preferably 0.001 to 1% by mass, with respect to the total amount of the photosensitive radiation- or radiation-sensitive resin composition (excluding the solvent).

<Onium Carboxylate Salt> The actinic radiation- or radiation-sensitive resin composition in the present invention may contain an onium carboxylate salt. Examples of the onium carboxylic acid salts include carboxylic acid phosphonium salts, carboxylic acid phosphonium salts, and carboxylic acid ammonium salts. In particular, onium carboxylate salts, sulfonium salts, and sulfonium salts are preferred. Moreover, it is preferable that the carboxylic acid ester residue of the carboxylic acid onium salt of the present invention does not contain an aromatic group and a carbon-carbon double bond. As a preferable anion part, a linear, branched, monocyclic or polycyclic cyclic alkylcarboxylic acid anion having a carbon number of 1 to 30 is more preferable. More preferred is an anion of a carboxylic acid in which some or all of these alkyl groups are substituted with fluorine atoms. The alkyl group may contain an oxygen atom. Thereby, the transparency and the resolution with respect to light of 220 nm or less are improved, and the density dependency and the exposure margin are improved.

<Decomposition compound that decomposes by the action of an acid and has an increased solubility in an alkaline developer and has a molecular weight of 3000 or less> The actinic radiation- or radiation-sensitive resin composition in the present invention may contain It dissolves due to the action and increases the solubility in an alkali developing solution, and a dissolution preventing compound having a molecular weight of 3,000 or less (hereinafter, also referred to as "dissolution preventing compound"). As a dissolution preventing compound, in order not to reduce the permeability below 220 nm, a lipid containing an acid-decomposable group, such as a bile acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724,355 (1996). Cyclic or aliphatic compounds are preferred. Examples of the acid-decomposable group and the alicyclic structure include the same compounds as those described for the resin A. Moreover, as a specific example of a dissolution preventing compound, the compound described in paragraph 0270 of the document A is mentioned, and the said content is incorporated into this specification.

<Other additives> The photosensitive radiation- or radiation-sensitive resin composition of the present invention may further contain a compound (for example, a compound that promotes solubility to a dye, a plasticizer, a photosensitizer, a light absorber, and a developing solution, if necessary) (for example, A phenol compound having a molecular weight of 1,000 or less, an alicyclic or aliphatic compound having a carboxyl group, and the like.

The total solid content concentration in the photosensitized radioactive or radiation-sensitive resin composition is preferably 1 to 10% by mass, more preferably 1 to 8% by mass, and even more preferably 1 to 6% by mass.

[Pattern forming method] The pattern forming method according to the embodiment of the present invention includes the following A to C processes. (A) Resist film formation process: A process of forming a photosensitive radiation- or radiation-sensitive resin composition film on a substrate using a photosensitive radiation- or radiation-sensitive resin composition. (B) Exposure process: A process of irradiating actinic radiation or radiation to a photoresistive or radiation-sensitive resin composition film. (C) Development process: A process for developing an actinic ray or radiation-sensitive resin composition film that has been irradiated with actinic rays or radiation using an alkali developing solution. The pattern forming method may include (A) to (C), and may include other processes. Hereinafter, aspects of each process will be described.

[(A) Resist film formation process] The resist film formation process uses a photosensitive radiation- or radiation-sensitive resin composition to form a photosensitive radiation- or radiation-sensitive resin composition film (resist on a substrate). Agent film) process.

Examples of a method for forming a resist film on a substrate include a method of applying a photosensitive radiation- or radiation-sensitive resin composition to a substrate. The coating method is not particularly limited, and a conventionally known spin coating method, spray coating method, roll coating method, or dipping method can be used, and a spin coating method is preferred.

After the resist film is formed, the substrate may be heated as needed (Prebake (PB)). Thereby, a film from which the insoluble residual solvent has been removed can be formed uniformly. The pre-baking temperature after the formation of the resist film is not particularly limited, but 50 ° C to 160 ° C is preferred, and 60 ° C to 140 ° C is more preferred.

The substrate for forming the resist film is not particularly limited, and inorganic substrates such as silicon, SiN, and SiO ₂ can be used; coating inorganic substrates such as SOG (Spin on Glass); semiconductor manufacturing processes such as IC (Integrated Circuit), liquid crystal, and Substrates and the like commonly used in the manufacturing process of circuit boards such as thermal sensors and other photolithographic processes such as photolithography.

The thickness of the resist film is not particularly limited, but is preferably 80 nm or less.

Before the resist film is formed, an anti-reflection film may be coated on the substrate in advance. As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, or amorphous silicon; an organic film type including a light absorbing agent and a polymer material can be used. In addition, as the organic antireflection film, DUV30 series, DUV-40 series manufactured by Brewer Science, Inc., AR-2, AR-3, AR-5 manufactured by Shipley Japan, Ltd., and NISSAN CHEMICAL INDUSTRIES. LTD. Commercially available organic anti-reflection films such as ARC series such as ARC29A.

[(B) Exposure Process] The exposure process is a process of irradiating a resist film with actinic rays or radiation. The exposure can be performed by a known method. For example, the resist film is irradiated with actinic rays or radiation through a predetermined mask. In this case, it is preferable to irradiate actinic rays or radiation through the liquid immersion liquid, but it is not limited thereto. The exposure amount can be appropriately set, and it is usually preferably 10 to 60 mJ / cm ² .

The wavelength of the light source used in the exposure device is not particularly limited, and light with a wavelength of 250 nm or less is preferred. Examples include KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), and F ₂ Excimer laser light (157nm), EUV light (13.5nm) and electron beam. Among them, ArF excimer laser light (193 nm) is preferred.

When performing the liquid immersion exposure, the surface of the resist film may be cleaned using an aqueous chemical solution before and / or after exposure and before heating.

Regarding the liquid immersion liquid, a liquid having a temperature coefficient of refractive index as small as possible is preferable so as to be transparent with respect to the exposure wavelength, and to suppress distortion of the optical image projected on the resist film to a minimum. In particular, when the exposure light source is ArF excimer laser light (wavelength; 193 nm), in addition to the above-mentioned viewpoints, in terms of availability and operability, water is preferred.

When water is used as the liquid immersion liquid, an additive (liquid) that increases the surface active force while reducing the surface tension of water can be added to water in a small proportion. This additive does not dissolve the resist film on the substrate, and it is preferable to be able to ignore the influence on the optical coating on the lower surface of the lens element. As the water used, distilled water is preferred. Further, pure water that has been filtered through an ion exchange filter or the like can be used. This makes it possible to suppress distortion of the optical image projected on the resist film due to the incorporation of impurities.

Furthermore, from the viewpoint of improving the refractive index, a medium having a refractive index of 1.5 or more can be used. The medium may be an aqueous solution or an organic solvent.

The above pattern forming method may include a plurality of exposure processes. In this case, the same light source may be used for multiple exposures, or different light sources may be used. It is better to use ArF excimer laser light (wavelength; 193 nm) in the first exposure.

After exposure, heating (baking) is preferably performed, and development is performed (preferably, further developing is performed). Thereby, a more favorable pattern can be obtained. The baking temperature is not particularly limited within a range in which a good pattern can be obtained, but is usually 40 ° C to 160 ° C. Baking can be performed once or multiple times.

[(C) Development Process] The development process is a process for developing a resist film that has been irradiated with the above-mentioned actinic rays or radiation using an alkali developing solution. In the development process, an alkali developer is used as follows. As the alkali developing solution of the photosensitive radiation- or radiation-sensitive resin composition, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia can be used; ethylamine, n-propylamine And other primary amines; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcoholamines such as dimethylethanolamine and triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; basic aqueous solutions such as cyclic amines such as pyrrole and piperidine. Furthermore, an appropriate amount of an alcohol or a surfactant can be added to the alkali developing solution and used.

The alkali concentration of the alkali developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0. Furthermore, an appropriate amount of an alcohol or a surfactant can be added to the alkaline aqueous solution and used. As the rinsing liquid, pure water can be used, and an appropriate amount of a surfactant can be added and used.

In addition, after the development process or the rinsing process, a process of removing the developing solution or the rinsing solution adhered to the pattern by a supercritical fluid can be performed.

The pattern forming method described above can be applied to a method of manufacturing an electronic component. In this specification, "electronic component" means a semiconductor device, a liquid crystal device, and electrical and electronic equipment (home appliances, media-related equipment, optical equipment, and communication equipment, etc.). [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, proportions, processing contents, and processing procedures shown in the following examples can be changed as appropriate without departing from the scope of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[Synthesis Example 1 Resin (C-1) Synthesis] 1,1,1,3,3,3-hexafluoro-2- (4-vinylphenyl) propane-2-ol (20 g) was dissolved in propylene glycol Monomethyl ether acetate (40 g) gave a solution. To this solution, 3 mol% of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the solution. This was dropped under a nitrogen atmosphere over 6 hours to propylene glycol monomethyl ether acetate (40 g) heated to 80 ° C. to obtain a reaction solution. After the dropping was completed, the reaction solution was stirred for two hours. After the reaction was completed, the reaction solution was cooled to room temperature, crystallized in 1000 mL of a methanol / water mixed solution (volume ratio 9/1), and the precipitated white powder was filtered to recover the target product. 12g of resin (C-1). The weight average molecular weight in terms of standard styrene calculated by GPC measurement was 9,600. In the same state, other resins shown in Table 1 were synthesized.

[Synthesis Example 2 Resin (1)] Under a nitrogen flow, 8.6 g of cyclohexanone was placed in a three-necked flask, and this was heated to 80 ° C. 9.8 g of 2-adamantyl isopropyl methacrylate, 4.4 g of dihydroxyadamantyl methacrylate, and 8.9 g of norbornane methacrylate were added thereto to obtain a monomer solution. Next, the polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was metered so that the total amount of the monomers became 8 mol%, and the polymerization initiator was dissolved in 79 g of the ring. A polymerization initiator solution of hexanone. The reaction solution was obtained by dripping the polymerization initiator solution from the monomer solution over 6 hours. After the dropping was completed, the reaction was further performed at 80 ° C for two hours. After the reaction solution was allowed to cool, it was dropped into a mixed solution of 800 mL of hexane / 200 mL of ethyl acetate over 20 minutes. The precipitated powder was filtered and dried to obtain 19 g of a resin (1). The weight average molecular weight of the obtained resin obtained by GPC measurement was 8800 in terms of standard polystyrene, and the degree of dispersion (Mw / Mn) was 1.9. In the same manner, other resin A shown below was synthesized. The structure of the acid-decomposable resin A used in the examples is shown below. In addition, Table 2-1 and Table 2-2 show the Mohr ratio (in order from the left side in the structural formula), the weight average molecular weight (Mw), and the dispersion (Mw / Mn) of the repeating units in each resin.

[Chemical Formula 42]

[Chemical Formula 43]

[Chemical Formula 44]

[table 2-1]

[Table 2-2]

[Preparation of a photosensitive radiation- or radiation-sensitive resin composition (resist composition)] The components shown in the following Tables 4 and 5 were dissolved in a solvent, and a solution having a solid content concentration of 5% by mass was prepared. A positive-type resist composition was prepared by filtering it with a polyethylene filter having a pore size of 0.1 μm. The prepared positive resist composition was evaluated by the following method, and the results are shown in Tables 4 and 5. The symbols in Tables 4 and 5 are the same as the following. The resin B, resin C1, resin C2, and resin C which generate an acid by irradiation with actinic rays or radiation correspond to those exemplified above.

[Basic compound] N-1: N, N-dibutylaniline N-2: N, N-dihexylaniline N-3: 2,6-diisopropylaniline N-4: tri-n-octylamine N -5: N, N-dihydroxyethylaniline N-6: 2,4,5-triphenylimidazole N-9: 2- [2-fluorene 2- (2,2-dimethoxy-phenoxy) Ethoxy) ethylfluorene-bis- (2-methoxyethyl)]-amine [surfactant] W-1: MegafacF176 (manufactured by DIC Corporation, fluorine-based) W-2: MegafacR08 (manufactured by DIC Corporation) , Fluorine-based and silicon-based) W-3: polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., silicon-based) W-4: Troy Sol S-366 (Troy Chemical Industries Inc. (Manufactured) W-5: PF656 (manufactured by OMNOVA SOLUTIONS INC., Fluorine-based) W-6: PF6320 (manufactured by OMNOVA SOLUTIONS INC., Fluorinated) [Solvent] SL-2: propylene glycol monomethyl ether acetate SL-3: Ethyl lactate SL-4: propylene glycol monomethyl ether SL-5: γ-butyrolactone SL-6: propylene carbonate

[Exposure Process and Development Process] A silicon wafer was coated with an organic anti-reflection film-forming composition ARC29A (manufactured by NISSAN CHEMICAL INDUSTRIES. LTD.), And baked at 205 ° C for 60 seconds to form 98 nm Anti-reflection film. The prepared positive resist composition was coated on the formed anti-reflection film, and baked at 130 ° C. for 60 seconds to form a 80 nm resist film. An ArF excimer laser immersion scanner (XT1250i, NA0.85, manufactured by ASML Holding NV) was used, and a 6% half-tone mask with a 1: 1 line and space pattern of 75 nm width was used to resist the obtained band. The wafer of the resist film was exposed. As the liquid immersion liquid, ultrapure water was used. Then, the exposed resist film was heated at 130 ° C for 60 seconds. Then, development was performed using a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, and after washing with pure water, spin drying was performed to obtain a resist pattern.

[Developability Evaluation] [Developability Evaluation 1: Pattern Collapse] Regarding pattern collapse, the exposure amount that reproduces a line and space pattern of 75 nm is taken as the optimal exposure amount, and the optimal exposure amount is used to densely line and space 1: 1. When the pattern and line are exposed with an isolated pattern of 1:10 in space, the line width analyzed without the pattern collapsed in the finer mask size is the limit pattern collapsed line width. A smaller value indicates that a finer pattern is less likely to collapse and be analyzed, and indicates that the pattern is less likely to collapse. In addition, "T-top" in Table 5 shows that the upper part of the pattern becomes thick, and indicates that the pattern collapses and measurement cannot be performed. The results are shown in Tables 4 and 5.

[Developability Evaluation 2: Line Edge Roughness (LER)] A 5 μm edge in the long-side direction of the line pattern will be measured from a scanning electron microscope (S-8840 by Hitachi, Ltd.) using a length measurement SEM The distance from the reference line that should have the edge is measured at 50 places, and the standard deviation is calculated to calculate 3σ. A smaller value indicates better performance. The values were evaluated by the following criteria, and the results are shown in Tables 4 and 5. It is preferable that C or more is used in practice.

A: The 3σ value is less than 5.0. B: The 3σ value is 5.0 or more and less than 6.0. C: The 3σ value is 6.0 or more and less than 7.0. D: The 3σ value is 7.0 or more.

[Developability Evaluation 3: Scum] The development residue (scum) in the resist pattern having a line width of 75 nm was observed with a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.), and evaluated based on the following criteria. . The results are shown in Tables 4 and 5. It is preferable that C or more is used in practice.

A: No residue was generated at all. B: Less residue is produced, but it is a level that is not a problem in practical use. C: A large number of residues are generated, but within the actual use range. D: A residue is severely generated.

[Developability Evaluation 4: Development Defect Evaluation] For the substrate with a resist film that has undergone the above-mentioned exposure process and development process, a defect inspection apparatus KLA2360 (product name) manufactured by KLA-Tencor Corporation was used to set the pixels of the defect inspection apparatus. The size is set to 0.16 μm, and the threshold is set to 20, and the measurement is performed in a random mode to detect the development defects extracted from the difference caused by the overlap of the comparison image and the pixel unit, and calculate the per unit area ( 1 cm ² ). The smaller the value of the number of developing defects per unit area, the better the performance. Evaluation was performed based on the following criteria, and the results are shown in Tables 4 and 5. It is preferable that C or more is used in practice.

A: The number of developing defects per unit area is less than 0.5. B: The number of development defects per unit area is 0.5 or more and less than 0.7. C: The number of development defects per unit area is 0.7 or more and less than 1.0. D: The number of developing defects per unit area is 1.0 or more.

[Evaluation of Water Followability] A silicon wafer was coated with the above-prepared resist composition and baked at 130 ° C for 60 seconds to form a 160 nm resist film and obtain a resist with tape Wafer film. Next, the obtained wafer with a resist film was arranged such that the resist film was opposed to the quartz glass substrate, and pure water was filled therebetween. In the above state, the quartz glass substrate was moved (scanned) in parallel with respect to the wafer surface, and the state of pure water following it was observed with the naked eye. The scanning speed of the quartz glass substrate was gradually increased, and the limit scanning speed (unit: nm / second) of pure water that could not follow the scanning speed of the quartz glass substrate and began to remain on the receding water droplets was evaluated to evaluate water followability. The larger the limit scanning speed is, the more the water can follow a higher high-speed scanning speed, and the water followability on the resist film is good. The results are shown in Tables 4 and 5. In addition, it is preferably 100 nm / second or more for practical use. In addition, the "mass%" in the columns of "resin C1", "resin C2", and "resin C" in Tables 4 and 5 indicates the content relative to the total solid content.

In Table 4, as the resin "C-34", a resin including the following repeating units was used. The molecular weight of the resin "C-34" is shown in the following table. [Chemical Formula 45]

[table 3]

[Table 4]

[Table 4 (continued)]

[Table 4 (continued)]

[table 5]

From the results shown in Tables 4 and 5, the implementation was performed by using a photosensitized radioactive or radiation-sensitive resin composition containing at least one of resin A, compound B, a combination of resin C1 and resin C2, and resin C. The pattern forming methods of Examples 1 to 37 can achieve a desired effect. However, the pattern forming methods of Comparative Examples 1 to 7 failed to obtain the desired effects. Compared with the pattern forming method of Example 17, the pattern forming method of the 19th aspect of the patent application scope of the photoresistive or radiation-sensitive resin composition satisfying the relationship of the second aspect of the patent application scope has more excellent developability and water. Followability. Compared with the pattern forming method of Example 1, the pattern forming method of Examples 5, 10, 11, 25 to 30 that satisfies the relationship between the actinic radiation or radiation-sensitive resin composition satisfies the third item in the scope of patent application, There is no "C" evaluation in the evaluation of properties, and it has more excellent developability. Compared with the pattern forming method of Example 1, the photosensitive radiation- or radiation-sensitive resin composition contains resin C, and further contains pattern formation of Example 2 selected from the group consisting of resin C1 and resin C2. The method has more excellent developability and water followability.

no.

Claims (32)

A pattern forming method includes: a resist film forming process, using a photosensitized radioactive or radiation-sensitive resin composition, to form a photosensitized radioactive or radiation-sensitive resin composition film on a substrate; an exposure process for the photosensitive Actinic radiation or radiation-sensitive resin composition film is irradiated with actinic radiation or radiation; and in a development process, the above-mentioned actinic radiation- or radiation-sensitive resin composition film that has been irradiated with actinic radiation or radiation is subjected to an alkali developing solution Development, in which the above-mentioned actinic radiation- or radiation-sensitive resin composition contains: resin A whose solubility in an alkali developing solution increases due to the action of acid; resin B which generates an acid by irradiation of the actinic ray or radiation And at least one of the combination of resin C1 and resin C2, and resin C; and said resin C1 contains a repeating unit represented by formula (X1), a group represented by formula (X2), and formula (X3) The resin C2 contains at least one selected from the group consisting of a group represented by the formula (Y1) and a group represented by the formula (Y3). And at least one of the group consisting of a repeating unit represented by formula (Y2), the resin C contains: selected from the repeating unit represented by formula (X1), a group represented by formula (X2), and At least one of the group consisting of the group represented by (X3); and selected from the group represented by formula (Y1), the group represented by formula (Y3), and the repeating unit represented by formula (Y2) At least one of the group, In the formula (X1), L represents a single bond or a linking group, R ₁ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, R _A represents a hydrogen atom or a monovalent substituent, and n1 represents an integer of 1 or more. In the formula (X2), L represents a single bond or a linking group, R ₂ represents a fluorine atom, an alkyl group substituted with at least one hydrogen atom by a fluorine atom, or -Si (R ₁₀ ) ₃ , and Ar represents an aromatic hydrocarbon ring group, n2 represents an integer of 1 or more, * represents a bonding position, and R ₁₀ represents an alkyl group. In the formula (X3), L represents a single bond or a linking group, R ₁₀ represents an alkyl group, and n3 represents an integer of 1 or more, * Represents a bonding position, in the formula (Y1), L represents a single bond or a linking group, R ₃ each independently represents a fluorine atom or an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and R represents a hydrogen atom or a monovalent substituent In formula (Y2), R _A and R each independently represent a hydrogen atom or a monovalent substituent. When R is a hydrogen atom, L _A represents a single bond, and when R is a monovalent substituent, L _A represents a link. Group, in the formula (Y3), L represents a single bond or a linking group, R represents a hydrogen atom or a monovalent substituent, and * represents a bonding position. The pattern forming method according to item 1 of the scope of patent application, wherein when the photosensitized radiation or radiation-sensitive resin composition includes one selected from the group consisting of the resin C1, the resin C2, and the resin C, or In the case of two or more specific resins, all of the above-mentioned specific resins contain a repeating unit derived from a monomer that satisfies at least one formula selected from the group consisting of formulas (3) to (5), P / Mw ≥0.03 (3) Q _F × M _F /Mw≥0.35 (4) Q _Si × M _Si /Mw≥0.15 (5) In formulas (3) to (5), P represents the ClogP value of the above monomers, Mw Represents the molecular weight of the monomer, Q _F represents the number of fluorine atoms in each molecule of the monomer, M _F represents the atomic weight of fluorine atoms, Q _Si represents the number of silicon atoms in each molecule of the monomer, M _Si represents the atomic weight of silicon atoms. The pattern forming method according to item 2 of the scope of patent application, wherein at least one of the above-mentioned specific resins contains a monomer derived from monomers satisfying formulas (4) and (6), or formulas (5) and (6) Repeating unit, Q _F × M _F /Mw≥0.35 (4) Q _Si × M _Si /Mw≥0.15 (5) P / Mw≥0.02 (6) In formulas (4) to (6), P represents the above unit ClogP value, Mw represents the molecular weight of the above monomer, Q _F represents the number of fluorine atoms in each molecule of the above monomer, Q _Si represents the number of silicon atoms in each molecule of the above monomer, and M _F represents The atomic weight of a fluorine atom, and M _Si represents the atomic weight of a silicon atom. The pattern forming method according to any one of claims 1 to 3, wherein R ₁ in the repeating unit represented by the above formula (X1) and R _{1 in} the group represented by the above formula (X2) R ₂ is an alkyl group substituted with three or more fluorine atoms. The pattern forming method according to any one of claims 1 to 3, wherein R in the repeating unit represented by the above formula (Y2), the group represented by the above formula (Y1), and the above R in the group represented by formula (Y3) is a hydrogen atom. The pattern forming method according to any one of claims 1 to 3, wherein R in the repeating unit represented by the above formula (Y2), the group represented by the above formula (Y1), and the above R in the group represented by formula (Y3) is an alkyl group, an aryl group, or an alkylamino group containing a substituent. The pattern forming method according to item 6 of the scope of patent application, wherein R in the repeating unit represented by the above formula (Y2), a group represented by the above formula (Y1), and a group represented by the above formula (Y3) Where R is an alkyl or aryl group which is removed under basic conditions. The pattern forming method according to any one of claims 1 to 3, wherein the resin C and the resin C2 include a repeating unit containing two or more units selected from the formula (Y1) At least one group in the group represented by the group represented by the formula (Y3). The pattern forming method according to any one of claims 1 to 3, wherein the resin C, the resin C1, and the resin C2 are selected from (meth) acrylate derivatives and styrene derivatives. And at least one polymer in the group consisting of allyl compounds. The pattern forming method according to any one of claims 1 to 3, wherein at least one resin selected from the group consisting of the resin C1, the resin C2, and the resin C contains an aromatic ring. The pattern forming method according to any one of claims 1 to 3 in the scope of the patent application, wherein the resin C1 and the resin C contain a repeating unit represented by formula (7), In the formula, R represents at least one selected from the group consisting of a trialkylsilyl group, a fluorinated alkyl group having a carbon number of 2 or more, and a tertiary alkyl group, R _A represents a hydrogen atom or a monovalent substituent, and n Represents an integer of 2 or more. The pattern forming method according to any one of claims 1 to 3, wherein the photosensitive radiation- or radiation-sensitive resin composition contains: the resin C, and a resin selected from the resin C1 and the resin At least one of the group consisting of C2. The pattern forming method according to any one of claims 1 to 3, wherein the resin A contains a repeating unit, and the repeating unit contains a lactone structure. The pattern forming method according to any one of claims 1 to 3, wherein the photosensitive radiation- or radiation-sensitive resin composition further contains a solvent D. The pattern forming method according to any one of claims 1 to 3, wherein the film thickness of the photosensitized radiation- or radiation-sensitive resin composition film is 80 nm or less. The pattern forming method according to any one of claims 1 to 3 in the scope of patent application, wherein the exposure process is a liquid immersion exposure process. A method for manufacturing an electronic component, comprising the pattern forming method according to any one of claims 1 to 16 of the scope of patent application. A photosensitive radiation- or radiation-sensitive resin composition, comprising: resin A whose solubility in an alkali developing solution increases due to the action of an acid; resin B which generates an acid by irradiation with actinic rays or radiation; and a resin A combination of C1 and resin C2 and at least one of resin C; and said resin C1 contains a repeating unit represented by formula (X1), a group represented by formula (X2), and a group represented by formula (X3) The resin C2 contains at least one selected from the group consisting of a group represented by formula (Y1), a group represented by formula (Y3), and a repeating unit represented by formula (Y2). At least one of the above resins C contains at least one selected from the group consisting of a repeating unit represented by formula (X1), a group represented by formula (X2), and a group represented by formula (X3) ; And at least one selected from the group consisting of a group represented by formula (Y1), a group represented by formula (Y3), and a repeating unit represented by formula (Y2), In the formula (X1), L represents a single bond or a linking group, R ₁ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, R _A represents a hydrogen atom or a monovalent substituent, and n1 represents an integer of 1 or more. In the formula (X2), L represents a single bond or a linking group, R ₂ represents a fluorine atom, an alkyl group substituted with at least one hydrogen atom by a fluorine atom, or -Si (R ₁₀ ) ₃ , and Ar represents an aromatic hydrocarbon ring group, n2 represents an integer of 1 or more, * represents a bonding position, and R ₁₀ represents an alkyl group. In the formula (X3), L represents a single bond or a linking group, R ₁₀ represents an alkyl group, and n3 represents an integer of 1 or more, * Represents a bonding position, in the formula (Y1), L represents a single bond or a linking group, R ₃ each independently represents a fluorine atom or an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and R represents a hydrogen atom or a monovalent substituent In formula (Y2), R _A and R each independently represent a hydrogen atom or a monovalent substituent. When R is a hydrogen atom, L _A represents a single bond, and when R is a monovalent substituent, L _A represents a linking group. Group, in the formula (Y3), L represents a single bond or a linking group, R represents a hydrogen atom or a monovalent substituent, and * represents a bonding position. The actinic radiation- or radiation-sensitive resin composition according to item 18 of the scope of the patent application, which contains one or two or more specific resins selected from the group consisting of the resin C1, the resin C2, and the resin C. All the above-mentioned specific resins contain repeating units derived from a monomer that satisfies at least one formula selected from the group consisting of formulas (3) to (5), P / Mw≥0.03 (3) Q _F × M _F /Mw≥0.35 (4) Q _Si × M _Si /Mw≥0.15 (5) In formulas (3) to (5), P represents the ClogP value of the above monomer, and Mw represents the molecular weight of the above monomer, Q _F represents the number of fluorine atoms in each molecule of the monomer, M _F represents the atomic weight of fluorine atoms, Q _Si represents the number of silicon atoms in each molecule of the monomer, and M _Si represents the atomic weight of silicon atoms. The actinic radiation- or radiation-sensitive resin composition according to item 19 of the scope of the patent application, wherein at least one of the specific resins mentioned above is derived from satisfying the formulas (4) and (6), or (5) and Repeating unit of monomer of formula (6), Q _F × M _F /Mw≥0.35 (4) Q _Si × M _Si /Mw≥0.15 (5) P / Mw≥0.02 (6) Formulas (4) to (6) ), P represents the ClogP value of the monomer, Mw represents the molecular weight of the monomer, Q _F represents the number of fluorine atoms in each molecule of the monomer, and Q _Si represents the silicon in each molecule of the monomer The number of atoms, M _F represents the atomic weight of the fluorine atom, and M _Si represents the atomic weight of the silicon atom. The photosensitized radioactive or radiation-sensitive resin composition according to any one of claims 18 to 20 in the scope of the patent application, wherein R ₁ in the repeating unit represented by the above formula (X1) and the above formula ( X2) of the group represented by R ₂ is substituted with three or more of fluorine atoms. The photosensitive radiation- or radiation-sensitive resin composition according to any one of claims 18 to 20 in the scope of the patent application, wherein R in the repeating unit represented by the above formula (Y2), and by the above formula (Y1 R in the group represented by) and the group represented by the above formula (Y3) is a hydrogen atom. The photosensitive radiation- or radiation-sensitive resin composition according to any one of claims 18 to 20 in the scope of the patent application, wherein R in the repeating unit represented by the above formula (Y2), and by the above formula (Y1 R in the group represented by) and the group represented by the above formula (Y3) is an alkyl group, an aryl group, or an alkylamino group containing a substituent. The photosensitive radiation- or radiation-sensitive resin composition according to item 23 of the scope of the patent application, wherein R in the repeating unit represented by the above formula (Y2), the group represented by the above formula (Y1), and the above R in the group represented by formula (Y3) is an alkyl group or an aryl group which is removed under basic conditions. The photosensitive radiation- or radiation-sensitive resin composition according to any one of claims 18 to 20 in the scope of the patent application, wherein the resin C and the resin C2 contain a repeating unit, and the repeating unit contains two or more At least one group selected from the group consisting of a group represented by formula (Y1) and a group represented by formula (Y3). The photosensitive radiation- or radiation-sensitive resin composition according to any one of claims 18 to 20 in the scope of the patent application, wherein the resin C, the resin C1, and the resin C2 are selected from (meth) acrylic acid At least one polymer in the group consisting of an ester derivative, a styrene derivative, and an allyl-containing compound. The actinic radiation- or radiation-sensitive resin composition according to any one of claims 18 to 20 of the scope of patent application, which is selected from the group consisting of the above resin C1, the above resin C2, and the above resin C At least one resin contains an aromatic ring. The photosensitized radioactive or radiation-sensitive resin composition according to any one of claims 18 to 20 in the scope of the patent application, wherein the resin C1 and the resin C contain a repeating unit represented by formula (7), In the formula, R represents at least one selected from the group consisting of a trialkylsilyl group, a fluorinated alkyl group having a carbon number of 2 or more, and a tertiary alkyl group, R _A represents a hydrogen atom or a monovalent substituent, and n Represents an integer of 2 or more. The actinic radiation- or radiation-sensitive resin composition according to any one of claims 18 to 20 in the scope of the patent application, comprising: the above-mentioned resin C, and selected from the group consisting of the above-mentioned resin C1 and the above-mentioned resin C2 At least one of them. The actinic radiation- or radiation-sensitive resin composition according to any one of claims 18 to 20, wherein the resin A contains a repeating unit, and the repeating unit contains a lactone structure. The photosensitive radiation- or radiation-sensitive resin composition according to any one of claims 18 to 20 of the scope of patent application, further comprising a solvent D. A resist film is formed by using the photosensitive radiation- or radiation-sensitive resin composition described in any one of claims 18 to 31 in the scope of patent application.