TW202107201A - Actinic-ray-sensitive or radiation-sensitive resin composition, method for forming pattern, and method for producing electronic device - Google Patents

Abstract

Provided is an actinic-ray-sensitive or radiation-sensitive resin composition which, when used in pattern formation with EUV light, gives patterns having few defects and which, even after long-term storage, gives patterns having excellent LWR performance. Also provided are a method for forming a pattern and a method for producing an electronic device which relate to the actinic-ray-sensitive or radiation-sensitive resin composition. The actinic-ray-sensitive or radiation-sensitive resin composition comprises an acid-decomposable resin and a compound that generates an acid upon irradiation with actinic rays or radiation, wherein the acid-decomposable resin includes repeating unit a1, which is represented by general formula (A1). In general formula (A1), RQ represents a hydrogen atom or an organic group.

Description

Sensitizing radiation-sensitive or radiation-sensitive resin composition, pattern forming method, and manufacturing method of electronic component

The present invention relates to a photosensitive radiation-sensitive or radiation-sensitive resin composition, a pattern forming method, and a manufacturing method of electronic components.

In the manufacturing process of semiconductor components such as Integrated Circuit (IC) and Large Scale Integrated Circuit (LSI), microfabrication is performed by using photolithography of photosensitive composition. As a method of lithography, a method of forming a resist film from a photosensitive composition, exposing the resulting film, and then developing it can be cited. In particular, in recent years, research has been conducted to use extreme ultraviolet (EUV) light for exposure (Patent Document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-85382

[The problem to be solved by the invention] In recent years, it has been required to further reduce defects in patterns formed using EUV light. In addition, it is required that the line width roughness (LWR) performance of the resulting pattern is good even when it is applied to pattern formation after long-term (for example, 180 days) storage after manufacturing.

Therefore, the subject of the present invention is to provide a sensitized radiation-sensitive or radiation-sensitive resin composition, which can suppress the occurrence of defects in patterns formed by EUV light, and can obtain excellent LWR performance even in the case of long-term storage. picture of. In addition, the subject of the present invention is to provide a method for forming a pattern of the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition and a method for manufacturing an electronic component. [Means to solve the problem]

The inventors of the present invention found that the problem can be solved by the following configuration.

通式（A1）中，R^Q 表示氫原子或有機基。 [2] 如[1]所述的感光化射線性或感放射線性樹脂組成物，其中所述重複單元a1包含具有酸分解性基的重複單元a2。 [3] 如[2]所述的感光化射線性或感放射線性樹脂組成物，其中所述重複單元a2包含通式（A2）所表示的重複單元a3； [化2]

通式（A2）中，R^Q1 ～R^Q3 分別獨立地表示烷基； R^Q1 ～R^Q3 中的兩個可彼此鍵結而形成環。 [4] 如[1]～[3]中任一項所述的感光化射線性或感放射線性樹脂組成物，其中所述重複單元a1包含R^Q 表示氫原子或基X的重複單元a4， 所述基X是具有選自由內酯基、磺內酯基、碳酸酯基、羥基、磺醯胺基、醯胺基、羧酸基及光酸產生基所組成的群組中的一個以上的特定基的基且並非為脫離基。 [5] 如[4]所述的感光化射線性或感放射線性樹脂組成物，其中所述重複單元a4包含重複單元a5，所述重複單元a5含有進而具有氟原子的所述基X。 [6] 如[5]所述的感光化射線性或感放射線性樹脂組成物，其中所述重複單元a5包含重複單元a6，所述重複單元a6含有具有六氟丙醇基的所述基X。 [7] 如[1]～[6]中任一項所述的感光化射線性或感放射線性樹脂組成物，其中所述酸分解性樹脂具有通式（B1）所表示的重複單元b5； [化3]

通式（B1）中，X表示氫原子、烷基或氟原子以外的鹵素原子； L^B 表示單鍵或-COO-； R^B1 表示基Z，所述基Z是具有選自由內酯基、磺內酯基、碳酸酯基、羥基、磺醯胺基、醯胺基、羧酸基及光酸產生基所組成的群組中的一個以上的特定基、且具有氟原子且並非為脫離基。 [8] 如[7]所述的感光化射線性或感放射線性樹脂組成物，其中所述重複單元b5包含重複單元b6，所述重複單元b6含有具有六氟丙醇基的所述基Z。 [9] 如[1]～[8]中任一項所述的感光化射線性或感放射線性樹脂組成物，其中所述藉由光化射線或放射線的照射而產生酸的化合物包含通式（PA-1）所表示的化合物； [化4]

通式（PA-1）中，A¹ 及A² 分別獨立地表示-SO₂ -R^P 或-CO-R^P ；R^P 表示有機基； M⁺ 表示陽離子。 [10] 如[1]～[9]中任一項所述的感光化射線性或感放射線性樹脂組成物，其中所述藉由光化射線或放射線的照射而產生酸的化合物包含通式（PB）所表示的化合物； M₁ ⁺ A^- -L-B^- M₂ ⁺ （PB） 通式（PB）中，M₁ ⁺ 及M₂ ⁺ 分別獨立地表示有機陽離子； L表示二價有機基； A^- 表示酸根陰離子基； 其中，在通式（PB）所表示的化合物的M₁ ⁺ 及M₂ ⁺ 分別經氫原子取代的HA-L-BH所表示的化合物中，HA所表示的基的pKa比BH所表示的基的pKa低； B^- 表示通式（B-1）～（B-4）中的任一者所表示的基； [化5]

所述通式（B-1）～（B-4）中，*表示鍵結位置； 所述通式（B-1）～（B-4）中，R^B 表示有機基。 [11] 如[1]～[10]中任一項所述的感光化射線性或感放射線性樹脂組成物，其中相對於總固體成分，所述藉由光化射線或放射線的照射而產生酸的化合物的含量為15質量%以上。 [12] 一種圖案形成方法，包括： 使用如[1]～[11]中任一項所述的感光化射線性或感放射線性樹脂組成物於基板上形成抗蝕劑膜的步驟； 對所述抗蝕劑膜進行曝光的步驟；以及 使用顯影液對所述經曝光的抗蝕劑膜進行顯影而形成圖案的步驟。 [13] 一種電子元件的製造方法，包括如[12]所述的圖案形成方法。 [發明的效果][1] A photosensitive ray-sensitive or radiation-sensitive resin composition comprising: an acid-decomposable resin and a compound that generates acid by irradiation with actinic rays or radiation, the acid-decomposable resin having the general formula (A1 ) The repeating unit a1; [化1]

In the general formula (A1), R ^Q represents a hydrogen atom or an organic group. [2] The actinic radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit a1 includes a repeating unit a2 having an acid-decomposable group. [3] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to [2], wherein the repeating unit a2 includes the repeating unit a3 represented by the general formula (A2); [化2]

In the general formula (A2), R ^Q1 to R ^Q3 each independently represent an alkyl group; two of R ^Q1 to R ^Q3 may be bonded to each other to form a ring. [4] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the repeating unit a1 includes ^{a repeating unit a4 in which R Q} represents a hydrogen atom or a group X, The group X has one or more selected from the group consisting of a lactone group, a sultone group, a carbonate group, a hydroxyl group, a sulfonamide group, an amide group, a carboxylic acid group, and a photoacid generating group The base of the specific base is not a detached base. [5] The actinic radiation-sensitive or radiation-sensitive resin composition according to [4], wherein the repeating unit a4 includes a repeating unit a5, and the repeating unit a5 includes the group X further having a fluorine atom. [6] The actinic radiation-sensitive or radiation-sensitive resin composition according to [5], wherein the repeating unit a5 includes a repeating unit a6, and the repeating unit a6 includes the group X having a hexafluoropropanol group. . [7] The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the acid-decomposable resin has a repeating unit b5 represented by the general formula (B1); [化3]

In the general formula (B1), X represents a halogen atom other than a hydrogen atom, an alkyl group or a fluorine atom; L ^B represents a single bond or -COO-; R ^B1 represents a group Z, the group Z is a radical selected from the group consisting of a lactone, One or more specific groups in the group consisting of a sultone group, a carbonate group, a hydroxyl group, a sulfonamide group, a amide group, a carboxylic acid group, and a photoacid generating group, and has a fluorine atom and is not a leaving group . [8] The actinic radiation-sensitive or radiation-sensitive resin composition according to [7], wherein the repeating unit b5 includes a repeating unit b6, and the repeating unit b6 includes the group Z having a hexafluoropropanol group. . [9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the compound that generates an acid by irradiation with actinic rays or radiation includes the general formula The compound represented by (PA-1); [化4]

Formula (PA-1) in, A ¹ and A ² each independently represent -SO ₂ -R ^P or -CO-R ^P; R ^P represents an organic group; M ⁺ represents a cation. [10] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the compound that generates an acid by irradiation with actinic rays or radiation includes the general formula (PB) compound represented; M ₁ ⁺ A ^-- LB ^- M ₂ ⁺ (PB) In the general formula (PB), M ₁ ⁺ and M ₂ ⁺ each independently represent an organic cation; L represents a divalent organic group; A ^- represents an acid radical anion group; wherein, in the compound represented _{by HA-L-BH in which M 1} ⁺ and M ₂ ⁺ of the compound represented by the general formula (PB) are replaced with hydrogen atoms, the group represented by HA is pKa is lower than the pKa of the group represented by BH; B ^- represents a group represented by any one of the general formulas (B-1) to (B-4); [化5]

In the general formula (B-1) ~ (B -4), * represents a bonding position; in the general formula (B-1) ~ (B -4), R B represents an organic group. [11] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10], wherein the resin composition is generated by irradiation of actinic rays or radiation with respect to the total solid content The content of the acid compound is 15% by mass or more. [12] A pattern forming method, comprising: forming a resist film on a substrate using the sensitized radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [11]; The step of exposing the resist film; and the step of developing the exposed resist film with a developing solution to form a pattern. [13] A method of manufacturing an electronic component, including the pattern forming method as described in [12]. [Effects of the invention]

According to the present invention, a photosensitive radiation-sensitive or radiation-sensitive resin composition can be provided, which can suppress the occurrence of defects in patterns formed by EUV light, and can obtain patterns with excellent LWR performance even under long-term storage. . In addition, according to the present invention, it is possible to provide a method for forming a pattern of the photosensitive ray-sensitive or radiation-sensitive resin composition and a method for manufacturing an electronic component.

Hereinafter, an example of a form for implementing the present invention will be described. In addition, in this specification, the numerical range shown using "-" means the meaning of the range including the numerical value described before and after "-" as the lower limit and the upper limit. In the expression of the group (atomic group) in this specification, the expression that does not describe substituted or unsubstituted also includes a group having no substituent and a group having a substituent. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). Unless otherwise specified, the substituent is preferably a monovalent substituent. The "organic group" in this specification refers to a group containing at least one carbon atom.

In this specification, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

The bonding direction of the divalent group described in this specification is not limited unless otherwise specified. For example, when Y in the compound represented by the general formula formed by "X-Y-Z" is -COO-, Y may be -CO-O- or -O-CO-. In addition, the compound may be "X-CO-O-Z" or "X-O-CO-Z".

The "(meth)acryl group" in this specification is a general term including an acrylic group and a methacryl group, and means "at least one of an acrylic group and a methacryl group". Similarly, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid".

The "actinic rays" or "radiation rays" in this manual refer to, for example, the bright-ray spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams. (EB: Electron Beam) and so on. The "light" in this specification refers to actinic rays or radiation. The "exposure" in this manual, unless otherwise specified, not only refers to exposure using the bright-line spectrum of a mercury lamp, extreme ultraviolet, extreme ultraviolet, X-ray and EUV light represented by excimer lasers, etc. Includes drawing using particle beams such as electron beams and ion beams.

In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion (also called molecular weight distribution) (Mw/Mn) of the resin are defined as by using gel permeation chromatography (Gel Permeation Chromatography, GPC) ) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL- manufactured by Tosoh) by the device (HLC-8120GPC manufactured by Tosoh) M. Column temperature: 40°C, flow rate: 1.0 mL/min, detector: Refractive Index Detector (Refractive Index Detector) obtained by polystyrene conversion value.

1 Å is 1×10 ^-10 m.

In this specification, the so-called acid dissociation constant (pKa) means the pKa in an aqueous solution. Specifically, the following software package 1 is used to obtain data based on Hammett's substituent constant and publicly known literature values. Value derived from the value of the library. The values of pKa described in this specification all indicate values obtained by calculation using the software package.

Software package 1: Advanced Chemistry Development (ACD/Labs) software V8.14 for Solaris (1994-2007 ACD/Labs) for Solaris.

On the other hand, pKa is also obtained by the molecular orbital calculation method. As this specific method, a method of calculating and calculating the H ⁺ dissociation free energy in the solvent based on the thermodynamic cycle can be cited. (Furthermore, in this specification, water is usually used as the solvent, and dimethylsulfoxide (DMSO) is used when the pKa cannot be obtained in water.) Regarding ^{the calculation method of H +} dissociation free energy, For example, the calculation can be performed by density functional theory (Density Functional Theory, DFT). In addition to this, various other methods have been reported in the literature, and they are not limited to this. Furthermore, there are many software that can implement DFT, for example, Gaussian 16 can be cited.

The so-called pKa in this specification refers to the value obtained by calculating the value of the database based on Hammett’s substituent constants and well-known literature values by using software package 1, as described above. Therefore, it cannot be calculated by this method. In the case of pKa, the value obtained by Gaussian 16 based on DFT (Density Functional Method) is used.

[Sensitizing radiation-sensitive or radiation-sensitive resin composition] The actinic radiation-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as "resist composition") of the present invention will be described. The resist composition of the present invention may be a positive type resist composition or a negative type resist composition. In addition, it may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention is typically a chemically amplified resist composition.

The resist composition of the present invention includes an acid-decomposable resin and a compound that generates an acid by irradiation with actinic rays or radiation, the acid-decomposable resin having a repeating unit a1, and the repeating unit a1 is described later The repeating unit represented by the general formula (A1). Although the mechanism for solving the problem of the present invention by using the above configuration is not necessarily clear, the inventors of the present invention consider as follows. EUV light has a wavelength of 13.5 nm, which is shorter than that of ArF (wavelength 193 nm) light, etc., so the number of incident photons when exposed with the same sensitivity is small. Therefore, the "photon shot noise" in which the number of photons is randomly dispersed has a large influence, resulting in an increase in defects in the resulting pattern and deterioration in LWR performance. Therefore, in the present invention, the acid-decomposable resin contained in the resist composition includes a repeating unit a1 which is an acrylic repeating unit (α-fluoroacrylic repeating unit) having a fluorine atom at the α position . It is believed that the presence of fluorine atoms in the α position of the repeating unit can improve the absorption efficiency of EUV light, and adjust the compatibility of the resin with the developer to an appropriate range, thereby suppressing the occurrence of defects in the formed pattern And the deterioration of LWR performance. In addition, it is considered that the fluorine atom in the α position has a small adverse effect on the stability of the acid-decomposable resin, and even when the resist composition is stored for a long period of time, the deterioration of the LWR performance of the formed pattern can be suppressed. Hereinafter, in this specification, the characteristic of the resist composition that can suppress the occurrence of defects in the formed pattern is also referred to as being excellent in defect-suppressive properties of the resist composition. In addition, the excellent LWR performance of the pattern formed after long-term storage of the resist composition is also referred to as the excellent LWR performance of the resist composition over time. It is also referred to as being excellent in at least one of the defect suppression properties of the resist composition and the LWR performance over time as the effect of the present invention.

[Components of resist composition] Hereinafter, the components that can be contained in the resist composition are described in detail.

＜(A) Acid decomposable resin＞ The resist composition contains an acid-decomposable resin (hereinafter also referred to as "resin (A)"). The resin (A) is typically a resin whose polarity increases due to the action of an acid, its solubility with respect to an alkaline developer increases, and its solubility with respect to an organic solvent decreases. The resin (A) has a group that is decomposed by the action of an acid to generate a polar group (in other words, the polar group is protected by a leaving group that is detached by the action of an acid). The group (structure) is also referred to as an acid-decomposable group. A resin having an acid-decomposable group (that is, a resin containing a repeating unit having an acid-decomposable group) increases in polarity due to the action of an acid, and has an increase in solubility with respect to an alkaline developer, and a decrease in solubility with respect to an organic solvent. In addition, as described later, the resin (A) may contain a repeating unit having a photoacid generating group. Among them, the resin (A) preferably has an acid group with an acid dissociation constant (pKa) of 13 or less. As described above, the acid dissociation constant of the acid group is preferably 13 or less, more preferably 3-13, and still more preferably 5-10. In the case of an acid group having the predetermined pKa, the resist composition has excellent storage stability, and development proceeds more satisfactorily. Examples of acid groups having an acid dissociation constant (pKa) of 13 or less include carboxylic acid groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, or sulfonamide groups Wait.

(Repeat unit a1) The resin (A) has a repeating unit a1. The repeating unit a1 is a repeating unit represented by the general formula (A1).

[化6]

In the general formula (A1), R ^Q represents a hydrogen atom or an organic group. The organic group represented by R ^{Q is} not limited, and, for example, it may be a group that forms an acid-decomposable group as a whole ^{-COO-R Q (in this case, R Q} is a leaving group), or may not be the group. A part or the whole of R ^Q may be a group that is an acid-decomposable group, or it may not be the group. R ^Q may be a polar group or a non-polar group. R ^Q can be selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group (which may be a non-aromatic hydroxyl group or an aromatic hydroxyl group), a sulfonamide group, an amide group, and a carboxylic acid group. The group of one or more specific groups in the group consisting of a photoacid generating group may not be the group. R ^Q may have a fluorine atom or may not have a fluorine atom.

In the resin (A), the content of the repeating unit represented by the general formula (A1) is preferably from 5 mol% to 100 mol%, and more preferably from 10 mol% to all the repeating units of the resin (A). 100 mol%, more preferably 20 mol% to 100 mol%. Two or more types of repeating units represented by general formula (A1) may also be used.

·Repeat unit a2 It is also preferable that the repeating unit a1 contains a repeating unit a2 having an acid-decomposable group. That is, the resin (A) also preferably has a repeating unit a2. In more detail, the repeating unit a2 is a repeating unit represented by the general formula (A1), and is a repeating unit having an acid-decomposable group (a repeating unit having a structure in which a polar group is separated by a leaving group separated by an acid unit). In other words, the repeating unit a2 is a form of the repeating unit a1.

The polar group in the repeating unit having a structure (acid-decomposable group) protected by a leaving group detached by the action of an acid is preferably an alkali-soluble group, for example, carboxylic acid group, phenolic hydroxyl group, fluorine Alcohol group, sulfonic acid group, sulfonamido group, sulfonamido group, (alkylsulfonyl) (alkylcarbonyl)methylene, (alkylsulfonyl) (alkylcarbonyl)imide Group, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imino, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imino, tri( Acidic groups such as alkylcarbonyl)methylene and tris(alkylsulfonyl)methylene, and alcoholic hydroxyl groups. Among them, the polar group is preferably a carboxylic acid group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group. In the case where the polar group is a carboxylic acid group, R ^Q in the general formula (A1) may be a radical body. That is, in this case, a polar group (carboxylic acid group) is formed with a structure (acid decomposable group) protected ^{by a leaving group (R Q ), and -COO-R Q} in the general formula (A1) as a whole constitutes an acid Decomposable base. ^{In addition, a part of R Q} in the general formula (A1) may contain an acid-decomposable group, and R ^Q as a whole may constitute an acid-decomposable group.

Examples of the leaving group to be released by the action of the acid include groups represented by formulas (Y1) to (Y4). Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y3): -C (R ₃₆ )(R ₃₇ )(OR ₃₈ ) Formula (Y4): -C(Rn)(H)(Ar)

In formula (Y1) and formula (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched), cycloalkyl (monocyclic or polycyclic), and alkenyl (linear or Branched), or aryl (monocyclic or polycyclic). Furthermore, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of _{Rx 1} to Rx _{3 are methyl groups.} Among them, Rx ₁ to Rx ₃ preferably each independently represent a linear or branched alkyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic ring or a polycyclic ring. The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl. The substituent that the alkyl group may have is preferably a hydroxyl group or a halogen atom. The alkyl group is preferably an unsubstituted alkyl group or an alkyl group having only a substituent selected from the group consisting of a hydroxyl group and a halogen atom. The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic group such as norbornyl, tetracyclodecyl, tetracyclododecyl, or adamantyl. Cycloalkyl. The aryl group of Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbons, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Rx ₁ to Rx ₃ is preferably a vinyl group. The ring formed by two bonding of Rx ₁ to Rx _{3 is preferably a cycloalkyl group.} The cycloalkyl formed by the two bonding of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl such as cyclopentyl or cyclohexyl, or norbornyl, tetracyclodecyl, tetracyclododecyl or Polycyclic cycloalkyl such as adamantyl. In _{the cycloalkyl group formed by two bonding of Rx 1} to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom, a group having a hetero atom such as a carbonyl group, or a vinylene group. In addition, one or more of the ethylene groups constituting the cycloalkane ring in these cycloalkyl groups may be substituted with ethylene groups. The substituent that the ring formed by the two bonding of Rx ₁ to Rx ₃ may have is preferably a perhalogenated alkyl group (which may be linear or branched. Preferably, it is a perfluoroalkyl group, more preferably Carbon number 1-3), hydroxyl or halogen atom. The ring is preferably an unsubstituted ring or a ring having only a substituent selected from the group consisting of a perhalogenated alkyl group, a hydroxyl group, and a halogen atom as a substituent. The group represented by the formula (Y1) or the formula (Y2) is preferably a form in which, for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the cycloalkyl group.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be bonded to each other to form a ring. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. R _{36 is} also preferably a hydrogen atom. In addition, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain heteroatoms such as oxygen atoms and/or groups having heteroatoms such as carbonyl groups. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more of, for example, a methylene group may be substituted with a heteroatom such as an oxygen atom and/or a heteroatom such as a carbonyl group.

Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[化7]

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these (for example, a group formed by combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination of these (For example, a group formed by combining an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one methylene group may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. The alkyl group is also preferably, for example, one or more hydrogen atoms are substituted with a fluorine atom to become a fluoroalkyl group (for example, a fluoroalkyl group having 1 to 5 carbon atoms). Furthermore, it is preferable that one of L ₁ and L ₂ is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. At least two of Q, M and L ₁ may be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring). In terms of the refinement of the pattern, L _{2 is} preferably a secondary alkyl group or a tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl, cyclohexyl, and norbornyl, and examples of the tertiary alkyl group include tertiary butyl and adamantyl. In these forms, since Tg (glass transition temperature) and activation energy become high, in addition to ensuring film strength, fog can also be suppressed.

In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may bond with each other to form a non-aromatic ring. Ar is preferably an aryl group.

In terms of the excellent acid decomposability of the repeating unit, in the leaving group for protecting the polar group, when the non-aromatic ring is directly bonded to the polar group (or a residue thereof), the non-aromatic ring It is also preferable that the ring member atoms adjacent to the ring member atoms directly bonded to the polar group (or a residue thereof) do not have a halogen atom such as a fluorine atom as a substituent.

The leaving group that is released by the action of the acid may also be 2-cyclopentenyl with substituents (alkyl etc.) such as 3-methyl-2-cyclopentenyl, and 1,1, Cyclohexyl having substituents (alkyl etc.) such as 4,4-tetramethylcyclohexyl.

··Repeat unit a3 It is also preferable that the repeating unit a2 includes the repeating unit a3 represented by the general formula (A2). That is, the resin (A) also preferably has a repeating unit a3. In other words, the repeating unit a3 is a repeating unit represented by the general formula (A2), and is a form of the repeating unit a2.

[化8]

In the general formula (A2), R ^Q1 to R ^Q3 each independently represent an alkyl group (linear or branched). The alkyl groups of R ^Q1 to R ^Q3 are preferably each independently an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary butyl. . The substituent that the alkyl group may have is preferably a hydroxyl group or a halogen atom. The alkyl group is preferably an unsubstituted alkyl group or an alkyl group having only a substituent selected from the group consisting of a hydroxyl group and a halogen atom.

Two of R ^Q1 to R ^Q3 may be bonded to each other to form a ring. The ring formed by bonding two of R ^Q1 to R ^{Q3 is preferably a cycloalkyl group.} The cycloalkyl formed by the two bonding of R ^Q1 to R ^Q3 is preferably a monocyclic cycloalkyl such as cyclopentyl or cyclohexyl, or norbornyl, tetracyclodecyl, or tetracyclododecyl Or polycyclic cycloalkyl such as adamantyl. In ^{the cycloalkyl group formed by bonding two of R Q1} to R ^Q3 , one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom, a group having a hetero atom such as a carbonyl group, or a vinylene group. In addition, one or more of the ethylene groups constituting the cycloalkane ring in these cycloalkyl groups may be substituted with ethylene groups. The substituent that the ring formed by the two bonding of R ^Q1 to R ^Q3 may have is preferably a perhalogenated alkyl group (which may be linear or branched. It is preferably a perfluoroalkyl group, more preferably It is carbon number 1 to 3), hydroxyl or halogen atom. The ring is preferably an unsubstituted ring or a ring having only a substituent selected from the group consisting of a perhalogenated alkyl group, a hydroxyl group, and a halogen atom as a substituent.

In the case where the resin (A) has the repeating unit a2 (preferably the repeating unit a3), the content of the repeating unit is preferably 5 mol% to 90 mol% relative to all the repeating units of the resin (A), It is more preferably 10 mol% to 85 mol%, and still more preferably 20 mol% to 70 mol%. The repeating unit a2 (preferably the repeating unit a3) may be used singly, or two or more may be used.

-Repeating unit a4 (repeating unit a5, repeating unit a6) It is also preferable that the repeating unit a1 includes the repeating unit a4. That is, the resin (A) also preferably has a repeating unit a4. The repeating unit a4 is a repeating unit represented by the general formula (A1) (repeating unit A1) where R ^Q represents a hydrogen atom or a repeating unit of the group X. The group X is selected from the group consisting of lactone, sultone, carbonate, hydroxy (non-aromatic hydroxy or aromatic), sulfonamide, amide, carboxylic acid and The group of one or more specific groups in the group consisting of the photoacid generating group is not a group leaving the group. The repeating unit a4 is a form of the repeating unit a1.

In the repeating unit a4, ^{the group X as an option for R Q} is a group having a specific group and is not a group leaving a group. The term "a group that is not a leaving group" refers to a group of "a leaving group that is detached by the action of an acid" which is not described for the repeating unit a2. Specifically, "the group that is not a leaving group" does not correspond to the group represented by the above-mentioned formulas (Y1) to (Y4). The repeating unit a4 is preferably different from the repeating unit a2 and/or the repeating unit a3.

When R ^Q is the base X, R ^Q may be a specific base itself, and ^{a part of R Q} may also include a specific base.

In the case where the resin (A) has the repeating unit a4, relative to all the repeating units of the resin (A), the content of the repeating unit is preferably 1 mol% to 70 mol%, more preferably 2 mol% to 60 mol%, more preferably 3 mol% to 50 mol%. One type of repeating unit a4 may be used alone, or two or more types may be used.

It is also preferable that the repeating unit a4 includes a repeating unit a5, and the repeating unit a5 contains a group X further having a fluorine atom. That is, the resin (A) also preferably has a repeating unit a5. In more detail, the repeating unit a5 is a repeating unit of the following form: in the repeating unit represented by the general formula (A1), R ^Q is the group X and the group X is a group having a fluorine atom. That is, the repeating unit a5 is one aspect of the repeating unit a4.

Among them, the repeating unit a5 also preferably includes the repeating unit a6, and the repeating unit a6 includes a group X having a hexafluoropropanol group (a group represented by _{"-C(CF 3} ) _{2 OH").} That is, it is also preferable that the resin (A) has a repeating unit a6. In more detail, the repeating unit 6 is a repeating unit of the following form: in the repeating unit represented by the general formula (A1), R ^Q is the group X and the group X is a group having a hexafluoroisopropanol group. That is, the repeating unit a6 may be one form of the repeating unit a4 and the repeating unit a5.

^{·· Repeating unit a4-0 When R Q} of the repeating unit represented by the general formula (A1) is a hydrogen atom, the repeating unit is also referred to as repeating unit a4-0. When the resin (A) has the repeating unit a4-0, the content of the repeating unit is preferably 1 mol% to 30 mol%, more preferably 2 mol%, relative to all the repeating units of the resin (A) %-20 mol%, more preferably 3 mol%-15 mol%.

·· Repeating unit a4-1 In the repeating unit a4, when R ^Q is a group X having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group as a specific group, The repeating unit a4 is also referred to as repeating unit a4-1.

The lactone group, the sultone group, and the carbonate group also preferably have a fluorine atom as a substituent. That is, the repeating unit a4-1 is also preferably the repeating unit a5.

The lactone group or sultone group of the repeating unit a4-1 should just have a lactone structure or a sultone structure. The lactone structure or the sultone structure is preferably a 5-membered cyclic lactone structure to a 7-membered cyclic lactone structure or a 5-membered cyclic sultone structure to a 7-membered cyclic sultone structure. Among them, the lactone structure is preferably a structure in which other ring structures are condensed in a 5-membered ring lactone structure to a 7-membered ring lactone structure in a form of forming a bicyclic structure or a spiro structure. The sultone structure is more preferably a structure formed by condensing a ring with another ring structure in a 5-membered ring sultone structure to a 7-membered ring sultone structure in a form of forming a bicyclic structure or a spiro structure. The lactone group is preferably a lactone group obtained by removing one or more hydrogen atoms from the ring member atoms of the lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-22) . The sultone group is preferably a sulfonic acid obtained by removing one or more hydrogen atoms from the ring member atoms of the sultone structure represented by any one of the following general formulas (SL1-1) to (SL1-3) Lactone group.

[化9]

[化10]

The lactone structure or the sultone structure part may also have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include, for example, alkyl groups having 1 to 8 carbons, cycloalkyl groups having 4 to 7 carbons, alkoxy groups having 1 to 8 carbons, and those having 1 to 8 carbons. An alkoxycarbonyl group, a carboxylic acid group, a halogen atom (preferably a fluorine atom), a hydroxyl group, a cyano group, and the like. n2 represents an integer of 0-4. When n2 is 2 or more, multiple existing Rb ₂ may be different, and multiple existing Rb ₂ may be bonded to each other to form a ring.

The repeating unit a4-1 having a lactone group obtained by removing one or more hydrogen atoms from the ring member atoms of the lactone structure represented by any one of the general formulas (LC1-1) to (LC1-22), And a repeating unit a4 having a sultone group formed by removing one or more hydrogen atoms from the ring member atoms of the sultone structure represented by any of the general formulas (SL1-1) to (SL1-3) -1 is preferably a repeating unit represented by general formula (A3).

[化11]

In the general formula (A3), Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxylic acid group, or a combination of these From the divalent base. Among them, a single bond or a linking group represented by _{-Ab 1 -COO- is preferred.} Ab ₁ is a single bond or a divalent linking group, and is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably methylene, ethylene, or ring extension Hexyl, adamantyl or norbornyl. V represents a group obtained by removing one hydrogen atom from the ring member atoms of the lactone structure represented by any of the general formulas (LC1-1) to (LC1-22), or from the general formula (SL1-1) A group obtained by removing one hydrogen atom from the ring member atoms of the sultone structure represented by any one of ~(SL1-3).

When an optical isomer is present in the repeating unit a4-1 having a lactone group or a sultone group, any optical isomer can be used. In addition, one kind of optical isomer may be used alone, or a plurality of optical isomers may be used in combination. In the case of mainly using one optical isomer, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

The carbonate group in the repeating unit a4-1 having a carbonate group is preferably contained in a cyclic carbonate group. The repeating unit a4-1 having a carbonate group is preferably a repeating unit represented by general formula (A4).

[化12]

In the general formula (A4), n represents an integer of 0 or more (preferably 0 to 3). R _A ² represents a substituent. When n is 2 or more, a plurality of R _A ² may be the same or different. A represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group (preferably with a carbon number of 1 to 4), a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, ether group, ester group, carbonyl group, carboxylic acid Group, or a divalent group formed by combining these groups. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula. The monocyclic or polycyclic ring formed by Z and the group represented by -O-CO-O- in the formula is preferably a 5-membered cyclic carbonate group, and more preferably is represented by the following general formula (CC1-1) Represents the cyclic carbonate structure. That is, A in the general formula (A4) is preferably bonded to a group obtained by removing one hydrogen atom from the ring member atoms of the cyclic carbonate structure represented by the following general formula (CC1-1).

[化13]

The cyclic carbonate structure part in general formula (CC1-1) may have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include, for example, alkyl groups having 1 to 8 carbons, cycloalkyl groups having 4 to 7 carbons, alkoxy groups having 1 to 8 carbons, and those having 1 to 8 carbons. An alkoxycarbonyl group, a carboxylic acid group, a halogen atom (preferably a fluorine atom), a hydroxyl group, a cyano group, and the like. n3 represents an integer of 0 or 1.

When resin (A) has repeating unit a4-1, relative to all repeating units of resin (A), the content of the repeating unit is preferably 3 mol% to 60 mol%, more preferably 5 mol% %～50 mol%, more preferably 7 mol%～45 mol%. One type of repeating unit a4-1 may be used alone, or two or more types may be used.

·· Repeating unit a4-2 In repeating unit a4, R ^Q is a group X having a non-aromatic hydroxyl group as a specific group, and the non-aromatic hydroxyl group is a hydroxyl group other than the hydroxyl group contained in the fluorinated alcohol group In the case of, the repeating unit a4 is also referred to as repeating unit a4-2. The non-aromatic hydroxyl group refers to a hydroxyl group other than an aromatic hydroxyl group, and for example, refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring. Examples of non-aromatic hydroxyl groups include alcoholic hydroxyl groups. The hydroxy group other than the hydroxy group contained in the fluorinated alcohol group means, for example, that a hydroxy group is bonded to a carbon atom and a fluorine atom and -CFR ₂ (two Each R independently represents a hydrogen atom or a substituent. Examples of _{-CFR 2} include the above-mentioned hydroxyl group in any one of _{-CF 3 and the like).} The repeating unit a4-2 is preferably different from the repeating unit a4-1. The repeating unit a4-2 preferably does not have a fluorinated alcohol group.

The repeating unit a4-2 is preferably a repeating unit represented by the general formula (A5).

[化14]

In the general formula (A5), R ^Q5 represents an alkyl group (linear or branched. Preferably, it has 1 to 5 carbon atoms) or a non-aromatic cyclic group.

Examples of the non-aromatic cyclic group include a monocyclic hydrocarbon ring group and a polycyclic hydrocarbon ring group. Examples of monocyclic hydrocarbon ring groups include cycloalkane ring groups having 3 to 12 carbon atoms (preferably 3 to 7 carbon atoms) and cycloolefin ring groups having 3 to 12 carbon atoms. As the polycyclic hydrocarbon ring group, for example, a ring assembly hydrocarbon ring group and a crosslinked cyclic hydrocarbon ring group can be cited. As a crosslinked cyclic hydrocarbon ring, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring, etc. are mentioned, for example. In addition, the crosslinked cyclic hydrocarbon ring may be a condensed ring formed by condensing a plurality of 5-membered cycloalkane rings to 8-membered cycloalkane rings. The crosslinked cyclic hydrocarbon ring group is preferably a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, or a tricyclic [5,2,1,0 ^2,6 ]decane ring group.

It is also preferable that the alkyl group and the non-aromatic cyclic group have no substituents other than _-(OH)q5.

In general formula (A5), q5 represents an integer of 1-5.

In the case where the resin (A) has the repeating unit a4-2, relative to all the repeating units of the resin (A), the content of the repeating unit is preferably 3 mol% to 60 mol%, more preferably 5 mol% %～50 mol%, more preferably 10 mol%～45 mol%. One type of repeating unit a4-2 may be used alone, or two or more types may be used.

··Repeating unit a4-3 In the repeating unit a4, when R ^Q is a group X having a non-aromatic hydroxyl group as a specific group, and the non-aromatic hydroxyl group is a hydroxyl group contained in a fluorinated alcohol group , The repeating unit a4 is also referred to as repeating unit a4-3. The hydroxyl group contained in the fluorinated alcohol group means, for example, that a hydroxyl group is bonded to a carbon atom, and a fluorine atom and -CFR ₂ are bonded to the carbon atom (α carbon) to which the hydroxyl group is bonded. It independently represents a hydrogen atom or a substituent. As -CFR ₂ , _{at least one of -CF 3} and the like) is mentioned above. That is, the repeating unit a4-3 corresponds to the repeating unit a5. The repeating unit a4-3 is preferably different from the repeating unit a4-1 and/or the repeating unit a4-2.

The hydroxyl group contained in the fluorinated alcohol group is preferably a hydroxyl group contained in a hexafluoroisopropanol group (a group represented by _{"-C(CF 3} ) _{2 OH").} That is, the repeating unit a4-3 preferably corresponds to the repeating unit a6.

The repeating unit a4-3 is preferably a repeating unit represented by general formula (A6).

[化15]

In the general formula (A6), R ^Q6 represents an alkyl group (linear or branched chain. Preferably, it has 1 to 5 carbon atoms), a non-aromatic cyclic group or an aromatic cyclic group.

Examples of the non-aromatic cyclic group include a monocyclic hydrocarbon ring group and a polycyclic hydrocarbon ring group. Examples of monocyclic hydrocarbon ring groups include cycloalkane ring groups having 3 to 12 carbon atoms (preferably 3 to 7 carbon atoms) and cycloolefin ring groups having 3 to 12 carbon atoms. As the polycyclic hydrocarbon ring group, for example, a ring assembly hydrocarbon ring group and a crosslinked cyclic hydrocarbon ring group can be cited. As a crosslinked cyclic hydrocarbon ring, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring, etc. are mentioned, for example. In addition, the crosslinked cyclic hydrocarbon ring may be a condensed ring formed by condensing a plurality of 5-membered cycloalkane rings to 8-membered cycloalkane rings. The crosslinked cyclic hydrocarbon ring group is preferably a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, or a tricyclic [5,2,1,0 ^2,6 ]decane ring group.

The aromatic ring group is preferably an aromatic ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, an anthracyclyl group or a biphenyl ring group.

It is also preferable that the alkyl group, the non-aromatic cyclic group, and the aromatic cyclic group do not have substituents other than _{-(-C(CF 3} ) ₂ OH) _q6.

In general formula (A6), q6 represents an integer of 1-5.

In the case where the resin (A) has the repeating unit a4-3, the content of the repeating unit is preferably 3 mol% to 50 mol%, more preferably 5 mol%, relative to all the repeating units of the resin (A) %～40 mol%, more preferably 10 mol%～35 mol%. One type of repeating unit a4-3 may be used alone, or two or more types may be used.

·· Repeating unit a4-4 In repeating unit a4, when R ^Q is a group X having a photoacid generating group as a specific group, the repeating unit a4 is also referred to as repeating unit a4-4. In the repeating unit a4-4, R ^Q also preferably has a fluorine atom. That is, the repeating unit a4-4 preferably corresponds to the repeating unit a5. The repeating unit a4-4 is preferably different from the repeating unit a4-1, the repeating unit a4-2, and/or the repeating unit a4-3.

The repeating unit a4-4 is preferably a repeating unit represented by general formula (A7).

[化16]

In the general formula (A7), two Xf each independently represent a hydrogen atom, a fluorine atom, or an alkyl group substituted with at least one fluorine atom (preferably CF ₃ ). At least one of the two Xf is preferably other than a hydrogen atom. The alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10. The alkyl group preferably has only a fluorine atom as a substituent.

In the general formula (A7), R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when there are a plurality of R ¹ and R ^{2, they} may be the same or different. The alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10. The substituent of the alkyl group is preferably a fluorine atom. When the alkyl group has a substituent, it preferably has only a fluorine atom as the substituent.

In the general formula (A7), L represents a divalent linking group, and when there are a plurality of L groups, L may be the same or different. The divalent linking group of L includes -COO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, cycloalkylene, alkenylene, and these The linking group formed by connecting a plurality of, etc. is preferably a linking group having a total carbon number of 12 or less.

In general formula (A7), x represents an integer of 1-20, y represents an integer of 0-10, and z represents an integer of 0-10.

In the general formula (A7), M ⁺ represents a cation. For details of M ⁺ , for example, the same cation as ^{M +} in the general formula (PA-1) described later can be used.

In the case of resin (A) having repeating unit a4-4, relative to all repeating units of resin (A), the content of the repeating unit is preferably 3 mol%-40 mol%, more preferably 5 mol% % To 25 mol%, more preferably 7 mol% to 20 mol%. One type of repeating unit a4-4 may be used alone, or two or more types may be used.

·Repeat unit a1-2 Repeating unit a1 may include a repeating unit that does not correspond to any of repeating unit a2, repeating unit a3, and repeating unit a4. That is, the resin (A) may have a repeating unit a1 that does not correspond to any of the repeating unit a2, the repeating unit a3, and the repeating unit a4. The repeating unit a1 is also referred to as repeating unit a1-2.

The repeating unit a1-2 is preferably a repeating unit represented by general formula (A1-2).

[化17]

In the general formula (A1-2), R ^Q12 represents an alkyl group (linear or branched. Preferably, it has 1 to 5 carbon atoms), a non-aromatic cyclic group or an aromatic cyclic group. Among them, R ^Q12 is not a leaving group.

Examples of the non-aromatic cyclic group include a monocyclic hydrocarbon ring group and a polycyclic hydrocarbon ring group. Examples of monocyclic hydrocarbon ring groups include cycloalkane ring groups having 3 to 12 carbon atoms (preferably 3 to 7 carbon atoms) and cycloolefin ring groups having 3 to 12 carbon atoms. As the polycyclic hydrocarbon ring group, for example, a ring assembly hydrocarbon ring group and a crosslinked cyclic hydrocarbon ring group can be cited. As a crosslinked cyclic hydrocarbon ring, a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, a tetracyclic hydrocarbon ring, etc. are mentioned, for example. In addition, the crosslinked cyclic hydrocarbon ring may be a condensed ring formed by condensing a plurality of 5-membered cycloalkane rings to 8-membered cycloalkane rings. The crosslinked cyclic hydrocarbon ring group is preferably a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, or a tricyclic [5,2,1,0 ^2,6 ]decane ring group.

The aromatic ring group is preferably an aromatic ring group having 6 to 18 carbon atoms, preferably a benzene ring group, a naphthalene ring group, an anthracyclyl group and a biphenyl ring group.

The alkyl group, the non-aromatic cyclic group, and the aromatic cyclic group do not have the specific group described with respect to the repeating unit a4 and a group containing a specific group in a part as a substituent. The alkyl group, the non-aromatic cyclic group, and the aromatic cyclic group are preferably unsubstituted.

In the case where the resin (A) has the repeating unit a1-2, the content of the repeating unit is preferably 1 mol% to 30 mol%, more preferably 3 mol% relative to all the repeating units of the resin (A) % To 25 mol%, more preferably 5 mol% to 20 mol%. One type of repeating unit a1-2 may be used alone, or two or more types may be used.

(Repeat unit b1) The resin (A) may have a repeating unit not corresponding to the repeating unit a1 (that is, a repeating unit not corresponding to the repeating unit represented by the general formula (A1)). The repeating unit that does not correspond to the repeating unit a1 is also referred to as the repeating unit b1. As repeating unit b1, the repeating unit represented by general formula (A1-b) is mentioned, for example.

[化18]

In the general formula (A1-b), X represents a halogen atom other than a hydrogen atom, an alkyl group, or a fluorine atom. The alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10. The substituent of the alkyl group is preferably a hydroxyl group or a halogen atom. When the said alkyl group has a substituent, it is preferable to have only a hydroxyl group and/or a halogen atom as a substituent. The alkyl group is preferably -CH ₃ . The halogen atom other than the fluorine atom is preferably a chlorine atom, a bromine atom or an iodine atom.

In the general formula (A1-b), L ^B represents a single bond or -COO-. The carbonyl carbon in -COO- is preferably directly bonded to the main chain of the repeating unit.

Formula (A1-b) R ^Q in general formula (A1) is the same as R ^Q.

In the resin (A), the content of the repeating unit b1 (repeating unit represented by the general formula (A1-b), etc.) relative to all repeating units of the resin (A) is preferably 0 mol% to 95 mol%, More preferably, it is 9 mol% to 90 mol%, and still more preferably 0 mol% to 80 mol%. Two or more types of repeating units represented by general formula (A1) may also be used.

·Repeating unit b2 The repeating unit b1 also preferably includes the repeating unit b2. That is, the resin (A) also preferably has a repeating unit b2. The repeating unit b2 is a repeating unit other than the repeating unit a1, and is a repeating unit having an acid-decomposable group (a repeating unit having a structure in which a polar group is protected by a leaving group detached by the action of an acid). The description of the acid-decomposable group, leaving group, and polar group is as described above.

··Repeating unit b3 The repeating unit b2 also preferably includes the repeating unit b3. The resin (A) also preferably has a repeating unit b3. The repeating unit b3 is a form of the repeating unit b2. The repeating unit b3 is a repeating unit represented by the general formula (A2-b).

[化19]

X in the general formula (A2-b) represents a halogen atom other than a hydrogen atom, an alkyl group or a fluorine atom, and is the same as X in the general formula (A1-b). The same as the formula (A2-b) of R ^Q1 ~ R ^Q3 general formula (A2), the R ^Q1 ~ R ^Q3.

In the case where the resin (A) has a repeating unit b2 (preferably a repeating unit b3), the content of the repeating unit is preferably 5 mol% to 90 mol% relative to all the repeating units of the resin (A), It is more preferably 10 mol% to 85 mol%, and still more preferably 20 mol% to 70 mol%. The repeating unit a2 (preferably the repeating unit a3) may be used singly, or two or more may be used. The total content of repeating unit a2 (preferably repeating unit a3) and repeating unit b2 (preferably repeating unit b3) in resin (A) is preferably 15 mol% relative to all repeating units of resin (A) ~98 mol%, more preferably 25 mol% to 85 mol%, and still more preferably 35 mol% to 80 mol%.

·Repeating unit b4 (repeating unit b5, repeating unit b6) The repeating unit b1 also preferably includes the repeating unit b4. That is, the resin (A) also preferably has a repeating unit b4. The repeating unit b4 is a repeating unit other than the repeating unit a1, and contains a group selected from a lactone group, a sultone group, a carbonate group, and a hydroxyl group (which may be a non-aromatic hydroxyl group or an aromatic hydroxyl group), A repeating unit of one or more specific groups in the group consisting of a sulfonamide group, an amide group, a carboxylic acid group, and a photoacid generating group. In the group having a specific group, the "group having a specific group" may be a specific group itself, or a specific group may be contained in a part of the "group having a specific group". The repeating unit b4 is preferably different from the repeating unit b2 and/or the repeating unit b3.

The repeating unit b4 is preferably a repeating unit represented by general formula (B0).

[化20]

In the general formula (B0), X represents a halogen atom other than a hydrogen atom, an alkyl group, or a fluorine atom. The alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10. The substituent of the alkyl group is preferably a hydroxyl group or a halogen atom. When the said alkyl group has a substituent, it is preferable to have only a hydroxyl group and/or a halogen atom as a substituent. The alkyl group is preferably -CH ₃ . In the general formula (B0), L ^B represents a single bond or -COO-. The carbonyl carbon in -COO- is preferably directly bonded to the main chain of the repeating unit. In the general formula (B0), R ^B0 represents a hydrogen atom or a group Y. However, when R ^B0 represents a hydrogen atom, L ^B represents -COO-, and -L ^B -R ^B0 as a whole represents -COOH. The group Y is selected from the group consisting of lactone, sultone, carbonate, hydroxy (non-aromatic hydroxy or aromatic), sulfonamide, amide, carboxylic acid and The group of one or more specific groups in the group consisting of the photoacid generating group is not a group leaving the group. Further, the so-called group Y 'is not a leaving group ", specifically refers to the case where L ^B is -COO-, in the -COO-R ^B0, R ^B0 (group Y) is not protected as a polar group ( Carboxylic acid group) leaving the group. The term "a group that is not a leaving group" refers to a group of "a leaving group that is detached by the action of an acid" which is not described for the repeating unit a2. Specifically, "the group that is not a leaving group" does not correspond to the group represented by the above-mentioned formulas (Y1) to (Y4). ^{R B0} in general formula (B0) is the same as ^{R Q} in repeating unit a4, for example.

Among them, the repeating unit b4 preferably includes the repeating unit b5. That is, the resin (A) also preferably has a repeating unit b5. The repeating unit b5 is a repeating unit represented by the general formula (B1).

[化21]

X in the general formula (B1) represents a halogen atom other than a hydrogen atom, an alkyl group or a fluorine atom, and is the same as X in the general formula (B0). In the general formula (B1), L ^B represents a single bond or -COO-. The carbonyl carbon in -COO- is preferably directly bonded to the main chain of the repeating unit. In the general formula (B1), R ^B1 represents the group Z. Group Z is selected from lactone group, sultone group, carbonate group, hydroxyl group (may be non-aromatic hydroxyl group or aromatic hydroxyl group), sulfonamide group, amide group, carboxylic acid group One or more specific groups in the group consisting of a photoacid generator and a photoacid generating group have a fluorine atom and are not a leaving group. Further, the so-called group Z 'is not a leaving group ", specifically refers to the case where L ^B is -COO-, in the -COO-R ^B1, R ^B1 (group Z) is not protected as a polar group ( Carboxylic acid group) leaving the group. The term "a group that is not a leaving group" refers to a group of "a leaving group that is detached by the action of an acid" which is not described for the repeating unit a2. Specifically, "the group that is not a leaving group" does not correspond to the group represented by the above-mentioned formulas (Y1) to (Y4). ^{R B1} (group Z) in the general formula (B1) is the same as ^{R Q} in the repeating unit a5, for example.

Among them, it is also preferable that the repeating unit b5 includes a repeating unit b6, and the repeating unit b6 includes a group Z having a hexafluoropropanol group (a group represented by _{“-C(CF 3} ) _{2 OH”).} That is, the resin (A) also preferably has a repeating unit b6. In more detail, the repeating unit b6 is a repeating unit in which R ^B1 is a group Z having a hexafluoropropanol group among the repeating units represented by the general formula (B1). The repeating unit b6 is also a form of the repeating unit b4 and the repeating unit b5.

In the case of resin (A) having repeating unit b4 (preferably repeating unit b5, more preferably repeating unit b6), the content of the repeating unit is preferably 1 mol relative to all repeating units of resin (A) %～80 mol%, more preferably 3 mol%～70 mol%, and still more preferably 5 mol%～65 mol%. One type of repeating unit a4 may be used alone, or two or more types may be used. In addition, with respect to all the repeating units of the resin (A), the total content of the repeating unit a4 and the repeating unit b4 in the resin (A) is preferably 1 mol% to 80 mol%, more preferably 3 mol% to 3 mol%. 70 mol%, more preferably 5 mol% to 65 mol%.

··Repeat unit b4-0 The repeating unit b4 may also be the repeating unit b4-0 having a carboxylic acid group as a specific group. As one aspect of the repeating unit b4-0, the fluorine atom directly bonded to the main chain of the repeating unit in the repeating unit a4-0 is substituted with the repeating unit of X in the general formula (B0). The preferable content of the repeating unit b4-0 is the same as that of the repeating unit a4-0. In addition, with respect to all the repeating units of the resin (A), the total content of the repeating unit a4-0 and the repeating unit b4-0 in the resin (A) is preferably 1 mol% to 30 mol%, more preferably 2 Mol%-20 mol%, more preferably 3 mol%-15 mol%.

··Repeating unit b4-1 The repeating unit b4 is a repeat having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group as a specific group (preferably as a specific group of the group Y or the group Z) In the case of a unit, the repeating unit b4 is also referred to as repeating unit b4-1. In the repeating unit b4-1 having a lactone group, the lactone group is preferably a ring member atom of the lactone structure represented by any one of the general formulas (LC1-1) to (LC1-22) The lactone group is formed by removing more than one hydrogen atom from it. In addition, one ring member atom of the lactone structure may be the main chain of the repeating unit, or may not be the main chain of the repeating unit. The two ring member atoms of the lactone structure may or may not be the main chain of the repeating unit. In the repeating unit b4-1 having a sultone group, the sultone group is preferably derived from the sultone structure represented by any one of the general formulas (SL1-1) to (SL1-3) A sultone group formed by removing more than one hydrogen atom from the ring member atoms. In addition, one ring member atom of the sultone structure may be the main chain of the repeating unit, or may not be the main chain of the repeating unit. The two ring member atoms of the sultone structure may or may not be the main chain of the repeating unit. In the repeating unit b4-1 having a carbonate group, the carbonate group is preferably one or more of the ring member atoms of the cyclic carbonate structure represented by any one of the general formula (CC-1) The sultone group formed by the hydrogen atom. In addition, one ring member atom of the cyclic carbonate structure may be the main chain of the repeating unit, or may not be the main chain of the repeating unit. The two ring member atoms of the cyclic carbonate structure may or may not be the main chain of the repeating unit.

As one form of the repeating unit b4-1, the repeating unit a4-1 (the repeating unit represented by the general formula (A3) or the repeating unit represented by the general formula (A4), etc.) is directly related to the main chain of the repeating unit. The bonded fluorine atom is substituted with the repeating unit of X in the general formula (B0). The repeating unit b4-1 is preferably different from the repeating unit b4-0. The preferable content of the repeating unit b4-1 is the same as that of the repeating unit a4-1. In addition, with respect to all the repeating units of the resin (A), the total content of the repeating unit a4-1 and the repeating unit b4-1 in the resin (A) is preferably 3 mol% to 60 mol%, more preferably 5 Mole%～50 mol%, more preferably 7 mol%～45 mol%.

··The repeating unit b4-2 in the repeating unit b4 is a repeating unit having a non-aromatic hydroxyl group as a specific group (preferably as a specific group of the group Y or the group Z), and the non-aromatic hydroxyl group is In the case of hydroxyl groups other than the hydroxyl group contained in the fluorinated alcohol group, the repeating unit b4 is also referred to as repeating unit b4-2. The repeating unit b4-2 is preferably different from the repeating unit b4-0 and/or the repeating unit b4-1. As one aspect of the repeating unit b4-2, the fluorine atom directly bonded to the main chain in the repeating unit a4-2 (repeating unit represented by the general formula (A5), etc.) is substituted with the general formula (B0 ) in X, the main chain of directly bonded -COO- substituted repeat unit of formula (B0) of the L ^B. The preferable content of the repeating unit b4-2 is the same as that of the repeating unit a4-2. In addition, with respect to all the repeating units of the resin (A), the total content of the repeating unit a4-2 and the repeating unit b4-2 in the resin (A) is preferably 3 mol% to 60 mol%, more preferably 5 Mole%～50 mol%, more preferably 10 mol%～45 mol%.

··The repeating unit b4-3 in the repeating unit b4 is a repeating unit having a non-aromatic hydroxyl group as a specific group (preferably as a specific group of the group Y or the group Z), and the non-aromatic hydroxyl group is In the case of the hydroxyl group contained in the fluorinated alcohol group, the repeating unit b4 is also referred to as repeating unit b4-3. The repeating unit b4-3 is preferably different from the repeating unit b4-0, the repeating unit b4-1, and/or the repeating unit b4-2. The repeating unit b4-3 is preferably equivalent to the repeating unit b6. As one aspect of the repeating unit b4-3, the fluorine atom directly bonded to the main chain in the repeating unit a4-3 (repeating unit represented by the general formula (A6), etc.) is substituted with the general formula (B0 ) in X, the main chain of directly bonded -COO- substituted repeating units of the general formula L ^B (B0) a. The preferable content of the repeating unit b4-3 is the same as that of the repeating unit a4-3. In addition, with respect to all the repeating units of the resin (A), the total content of the repeating unit a4-3 and the repeating unit b4-3 in the resin (A) is preferably 3 mol% to 50 mol%, more preferably 5 mol% Mole%-40 mol%, more preferably 10 mol% to 35 mol%.

··Repeating unit b4-4 When the repeating unit b4 is a repeating unit having a photoacid generating group as a specific group (preferably as a specific group of the group Y or the group Z), the repeating unit b4 Called repeating unit b4-4. The repeating unit b4-4 is preferably equivalent to the repeating unit b5. The repeating unit b4-4 is preferably different from the repeating unit b4-0, the repeating unit b4-1, the repeating unit b4-2, and/or the repeating unit b4-3. As one aspect of the repeating unit b4-4, the fluorine atom directly bonded to the main chain in the repeating unit a4-4 (repeating unit represented by the general formula (A7), etc.) is substituted with the general formula (B0 ) in X, the main chain of directly bonded -COO- substituted repeat unit of formula (B0) of the L ^B. The preferable content of the repeating unit b4-4 is the same as that of the repeating unit a4-4. In addition, with respect to all the repeating units of the resin (A), the total content of the repeating unit a4-4 and the repeating unit b4-4 in the resin (A) is preferably 3 mol% to 40 mol%, more preferably 5 Mole% to 25 mole%, more preferably 7 mole% to 20 mole%.

··Repeat unit b4-5 When the repeating unit b4 is a repeating unit containing a group having an aromatic hydroxyl group as a specific group (preferably as a specific group of the group Y or the group Z), the repeating unit b4 is also referred to as a repeating unit b4-5. The repeating unit b4-5 is preferably different from the repeating unit b4-0, the repeating unit b4-1, the repeating unit b4-2, the repeating unit b4-3, and/or the repeating unit b4-4. The repeating unit b4-5 is preferably a repeating unit represented by the general formula (B2).

[化22]

In the general formula (B2), X represents a halogen atom other than a hydrogen atom, an alkyl group or a fluorine atom, and is the same as X in the general formula (B0).

In the general formula (B2), X ₄ represents a single bond, -COO- or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group (which may be linear or branched. The carbon number is preferably 1 to 5). The carbonyl carbon in -COO- is preferably directly bonded to the main chain of the repeating unit.

In the general formula (B2), L ₄ represents a single bond or an alkylene group (which may be linear or branched. It preferably has 1 to 20 carbon atoms).

In the general formula (B2), Ar ₄ represents an (n+1)-valent aromatic ring group. The aromatic ring group is preferably a phenyl ring group, a naphthalene ring group, an anthracyclyl group, and other carbon 6 to 18 arylidene groups, or a thiophene ring group, a furan ring group, a pyrrolyl ring group, a benzothiophene ring group, or a benzene ring group. Aromatic ring groups containing heterocycles, such as oxofuran ring group, benzopyrrole ring group, triazine ring group, imidazole ring group, benzimidazole ring group, triazole ring group, thiadiazole ring group and thiazole ring group, more It is preferably a phenyl ring group.

In general formula (B2), n represents an integer of 1-5. The (n+1)-valent aromatic ring group may further have a substituent.

Examples of substituents that the alkyl group of R ₆₄ , the alkylene group of L ₄ and _{the (n+1)-valent aromatic ring group of Ar 4} may have include halogen atoms (preferably fluorine atoms), methoxy Alkoxy groups such as ethoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group; aryl groups such as phenyl group, etc. In addition, as _{a substituent that the (n+1)-valent aromatic ring group of Ar 4} may have, for example, an alkyl group (which may be linear or branched. Preferably, it has 1 to 20 carbon atoms).

Hereinafter, specific examples of the repeating unit b4-5 are shown, but the present invention is not limited to this. In the formula, a represents 1 or 2.

[化23]

[化24]

[化25]

Furthermore, among the repeating units, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents an integer of 1-3.

[化26]

In the case of resin (A) having repeating unit b4-5, relative to all repeating units of resin (A), the content of the repeating unit is preferably 3 mol% to 70 mol%, more preferably 10 mol% %~65 mol%, and more preferably 7 mol%~60 mol%. One type of repeating unit b4-5 may be used alone, or two or more types may be used.

The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). According to the GPC method, the weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and still more preferably 4,500 to 15,000 in terms of polystyrene conversion value. If the weight average molecular weight of the resin (A) is 1,000 to 200,000, the deterioration of heat resistance and dry etching resistance can be prevented, and the deterioration of developability and the increase in viscosity and the deterioration of film forming properties can be prevented. The degree of dispersion (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and still more preferably 1.2 to 2.0. The smaller the dispersion, the better the resolution and resist shape, and the smoother the sidewall of the resist pattern, the better the roughness performance.

The resin (A) is preferably one having a high glass transition temperature (Tg) in terms of suppressing excessive diffusion of the generated acid and/or pattern collapse during development. The Tg is preferably more than 90°C, more preferably more than 100°C, still more preferably more than 110°C, and particularly preferably more than 125°C. Furthermore, too high Tg will cause the dissolution rate in the developer to decrease, so Tg is preferably 400°C or less, more preferably 350°C or less. In addition, in this specification, the glass transition temperature (Tg) of the polymer, such as resin (A), is calculated by the following method. First, by the Bicerano method, the Tg of a homopolymer composed only of each repeating unit contained in the polymer is calculated. Hereinafter, the calculated Tg is referred to as "Tg of the repeating unit". Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, using Fox’s formula (described in "Materials Letters" 62 (2008) 3152, etc.), calculate the Tg in each mass ratio, and sum these to be the Tg (℃) of the polymer . The Bicerano method is described in "Prediction of polymer properties", Marcel Dekker Inc, New York (1993), etc. In addition, the calculation of Tg based on the Bicerano method can be performed using polymer physical property estimation software MDL polymer (Polymer) (MDL Information Systems, Inc.).

In order to make the Tg of the resin (A) greater than 90° C., it is preferable to reduce the mobility of the main chain of the resin (A). As a method of reducing the mobility of the main chain of the resin (A), the following methods (a) to (e) can be cited. (A) Introduce bulky substituents into the main chain (B) Introduce multiple substituents into the main chain (C) Introduction of substituents that induce the interaction between resins (A) near the main chain (D) Form the main chain with a ring structure (E) The connection between the ring structure and the main chain Furthermore, it is preferable that the resin (A) has a repeating unit whose Tg of a homopolymer shows 130 degreeC or more. In addition, the type of the repeating unit whose Tg of the homopolymer shows 130°C or higher is not particularly limited, as long as it is a repeating unit whose Tg of the homopolymer calculated by the Bicerano method is 130°C or higher. In addition, depending on the type of the functional group in the repeating unit represented by the formula (A) to the formula (E) described later, the Tg corresponding to the homopolymer shows a repeating unit of 130° C. or more.

As a specific method of achieving the (a), for example, a method of introducing a repeating unit represented by the formula (A) into the resin (A) is exemplified.

[化27]

Of formula _(A), R A represents a group having a polycyclic structure. R _x represents a hydrogen atom, a methyl group or an ethyl group. The group having a polycyclic structure refers to a group having a plurality of ring structures, and the plurality of ring structures may or may not be condensed. Examples of the repeating unit represented by formula (A) include the following repeating units.

[化28]

[化29]

In the formula, R represents a hydrogen atom, a methyl group, or an ethyl group. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR'"Or-COOR"':R'" is an alkyl group having 1 to 20 carbons or a fluorinated alkyl group) or a carboxylic acid group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by Ra may be substituted with a fluorine atom or an iodine atom. In addition, R'and R'' each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen atom. , Ester group (-OCOR''' or -COOR''': R''' is an alkyl group with 1 to 20 carbons or a fluorinated alkyl group) or a carboxylic acid group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the groups represented by R′ and R″ may be substituted with a fluorine atom or an iodine atom. L represents a single bond or a divalent linking group. Examples of the divalent linking group include -COO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, cycloalkylene, alkenylene, and these The connecting base formed by the multiple connections. m and n each independently represent an integer of 0 or more. The upper limit of m and n is not particularly limited, and there are many cases of 2 or less, and more cases of 1 or less.

As a specific method of achieving the above (b), for example, a method of introducing a repeating unit represented by formula (B) into the resin (A) can be cited.

[化30]

In formula (B), R _b1 to R _b4 each independently represent a hydrogen atom or an organic group, and at least two of _{R b1} to R _{b4 represent an organic group.} In addition, when at least one of the organic groups is a group in which a ring structure is directly connected to the main chain in the repeating unit, the type of other organic groups is not particularly limited. In addition, when none of the organic groups is a group in which a ring structure is directly connected to the main chain of the repeating unit, at least two of the organic groups have three constituent atoms other than hydrogen atoms. The above substituents.

Examples of the repeating unit represented by formula (B) include the following repeating units.

[化31]

In the above formula, R each independently represents a hydrogen atom or an organic group. As an organic group, organic groups, such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group which may have a substituent, are mentioned, for example. R'each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR "Or -COOR": R" is an alkyl group having 1 to 20 carbons or a fluorinated alkyl group) or a carboxylic acid group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R′ may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and there are many cases of 2 or less, and more cases of 1 or less.

As a specific method of achieving the above (c), for example, a method of introducing a repeating unit represented by formula (C) into the resin (A) can be cited.

[化32]

In the formula (C), R _c1 to R _c4 each independently represent a hydrogen atom or an organic group, _{and at least one of R c1} to R _c4 is a group having a hydrogen-bonding hydrogen atom with 3 or less autonomous carbon atoms. Among them, it is preferable to induce an interaction between the main chains of the resin (A) and have a hydrogen atom having hydrogen bonding properties within 2 atoms (more on the side near the main chain).

Examples of the repeating unit represented by formula (C) include the following repeating units.

[化33]

In the formula, R represents an organic group. Examples of the organic group include an optionally substituted alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, and ester group (-OCOR or -COOR: R is an alkyl group having 1 to 20 carbons or Fluorinated alkyl) and so on. R'represents a hydrogen atom or an organic group. Examples of the organic group include organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. Furthermore, the hydrogen atom in the organic group may be substituted with a fluorine atom or an iodine atom.

As a specific method of achieving the (d), for example, a method of introducing a repeating unit represented by the formula (D) into the resin (A) can be cited. When the resin (A) contains the repeating unit represented by the formula (D), the content of the repeating unit is preferably 1 mol% to 50 mol% relative to all the repeating units of the resin (A), and more preferably It is 3 mol% to 40 mol%, and more preferably 5 mol% to 30 mol%.

[化34]

In formula (D), "Cyclic" represents a group that forms a main chain with a cyclic structure. The number of atoms constituting the ring is not particularly limited.

Examples of the repeating unit represented by formula (D) include the following repeating units.

[化35]

In the formula, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen group. Atom, ester group (-OCOR" or -COOR": R" is an alkyl group or fluorinated alkyl group having 1 to 20 carbons) or a carboxylic acid group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom. In the formula, R'each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, Ester group (-OCOR" or -COOR": R" is an alkyl or fluorinated alkyl group having 1 to 20 carbons) or a carboxylic acid group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R′ may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and there are many cases of 2 or less, and more cases of 1 or less.

As a specific method of achieving the above (e), for example, a method of introducing a repeating unit represented by formula (E) into the resin (A) can be cited. When the resin (A) contains the repeating unit represented by the formula (E), the content of the repeating unit is preferably 1 mol% to 50 mol% relative to all the repeating units of the resin (A), and more preferably It is 3 mol% to 40 mol%, and more preferably 5 mol% to 30 mol%.

[化36]

In formula (E), Re each independently represents a hydrogen atom or an organic group. As an organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group etc. which may have a substituent are mentioned, for example. "Cyclic" is a cyclic group containing carbon atoms of the main chain. The number of atoms contained in the cyclic group is not particularly limited.

Examples of the repeating unit represented by formula (E) include the following repeating units.

[化37]

In the above formula, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen group. Atom, ester group (-OCOR" or -COOR": R" is an alkyl group or fluorinated alkyl group having 1 to 20 carbons) or a carboxylic acid group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom. R'each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester group (-OCOR" or -COOR": R" is an alkyl group having 1 to 20 carbons or a fluorinated alkyl group) or a carboxylic acid group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R′ may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, and there are many cases of 2 or less, and more cases of 1 or less. In addition, in formula (E-2), formula (E-4), formula (E-6), and formula (E-8), two Rs may be bonded to each other to form a ring.

In the resist composition, in the total solid content, the content of the resin (A) is preferably 50% by mass to 99.9% by mass, more preferably 60% by mass to 99.0% by mass. In addition, one type of resin (A) may be used, or two or more types may be used.

<(B) Compounds that generate acid by irradiation with actinic rays or radiation> The resist composition may also contain a compound (photoacid generator) that generates acid by irradiation with actinic rays or radiation. The photoacid generator is a compound that generates acid by exposure (preferably exposure of EUV light). The photoacid generator may be in the form of a low-molecular compound, or may be incorporated in a part of the polymer. In addition, the form of the low-molecular compound and the form incorporated into a part of the polymer may be used in combination. When the photoacid generator is in the form of a low-molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less. When the photoacid generator is a form incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or may be incorporated into a resin different from the resin (A). In the present invention, the photoacid generator is preferably in the form of a low-molecular compound. The photoacid generator is not particularly limited. Among them, a compound that generates an organic acid by EUV light irradiation is preferred, and a photoacid generator having a fluorine atom or an iodine atom in the molecule is more preferred. As the organic acid, for example, sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphor sulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkyl carboxylic acid, etc.), Carbonylsulfonimidic acid, bis(alkylsulfonyl)imidic acid and tris(alkylsulfonyl)methide acid, etc.

The volume of the acid generated by the photoacid generator is not particularly limited. In terms of suppressing the diffusion of the acid generated by exposure to the non-exposed area and improving the resolution, it is preferably 240 Å ³ or more, more preferably 305 Å ³ or more, ^{more preferably 350 Å 3} or more, and particularly preferably 400 Å ³ or more. Furthermore, it is a sense in terms of the solubility of the solvent or in a coating, the volume of the acid generated from the photoacid generator is preferably 1500 Å ³ or less, more preferably 1000 Å ³ or less, and further good as 700 Å ³ or less. The value of the volume is obtained using "WinMOPAC" manufactured by Fujitsu Co., Ltd. When calculating the value of the volume, firstly, input the chemical structure of the acid of each example, and secondly, use the structure as the initial structure, and determine the molecular force field calculation using the 3 method of Molecular Mechanics (MM). The most stable three-dimensional conformation of the acid, after which the most stable three-dimensional conformation is calculated using the parameterized model number (PM) 3 method to calculate the "accessible volume" of each acid.

The structure of the acid generated by the photoacid generator is not particularly limited. In terms of suppressing the diffusion of the acid and improving the resolution, the interaction between the acid generated by the photoacid generator and the resin (A) is preferred. The effect is strong. In this respect, when the acid generated by the photoacid generator is an organic acid, for example, it is preferably in addition to a sulfonic acid group, a carboxylic acid group, a carbonyl sulfonylimine group, and a bissulfonylimine group. In addition to organic acid groups such as trisulfonyl methide acid groups, it has a polar group. Examples of polar groups include ether groups, ester groups, amide groups, amide groups, sulfo groups, sulfonyloxy groups, sulfonamide groups, thioether groups, thioester groups, urea groups, carbonate groups, and amines. Carbamate, hydroxyl and mercapto groups. The number of polar groups that the generated acid has is not particularly limited, and it is preferably one or more, and more preferably two or more. Among them, in terms of suppressing excessive development, the number of polar groups is preferably less than six, and more preferably less than four.

The photoacid generator is preferably a photoacid generator that generates the acid exemplified below. Furthermore, in part of the example, the calculated value of the volume (in Å ³ ) is marked.

[化38]

[化39]

[化40]

In terms of more excellent effects of the present invention, the photoacid generator is preferably a photoacid generator having anions and cations.

(Compound represented by general formula (PA-1)) The photoacid generator preferably contains a compound represented by general formula (PA-1).

[化41]

Formula (PA-1) in, A ¹ and A ² each independently represent -SO ₂ -R ^P or -CO-R ^P. R ^P represents an organic group. ^{The two R P} present in the general formula (PA-1) may be the same or different. Formula (PA-1) in the presence of two carbon atoms for R ^P corresponds each independently is preferably from 1 to 25, more preferably 1 to 15. The number of atoms other than two hydrogen atoms for R ^P corresponds formula (PA-1) is preferably present in each independently from 2 to 30, more preferably 4 to 20. R ^{P is} preferably a group represented by the general formula (RF). -L ^RF -R ^RF (RF)

In the general formula (RF), L ^RF represents a single bond or a divalent linking group. Examples of the divalent linking group include: -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene groups (which may be linear It can also be branched. Preferably it has 1 to 6 carbons, cycloalkylene (preferably 3 to 15 carbons), and alkenylene (which can be straight or branched. It is preferred. These are 2-6 carbon atoms and a divalent linking group formed by combining a plurality of these. In addition, the substituents that these divalent linking groups may have when possible are preferably halogen atoms, and more preferably fluorine atoms. For example, the alkylene group (including the alkylene group that may be contained in the divalent linking group formed by combining a plurality of groups) is also preferably a perfluoroalkylene group. The divalent linking group is preferably -alkylene-COO- or -alkylene-SO ₂ -. -Alkylene-COO- and -alkylene-SO ₂ -preferably have an alkylene on the N ^- side.

In the general formula (RF), R ^RF represents a cycloalkyl group or an alkyl group. When R ^RF is a cycloalkyl group, the cycloalkyl group may be monocyclic or polycyclic. The carbon number of the cycloalkyl group is preferably 3-15, more preferably 5-10. Examples of the cycloalkyl group include norbornyl group, decalinyl group, and adamantyl group. The substituent that the cycloalkyl group may have is preferably an alkyl group (which may be linear or branched. It preferably has 1 to 5 carbon atoms). The cycloalkyl group preferably has no other substituents. One or more carbon atoms among the carbon atoms of the ring member atoms of the cycloalkyl group may be substituted with carbonyl carbon atoms and/or heteroatoms. ^{For example, the carbon atom (-CH<) bonded to L RF} in the cycloalkyl group may be substituted with a nitrogen atom (-N<). When R ^RF is an alkyl group, the alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10, more preferably 1-5. The substituent that the alkyl group may have is preferably a cycloalkyl group, a fluorine atom, or a cyano group. It is also preferable that the alkyl group does not have substituents other than these. Examples of the cycloalkyl group as the substituent are similarly exemplified in the cycloalkyl group described in the case where ^{R RF is a cycloalkyl group.} When the alkyl group has a fluorine atom as the substituent, the alkyl group may or may not be a perfluoroalkyl group. When the alkyl group has a fluorine atom as the substituent, a part or all of the alkyl group is also preferably a perfluoromethyl group.

In the general formula (PA-1), two R ^{P contained in "A 1} -N ^-- A ² "may be bonded to each other to form a ring.

In the general formula (PA-1), M ⁺ represents a cation. The cation of M ⁺ is preferably an organic cation. The organic cations are preferably cations represented by general formula (ZaI) (cations (ZaI)) or cations represented by general formula (ZaII) (cations (ZaII)), respectively.

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In the general formula (ZaI), 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 1-30, preferably 1-20.} In addition, two of R ²⁰¹ to R ²⁰³ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amido group, or a carbonyl group. Examples of the group formed by bonding two of R ²⁰¹ to R ²⁰³ include an alkylene group (for example, a butylene group and a pentylene group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

Examples of the cation in the general formula (ZaI) include the cation (ZaI-1), the cation (ZaI-2), the cation represented by the general formula (ZaI-3b) (the cation (ZaI-3b)), and A cation (cation (ZaI-4b)) represented by the general formula (ZaI-4b).

First, the cation (ZaI-1) will be described. The cation (ZaI-1) is an aryl cation in which at least one ^{of R 201} to R ^{203 of the general formula (ZaI) is an aryl group.} The aryl sulfonium cation may be that all of R ²⁰¹ to R ²⁰³ are aryl groups, or part of R ²⁰¹ to R ²⁰³ may be aryl groups, and the remainder may be alkyl groups or cycloalkyl groups. In addition, one of R ²⁰¹ to R ²⁰³ is an aryl group, ^{and the remaining two of R 201} to R ²⁰³ may be bonded to form a ring structure. The ring may also contain oxygen atoms, sulfur atoms, ester groups, amide groups or Carbonyl. Examples of the group formed by bonding two of R ²⁰¹ to R ²⁰³ include an alkylene group in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amido group, and/or a carbonyl group ( For example, butylene, pentylene or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -). Examples of the aryl sulfonium cation include triaryl sulfonium cation, diaryl alkyl sulfonium cation, aryl dialkyl sulfonium cation, diaryl cycloalkyl sulfonium cation, and aryl dicycloalkyl sulfonium cation.

The aryl group contained in the aryl alumium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl alumium cation has two or more aryl groups, the two or more aryl groups it has may be the same or different. The alkyl group or cycloalkyl group that the aryl cation has as necessary is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms For example, a methyl group, an ethyl group, a propyl group, a n-butyl group, a second butyl group, a tertiary butyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, etc. are mentioned.

The substituents that the aryl group, alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ may have are each independently an alkyl group (for example, carbon number 1-15), cycloalkyl group (for example, carbon number 3-15), An aryl group (for example, a carbon number of 6 to 14), an alkoxy group (for example, a carbon number of 1 to 15), a cycloalkylalkoxy group (for example, a carbon number of 1 to 15), a halogen atom, a hydroxyl group, or a thiophenyl group. The substituent may further have a substituent when possible. For example, the alkyl group may have a halogen atom as a substituent and become a halogenated alkyl group such as a trifluoromethyl group.

Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation in which R ²⁰¹ to R ²⁰³ in the formula (ZaI) each independently represent an organic group without an aromatic ring. Here, the term "aromatic ring" also includes aromatic rings containing heteroatoms. The organic group having no aromatic ring as R ²⁰¹ to R ²⁰³ usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. R ²⁰¹ to R ^{203 are} preferably each independently an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group and a 2-oxocycloalkane Group or alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

Examples of the alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ include a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl , Butyl and pentyl), and cycloalkyl groups with 3 to 10 carbon atoms (such as cyclopentyl, cyclohexyl and norbornyl). R ²⁰¹ to R ²⁰³ may be further substituted with a halogen atom, an alkoxy group (for example, a carbon number of 1 to 5), a hydroxyl group, a cyano group, or a nitro group.

Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following general formula (ZaI-3b).

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In the general formula (ZaI-3b), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, Cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group (tertiary butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _1c to R _{5c , R 5c} and R _6c , R _6c and R _7c , R _5c and R _x, and R _x and R _y may be bonded respectively to form a ring, and the ring may also be independently Contains oxygen atom, sulfur atom, ketone group, ester bond or amide bond. Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring include a 3-membered ring to a 10-membered ring, preferably a 4-membered ring to an 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

Examples of groups formed by bonding any two or more of R _1c to R _{5c , R 6c} and R _7c , and R _x and R _y include alkylene groups such as butylene and pentylene. The methylene group in the alkylene group may be substituted with heteroatoms such as oxygen atoms. The group formed by bonding R _5c and R _6c and R _5c and R _{x is} preferably a single bond or an alkylene group. As the alkylene group, for example, a methylene group, an ethylene group, etc.

Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following general formula (ZaI-4b).

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In the general formula (ZaI-4b), l represents an integer of 0-2. r represents an integer of 0-8. R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (the cycloalkyl group may be a cycloalkyl group itself, or a group containing a cycloalkyl group in a part). These groups may have a substituent. R ₁₄ represents a hydroxy group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (the cycloalkyl group itself may be Is a group containing a cycloalkyl group in a part). These groups may have a substituent. When _{a plurality of R 14} are present, each independently represents the aforementioned groups such as a hydroxyl group. R ₁₅ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, a hetero atom such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. In one aspect, it is preferable that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure.

In the general formula (ZaI-4b), _{the alkyl groups of R 13} , R ₁₄ and R ₁₅ are linear or branched. The number of carbon atoms in the alkyl group is preferably 1-10. The alkyl group is more preferably methyl, ethyl, n-butyl or tertiary butyl.

Next, the general formula (ZaII) will be explained. In the general formula (ZaII), R ²⁰⁴ and R ²⁰⁵ each independently represent an aryl group, an alkyl group, or a cycloalkyl group. The aryl group of R ²⁰⁴ and R ²⁰⁵ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ²⁰⁴ and R ²⁰⁵ may be an aryl group containing a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic ring include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. The alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ are preferably a linear alkyl group having 1 to 10 carbons or a branched alkyl group having 3 to 10 carbons (for example, methyl, ethyl, propyl, butyl, etc.). Group or pentyl group), or a cycloalkyl group having 3 to 10 carbons (for example, cyclopentyl, cyclohexyl or norbornyl).

The aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ and R ^{205 may each independently have a substituent.} Examples of substituents that the aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may have include alkyl groups (for example, carbon numbers 1 to 15), cycloalkyl groups (for example, carbon numbers 3 to 15), and aromatic groups. Group (for example, carbon number 6-15), alkoxy (for example, carbon number 1-15), halogen atom, hydroxyl group, thiophenyl group, etc.

(Compound represented by general formula (PB)) The photoacid generator preferably contains a compound represented by general formula (PB). M ₁ ⁺ A ^-- LB ^- M ₂ ⁺ (PB)

Compounds of general formula (PB) comprises a structure represented by the equivalent of having a photoacid generating agent is generally a function of (the equivalent of "A M ₁ ^{+ -} -" moiety) in one molecule, and having the equivalent of the acid diffusion controller The functional structure (corresponding to the part of "-B ^- M ₂ ⁺ ") of the two, so in the resist film, the existence ratio of each of the structures can be fixed. Therefore, the inventors of the present invention speculate that even when the resist film is exposed to light, the amount and diffusion of acid generated in the resist film are likely to become uniform, and the width of the pattern obtained after development is stable.

In the general formula (PB), M ₁ ⁺ and M ₂ ⁺ each independently represent an organic cation. As _{the organic cations of M 1} ⁺ and M ₂ ⁺ , the organic cations listed in the description ^{of M +} of the general formula (PA-1) can be used independently of each other in the same manner.

In the general formula (PB), L represents a divalent organic group. As the divalent organic group, for example, -COO-, -CONH-, -CO-, alkylene (preferably carbon number 1 to 6. It may be linear or branched), extension Cycloalkyl (preferably carbon number 3-15), alkenylene group (preferably carbon number 2-6), and a divalent linking group formed by combining a plurality of these. One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be substituted with a carbonyl carbon and/or a heteroatom (oxygen atom, etc.). The divalent linking groups preferably further have a group selected from the group consisting of -O-, -S-, -SO- and -SO ₂ -.

Among them, L is preferably a group represented by the following general formula (L). *A-LA-LB-LC-LD-LE-*B (L)

In the general formula (L), *A represents the bonding position ^{with A-in the general formula (PB).} In the general formula (L), *B represents the bonding position ^{with B-in the general formula (PB).}

In the general formula (L), LA represents -(C(R _LA1 )(R _LA2 )) _XA -. The XA represents an integer of 1 or more, preferably 1-10, more preferably 1-3. R _LA1 and R _LA2 each independently represent a hydrogen atom or a substituent. The substituents of R _LA1 and R _LA2 are preferably each independently a fluorine atom or a fluoroalkyl group, more preferably a fluorine atom or a perfluoroalkyl group, and still more preferably a fluorine atom or a perfluoromethyl group. When XA is 2 or more, XA R _LA1 may be the same or different. When XA is 2 or more, R _LA2 in which XA is present may be the same or different. -(C(R _LA1 )(R _LA2 ))- is preferably -CH ₂ -, -CHF-, -CH(CF ₃ )- or -CF ₂ -. Among them, -(C(R _LA1 )(R _LA2 ))- which is ^{directly bonded to A-} in general formula (PB) is _{preferably -CH 2} -, -CHF-, -CH(CF ₃ )- or- CF ₂ -. Other than -(C(R _LA1 )(R _LA2 ))- which is ^{directly bonded to A-} in the general formula (PB) _{-(C(R LA1} )(R _LA2 ))- is preferably each independently- CH ₂ -, -CHF- or -CF ₂ -.

In the general formula (L), LB represents a single bond, an ester group (-COO-) or a sulfonyl group (-SO ₂ -).

In the general formula (L), LC represents a single bond, an alkylene group, a cycloalkylene group, or a combination of these ("-alkylene group-cycloalkylene group-"), etc.). The alkylene group may be linear or branched. The carbon number of the alkylene group is preferably 1-5, more preferably 1-2, and still more preferably 1. The carbon number of the cycloalkylene group is preferably 3-15, more preferably 5-10. The cycloalkylene group may be monocyclic or polycyclic. Examples of the cycloalkylene group include norbornanediyl and adamantanediyl. The substituent that the cycloalkylene group may have is preferably an alkyl group (which may be linear or branched. Preferably, it has 1 to 5 carbon atoms). One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be substituted with a carbonyl carbon and/or a heteroatom (oxygen atom, etc.). When LC is "-alkylene-cycloalkylene-", the alkylene moiety is preferably present on the LB side. When LB is a single bond, LC is preferably a single bond or a cycloalkylene group.

In the general formula (L), LD represents a single bond, an ether group (-O-), a carbonyl group (-CO-), or an ester group (-COO-).

In the general formula (L), LE represents a single bond or -(C(R _LE1 )(R _LE2 )) _XE -. _XE in the -(C(R _LE1 )(R _LE2 )) XE-represents an integer of 1 or more, preferably 1-10, more preferably 1-3. R _LE1 and R _LE2 each independently represent a hydrogen atom or a substituent. When XE is 2 or more, XE R _LE1 may be the same or different. When XE is 2 or more, XE R _LE2 may be the same or different. Among them, -(C(R _LE1 )(R _LE2 ))- is preferably -CH ₂ -. In the general formula (L), when LB, LC and LD are single bonds, it is preferable that LE is also a single bond.

In the general formula (PB), A ^- represents an acid radical anion group. The acid anion group is a group having an anion atom. Specifically, A ^-is preferably a group represented by any one of general formulas (A-1) to (A-2).

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In the general formulas (A-1) to (A-2), * represents the bonding position. Formula (A-2) in, R ^A represents an organic group. R ^{A is} preferably an alkyl group. The alkyl group may be linear or branched. The carbon number of the alkyl group is preferably 1-10, more preferably 1-5. The substituent that the alkyl group may have is preferably a fluorine atom. The alkyl group having a fluorine atom as a substituent may or may not be a perfluoroalkyl group.

In general formula (PB), B ^- represents a group represented by any one of general formulas (B-1) to (B-4). B ^-is preferably a group represented by any of the general formulas (B-1) to (B-3), more preferably a group represented by any of the general formulas (B-1) to (B-2) Represents the base.

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In the general formulas (B-1) to (B-4), * represents the bonding position. In the general formula (B-1) ~ (B -4), R B represents an organic group. R ^{B is} preferably a cycloalkyl group or an alkyl group. In the case where R ^B is a cycloalkyl group, the cycloalkyl group preferably having a carbon number of 3 to 15, more preferably from 5 to 10. The cycloalkyl group may be monocyclic or polycyclic. Examples of the cycloalkyl group include norbornyl group and adamantyl group. The substituent that the cycloalkyl group may have is preferably an alkyl group (which may be linear or branched. It preferably has 1 to 5 carbon atoms). One or more carbon atoms among the carbon atoms of the ring member atoms of the cycloalkyl group may be substituted with a carbonyl carbon atom. Under a case where R ^B is an alkyl group, the alkyl group may be linear or branched or. The carbon number of the alkyl group is preferably 1-10, more preferably 1-5. The substituent that the alkyl group may have is preferably a cycloalkyl group, a fluorine atom, or a cyano group. Cycloalkyl described case of the Examples of the cycloalkyl group may be substituted in the same manner as R ^B is exemplified a cycloalkyl group. When the alkyl group has a fluorine atom as the substituent, the alkyl group may or may not be a perfluoroalkyl group. When the alkyl group has a fluorine atom as the substituent, a part or all of the alkyl group is also preferably a perfluoromethyl group.

_{In the compound represented by HA-L-BH in which M 1} ⁺ and M ₂ ⁺ of the compound represented by the general formula (PB) are each substituted with a hydrogen atom, the pKa of the group represented by HA is higher than the pKa of the group represented by BH low. More specifically, in the case of calculating the acid dissociation constant for the compound represented by HA-L-BH ^{, the pKa when "HA-L-BH" becomes "A--} L-BH" is referred to as "HA The pKa of the base represented by "A ^-- L-BH ^{", and the pKa when "A--} LB ^- " becomes "A--LB -" is further defined as the "pKa of the base represented by BH". "The pKa of the base represented by HA" and "the pKa of the base represented by BH" are obtained using "Package 1" or "Gaussian 16", respectively. Among them, the pKa of the group represented by HA is preferably -12.00 to 1.00, more preferably -7.00 to 0.50, and still more preferably -5.00 to 0.00. The pKa of the group represented by HB is preferably -4.00 to 14.00, more preferably -2.00 to 12.00, and still more preferably -1.00 to 5.00. The difference between the pKa of the group represented by HB and the pKa of the group represented by HA ("pKa of the group represented by HB"-"pKa of the group represented by HA") is preferably 0.10 to 20.00, more preferably 0.50 to 17.00, more preferably 2.00 to 15.00.

(Other photo-acid generators) The resist composition may use photo-acid generators other than those mentioned above. As another photoacid generator, for example, "M ⁺ Z ^- (M ⁺ represents a cation, Z ^- represents an anion)" compound (salt) represented.

"M ⁺ Z ^-" compound represented by, M ⁺ represents a cation of the same, may include the general formula (PA-1) cations cation. "M ⁺ Z ^-" compound represented by, Z ^- represents an anion, preferably the ability to cause nucleophilic reaction is significantly low anion. Examples of the anion include sulfonate anions (aliphatic sulfonate anions such as fluoroalkylsulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic Group carboxylate anions and aralkyl carboxylate anions, etc.), and tri(alkylsulfonyl) methide anions.

The aliphatic part in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and a carbon number 3-30 cycloalkyl.

The aromatic ring group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the substituents that the alkyl group, cycloalkyl group, and aryl group may have include halogen atoms such as nitro group and fluorine atom, carboxylic acid group, hydroxyl group, amino group, cyano group, and alkoxy group (more Preferred are carbon number 1-15), cycloalkyl (preferably carbon number 3-15), aryl group (preferably carbon number 6-14), alkoxycarbonyl (preferably carbon number 2-7) , Alkyl (preferably carbon number 2-12), alkoxycarbonyloxy (preferably carbon number 2-7), alkylthio (preferably carbon number 1-15), alkylsulfonyl (Preferably carbon number 1-15), alkyliminosulfonyl group (preferably carbon number 1-15), aryloxysulfonyl group (preferably carbon number 6-20), alkyl aryl Oxysulfonyl (preferably carbon number 7-20), cycloalkylaryloxysulfonyl (preferably carbon number 10-20), alkoxy alkoxy (preferably carbon number 5-20) 20) and cycloalkylalkoxyalkoxy (preferably carbon number 8-20).

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl.

The alkyl group in the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents of these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkyl aryl groups. The oxysulfonyl group is preferably a fluorine atom or an alkyl group substituted with a fluorine atom.

As other non-nucleophilic anion, and examples thereof include phosphorus fluoride (e.g., PF ₆ ^-), boron trifluoride (e.g., BF ₄ ^-) and antimony trifluoride (e.g., SbF ₆ ^-).

The non-nucleophilic anion is preferably an aliphatic sulfonate anion substituted with a fluorine atom in at least the α position of a sulfonic acid, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, or an alkyl group substituted with a fluorine atom Tris(alkylsulfonyl)methide anion. Among them, more preferred are perfluoroaliphatic sulfonate anions (preferably carbon number 4-8) or benzenesulfonate anions having a fluorine atom, and more preferred are nonafluorobutanesulfonate anion, perfluorooctanesulfonate anion, five Fluorobenzenesulfonate anion or 3,5-bis(trifluoromethyl)benzenesulfonate anion.

In terms of acid strength, in order to increase sensitivity, it is preferable that the pKa for generating acid is -1 or less.

In addition, the non-nucleophilic anion is also preferably an anion represented by the following general formula (AN1).

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In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when there are a plurality of R ¹ and R ^{2, they} may be the same or different. L represents a divalent linking group, and when there are a plurality of L, L may be the same or different. A represents a cyclic organic group. x represents an integer of 1-20, y represents an integer of 0-10, and z represents an integer of 0-10.

The general formula (AN1) is explained in more detail. The carbon number of the alkyl group in the alkyl group substituted with a fluorine atom of Xf is preferably 1-10, more preferably 1-4. In addition, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F _9, etc. Among them, a fluorine atom or CF _{3 is} preferred. It is particularly preferable that two Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and the number of carbons in the substituent is preferably 1-4. The substituent is preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Examples of the substituted alkyl groups of R ¹ and R ² _{include CF 3} , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , and C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ etc., among which CF _{3 is} preferred. R ¹ and R ^{2 are} preferably a fluorine atom or CF ₃ .

x is preferably an integer of 1-10, more preferably 1-5. y is preferably an integer of 0-4, more preferably 0. z is preferably an integer of 0-5, more preferably an integer of 0-3. Examples of the divalent linking group of L include -COO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, cycloalkylene, alkenylene, And the linking group etc. formed by linking a plurality of these are preferably a linking group having a total carbon number of 12 or less. Among them, -COO-, -CO- or -O- is preferred, and -COO- is more preferred.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure. Examples include alicyclic groups, aromatic cyclic groups, and heterocyclic groups (not only those having aromatic properties, but also those having non-aromatic properties. )Wait. The alicyclic group may be monocyclic or polycyclic, preferably monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. In addition, it is also preferably norbornyl and tricyclodecyl , Tetracyclodecyl, tetracyclododecyl and adamantyl and other polycyclic cycloalkyls. Among them, in terms of suppressing the diffusibility in the film in the heating step after exposure and improving the Mask Error Enhancement Factor (MEEF), norbornyl, tricyclodecyl, and tetracyclodecyl are preferred. Alicyclic group having a bulky structure with 7 or more carbon atoms, such as tetracyclododecyl group, and adamantyl group. As an aromatic ring group, a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, etc. are mentioned, for example. Examples of heterocyclic groups include groups derived from furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, and the like. Among them, preferred is a group derived from a furan ring, a thiophene ring, or a pyridine ring.

Moreover, as a cyclic organic group, a lactone structure can also be mentioned, As a specific example, the lactone structure represented by the said general formula (LC1-1)-(LC1-22) is mentioned.

The cyclic organic group may have a substituent. Examples of the substituent include: alkyl (which may be linear or branched, and may contain a cyclic structure. Preferably, the number of carbon atoms is 1 to 12), cycloalkyl (which may be monocyclic or polycyclic) Any one of these may be a spiro ring when it is a polycyclic ring. Preferably it is a carbon number of 3-20), an aryl group (preferably a carbon number of 6-14), a hydroxyl group, an alkoxy group, an ester group, and an acyl group Amine group, urethane group, urea group, thioether group, sulfonamide group, sulfonate group, etc. Furthermore, the carbon (carbon that contributes to ring formation) constituting the cyclic organic group may be a carbonyl carbon.

In addition, the photoacid generator may be a betaine compound having a structure in which a cation part and an anion part, and the two are connected by a covalent bond.

As the photoacid generator, paragraphs [0368] to [0377] of Japanese Patent Laid-Open No. 2014-41328 and paragraphs [0240] to [0262] of Japanese Patent Laid-Open No. 2013-228681 (corresponding U.S. Patent Application Publication No. 2015/004533 Specification [0339]), and incorporated these contents into the specification of this case. In addition, as preferred specific examples, the following compounds can be cited. In the following compounds, where possible, anions and cations can be exchanged arbitrarily.

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The content of the photoacid generator in the resist composition is not particularly limited. In terms of the more excellent effect of the present invention, it is preferably 5% by mass or more with respect to the total solid content of the composition, and more preferably 9% by mass or more, more preferably 15% by mass or more. In addition, the content is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. One type of photoacid generator may be used alone, or two or more types may be used.

＜(C) Solvent＞ The resist composition may also contain a solvent. The solvent preferably contains at least one of (M1) propylene glycol monoalkyl ether carboxylate and (M2), and the (M2) is selected from the group consisting of propylene glycol monoalkyl ether, lactate, acetate, alkoxy At least one of the group consisting of propyl propionate, chain ketone, cyclic ketone, lactone, and alkylene carbonate. In addition, the solvent may further contain components other than components (M1) and (M2).

The inventors of the present invention found that when the solvent is used in combination with the resin, the coating properties of the composition are improved and a pattern with a small number of development defects can be formed. Although the reason is not necessarily clear, the present inventors believe that the reason is that these solvents have a good balance of solubility, boiling point, and viscosity of the resin, so that the film thickness unevenness of the composition film and the spin coating can be suppressed. The production of precipitates and so on.

Component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethylether acetate (PGMEA: propylene glycol monomethylether acetate), propylene glycol monomethyl ether propionate and propylene glycol monoethyl ether acetate, and Preferably, it is propylene glycol monomethyl ether acetate (PGMEA).

The component (M2) is preferably the following solvent. The propylene glycol monoalkyl ether is preferably propylene glycol monomethylether (PGME) and propylene glycol monoethyl ether (PGEE). The lactate is preferably ethyl lactate, butyl lactate or propyl lactate. The acetate is preferably methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or acetic acid. -Methoxybutyl ester. In addition, butyl butyrate is also preferred. The alkoxy propionate is preferably methyl 3-Methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP). The chain ketone is preferably 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diiso Butyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetonyl acetone, ionone, diacetone alcohol, acetoacetone, acetophenone, methyl naphthalene Base ketone or methyl amyl ketone. The cyclic ketone is preferably methylcyclohexanone, isophorone, cyclopentanone or cyclohexanone. The lactone is preferably γ-butyrolactone. The alkylene carbonate is preferably propylene carbonate.

The component (M2) is more preferably propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, amyl acetate, and γ-butyl Lactone or propylene carbonate.

In addition to the above-mentioned components, it is preferable to use an ester solvent having a carbon number of 7 or more (preferably 7 to 14, more preferably 7 to 12, and still more preferably 7 to 10) and a heteroatom of 2 or less.

Examples of ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include pentyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, Hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate, etc., preferably isoamyl acetate.

The component (M2) is preferably a solvent having a flash point (hereinafter also referred to as fp) of 37°C or higher. The component (M2) is preferably propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methylpentyl Ketone (fp: 42°C), cyclohexanone (fp: 44°C), amyl acetate (fp: 45°C), methyl 2-hydroxyisobutyrate (fp: 45°C), γ-butyrolactone (fp : 101°C) or propylene carbonate (fp: 132°C). Among these, propylene glycol monoethyl ether, ethyl lactate, amyl acetate or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is still more preferred. In addition, here, the "flash point" refers to the value described in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.

The solvent preferably contains the component (M1). It is more preferable that the solvent contains substantially only the component (M1) or is a mixed solvent of the component (M1) and other components. In the latter case, the solvent further preferably contains both the component (M1) and the component (M2).

The mass ratio (M1/M2) of the component (M1) to the component (M2) is preferably "100/0" to "0/10", more preferably "100/0" to "15/85", and still more preferably "100/0"～"40/60", especially "100/0"～"60/40". That is, when the solvent contains both the component (M1) and the component (M2), the mass of the component (M1) relative to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and further Preferably, it is 60/40 or more. According to this configuration, the number of development defects can be further reduced.

In addition, when the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is set to 99/1 or less, for example.

As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of components other than the components (M1) and (M2) is preferably 5% by mass to 30% by mass relative to the total amount of the solvent.

The content of the solvent in the resist composition is preferably set so that the solid content concentration is 0.5% by mass to 30% by mass, and more preferably set so that the solid content concentration is 1% by mass to 20% by mass. In this way, the coatability of the resist composition can be further improved. In addition, the term "solid content" refers to all components other than the solvent.

＜(D) Acid diffusion control agent＞ The resist composition may further contain an acid diffusion control agent. The acid diffusion control agent functions as a quencher that traps the acid generated by the photoacid generator, and also functions to control the diffusion phenomenon of the acid in the resist film. The acid diffusion control agent may be, for example, a basic compound. The basic compound is preferably a compound having a structure represented by the following general formula (A) to general formula (E).

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In general formula (A) and general formula (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and represent a hydrogen atom, an alkyl group (preferably with 1 to 20 carbon atoms), a cycloalkyl group (preferably It is a carbon number of 3-20) or an aryl group (preferably a carbon number of 6-20). Here, R ²⁰¹ and R ²⁰² may also be bonded to each other to form a ring.

Regarding the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and represent an alkyl group having 1 to 20 carbon atoms. It is more preferable that the alkyl group in these general formula (A) and general formula (E) is unsubstituted.

The basic compound is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine (the alkyl part may be linear or branched) In the form, a part may be substituted with ether groups and/or ester groups. The total number of all atoms other than hydrogen atoms in the alkyl part is preferably 1-17), piperidine, or the like. Among them, more preferred are compounds having an imidazole structure, a diazabicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, and an alkyl group having a hydroxyl group and/or an ether bond. Amine derivatives, or aniline derivatives having a hydroxyl group and/or ether bond, etc.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of the compound having a diazabicyclic structure include: 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5 -Ene and 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of the compound having an onium hydroxide structure include triaryl sulfonium hydroxide, benzyl methyl sulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. Specifically, examples include: triphenyl sulfonium hydroxide, tris(tertiary butylphenyl) sulfonium hydroxide, bis(tertiary butylphenyl) iodine hydroxide, benzylmethylthiophenium hydroxide, and 2-oxopropyl thiophenium hydroxide and the like. The compound having an onium carboxylate structure is one in which the anion portion of the compound having an onium hydroxide structure becomes a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the aniline compound include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of alkylamine derivatives having hydroxyl groups and/or ether bonds include ethanolamine, diethanolamine, triethanolamine, tris(methoxyethoxyethyl)amine, and (HO-C ₂ H ₄ -OC ₂ H ₄ ) ₂ N(-C ₃ H ₆ -O-CH ₃ ) and so on. As an aniline derivative which has a hydroxyl group and/or an ether bond, N,N-bis(hydroxyethyl) aniline etc. are mentioned, for example.

As a basic compound, the amine compound which has a phenoxy group and the ammonium salt compound which has a phenoxy group are mentioned suitably.

As the amine compound, for example, primary, secondary, and tertiary amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferred. The amine compound is more preferably a tertiary amine compound. In the amine compound, if at least one alkyl group (preferably carbon number 1-20) is bonded to a nitrogen atom, in addition to the alkyl group, a cycloalkyl group (preferably a carbon number 3-20) or an aryl group (preferably It has 6 to 12 carbon atoms) and can also be bonded to a nitrogen atom. In addition, the amine compound preferably has an oxyalkylene group. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3-9, and still more preferably 4-6. The oxyalkylene group is also preferably an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group (-CH(CH ₃ )CH ₂ O- or CH ₂ CH ₂ CH ₂ O-), more preferably For oxyethylene.

Examples of the ammonium salt compound include primary, secondary, tertiary, and quaternary ammonium salt compounds, and ammonium salt compounds in which at least one alkyl group is bonded to a nitrogen atom are preferred. In the ammonium salt compound, if at least one alkyl group (preferably carbon number 1-20) is bonded to a nitrogen atom, in addition to the alkyl group, a cycloalkyl group (preferably a carbon number 3-20) or an aryl group (more Preferably, the carbon number is 6-12) and it can also be bonded to the nitrogen atom. The ammonium salt compound preferably has an oxyalkylene group. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3-9, and still more preferably 4-6. The oxyalkylene group is also preferably an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-), and more Preferably it is oxyethylene. As an anion of an ammonium salt compound, a halogen atom, a sulfonate, a borate, a phosphate, etc. are mentioned, for example, Among these, a halogen atom or a sulfonate is preferable. The halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom. The sulfonate is preferably an organic sulfonate having 1 to 20 carbon atoms. Examples of organic sulfonates include alkyl sulfonates and aryl sulfonates having 1 to 20 carbon atoms. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aromatic ring group. Examples of alkyl sulfonates include methanesulfonate, ethanesulfonate, butanesulfonate, hexylsulfonate, octylsulfonate, benzylsulfonate, trifluoromethanesulfonate, five Fluoroethanesulfonate and nonafluorobutanesulfonate, etc. Examples of the aryl group of the arylsulfonate include a benzene ring group, a naphthalene ring group, and an anthracene ring group. The substituent which the benzene ring group, naphthyl ring group, and anthracyclyl group may have is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. Examples of linear or branched alkyl groups and cycloalkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, and Cyclohexyl and so on. Examples of other substituents include alkoxy groups having 1 to 6 carbon atoms, halogen atoms, cyano groups, nitro groups, acyl groups, and acyloxy groups.

The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group refer to a compound having a phenoxy group at the end of the alkyl group of the amine compound or the ammonium salt compound on the opposite side to the nitrogen atom. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxylic acid group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, and an Oxy and aryloxy, etc. The substitution position of the substituent may be any of the 2-position to the 6-position. The number of substituents may be any one of 1-5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3-9, and still more preferably 4-6. The oxyalkylene group is also preferably an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-), and more Preferably it is oxyethylene.

The amine compound having a phenoxy group can be obtained by heating and reacting a primary or secondary amine having a phenoxy group and a halogenated alkyl ether, and then adding a strong base (such as sodium hydroxide, potassium hydroxide, etc.) to the reaction system. And an aqueous solution of tetraalkylammonium, etc.), and then extract the reaction product with an organic solvent (for example, ethyl acetate, chloroform, etc.) to obtain it. Alternatively, it can be obtained by heating and reacting a primary amine or a secondary amine and a halogenated alkyl ether having a phenoxy group at the end, adding an aqueous solution of a strong base to the reaction system, and then extracting the reaction product with an organic solvent.

(Compounds (PA) that have a proton-accepting functional group and are decomposed by the irradiation of actinic rays or radiation to produce a compound (PA) whose proton-accepting properties are reduced, disappeared, or changed from proton-accepting properties to acidic properties) The resist composition may also contain: a compound having a proton-accepting functional group that is decomposed by irradiation with actinic rays or radiation to produce a compound whose proton-accepting property decreases or disappears or changes from proton-accepting property to acidity (Hereinafter, it is also referred to as a compound (PA)) as an acid diffusion control agent.

The so-called proton-accepting functional group refers to a functional group having a group or electrons that can electrostatically interact with protons. For example, it refers to a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group containing A functional group that conjugates the nitrogen atom of a non-shared electron pair. The nitrogen atom having a non-shared electron pair that does not contribute to π-conjugation means, for example, a nitrogen atom having a partial structure represented by the following general formula.

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Examples of preferable partial structures of the proton-accepting functional group include a crown ether structure, an aza crown ether structure, a primary amine structure to a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

The compound (PA) is decomposed by irradiation with actinic rays or radiation to produce a compound in which the proton acceptor property decreases or disappears, or the proton acceptor property changes to acidity. Here, the decrease or disappearance of proton acceptor property or the change from proton acceptor property to acidity refers to the change in proton acceptor property caused by the addition of protons to the proton acceptor functional group. Specifically, it means that when a proton adduct is generated from a compound (PA) having a proton-accepting functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium decreases.

As the compound (PA), for example, the compounds described in paragraphs [0421] to [0428] of JP 2014-41328 and paragraphs [0108] to [0116] of JP 2014-134686 can be cited. , Incorporate these contents into this manual.

A low-molecular compound having a nitrogen atom and having a group detached by the action of an acid can also be used as an acid diffusion control agent. The low-molecular compound is preferably an amine derivative having a group detached by the action of an acid on the nitrogen atom. The group to be removed by the action of an acid is preferably an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group or a semiamine acetal ether group, more preferably a urethane group or Semiamine acetal ether group. The molecular weight of the low-molecular compound is preferably 100-1000, more preferably 100-700, and still more preferably 100-500. The low-molecular compound may also have a urethane group containing a protective group on the nitrogen atom.

The specific example of the acid diffusion control agent is as follows, but the present invention is not limited to this.

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When the resist composition contains an acid diffusion control agent, the content of the acid diffusion control agent is preferably 0.001% by mass to 15% by mass, more preferably 0.01% by mass relative to the total solid content of the resist composition ～8% by mass. One kind of acid diffusion control agent may be used alone, or two or more kinds may be used. In addition, when the resist composition contains a compound represented by general formula (PB) as a photoacid generator, the compound represented by general formula (PB) contains a structure having a function equivalent to an acid diffusion control agent, Therefore, it is also preferable that the resist composition does not substantially contain an acid diffusion control agent. Here, the term "substantially not containing the acid diffusion control agent" means that the content of the acid diffusion control agent is 5% by mass or less with respect to the content of the compound represented by the general formula (PB).

The use ratio of the photoacid generator and the acid diffusion control agent in the resist composition is preferably the photoacid generator/acid diffusion control agent (molar ratio)=2.5-300. In terms of sensitivity and resolution, the molar ratio is preferably 2.5 or more. In terms of suppressing the decrease in resolution due to the thickening of the resist pattern over time until the heat treatment after exposure, it is not The ear ratio is preferably 300 or less. The photoacid generator/acid diffusion control agent (mole ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

As the acid diffusion control agent, for example, the compounds described in paragraphs [0140] to [0144] of Japanese Patent Laid-Open No. 2013-11833 (amine compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic rings) Compounds, etc.).

＜(E) Hydrophobic resin＞ The resist composition may contain a hydrophobic resin different from the resin (A) in addition to the resin (A). The hydrophobic resin is preferably designed to be biased to exist on the surface of the resist film, but unlike surfactants, it is not necessary to have a hydrophilic group in the molecule, and it may not help uniformly mix polar and non-polar substances. As an effect of adding a hydrophobic resin, control of the static and dynamic contact angle of the surface of the resist film with respect to water, suppression of gas escape, and the like can be cited.

In terms of the existence of bias toward the film surface layer, the hydrophobic resin preferably has any one or more of _{"fluorine atom", "silicon atom", and "CH 3 partial structure contained in the side chain part of the resin",} More preferably, there are two or more types. In addition, the hydrophobic resin preferably has a hydrocarbon group with 5 or more carbon atoms. These groups may exist in the main chain of the resin, or may be substituted in the side chain.

When the hydrophobic resin contains fluorine atoms and/or silicon atoms, the fluorine atoms and/or silicon atoms in the hydrophobic resin may be included in the main chain of the resin, or may be included in the side chain.

When the hydrophobic resin contains a fluorine atom, the partial structure having a fluorine atom is preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. The alkyl group having a fluorine atom (preferably with 1 to 10 carbons, more preferably with 1 to 4 carbons) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have Substituents other than fluorine atoms. The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. Examples of the aryl group having a fluorine atom include a group in which at least one hydrogen atom of an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and it may further have a substituent other than a fluorine atom. As the repeating unit having a fluorine atom or a silicon atom, for example, the repeating unit exemplified in paragraph [0519] of US2012/0251948A1 can be cited.

In addition, as described above, it is also preferable that the hydrophobic resin contains a CH ₃ partial structure in the side chain portion. Here, the side chain portion of the hydrophobic resin has a partial structure comprising a CH _{3 3} ethyl and propyl partial structure possessed CH. On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) is biased toward the surface of the hydrophobic resin due to the influence of the main chain. The contribution is small, so it is not included in the CH ₃ partial structure of the present invention.

Regarding the hydrophobic resin, reference can be made to the description of paragraphs [0348] to [0415] of JP 2014-010245 A, and these contents are incorporated into the specification of the present application.

In addition, as the hydrophobic resin, the resins described in Japanese Patent Application Publication No. 2011-248019, Japanese Patent Application Publication No. 2010-175859, and Japanese Patent Application Publication No. 2012-032544 may also be preferably used.

When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 15%, relative to the total solid content of the resist composition. quality%.

＜(F) Surfactant＞ The resist composition may also contain a surfactant. If a surfactant is contained, a pattern with more excellent adhesiveness and fewer development defects can be formed. The surfactant is preferably a fluorine-based and/or silicon-based surfactant. Examples of the fluorine-based and/or silicon-based surfactants include the surfactants described in paragraph [0276] of the specification of US Patent Application Publication No. 2008/0248425. In addition, Eftop EF301 or EF303 (manufactured by New Akita Chemical Co., Ltd.); Fluorad FC430, 431 and 4430 (manufactured by Sumitomo 3M Co., Ltd.) can also be used; Megafac F171 , F173, F176, F189, F113, F110, F177, F120 and R08 (manufactured by DIC (Stock)); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (Asahi Glass (Stock) Manufacturing); Troysol S-366 (manufactured by Troy Chemical (stock)); GF-300 or GF-150 (manufactured by Dongya Synthetic Chemical Co., Ltd.), saflon (Surflon) S- 393 (manufactured by Seimi Chemical (shares)); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (Jemco) (shares) ) Manufacturing); PF636, PF656, PF6320, and PF6520 (manufactured by Onofa (OMNOVA)); KH-20 (manufactured by Asahi Kasei (Stock)); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D And 222D (manufactured by NEOS (stock)). Furthermore, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition, the surfactant can also be used by short-chain polymerization (telomerization) method (also known as telomerization method) or oligomerization method (also known as oligomerization) in addition to the well-known surfactants shown above. Oligomer method) to produce fluorinated aliphatic compounds. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can also be used as a surfactant. The fluorinated aliphatic compound can be synthesized, for example, by the method described in Japanese Patent Laid-Open No. 2002-90991. In addition, the fluorine-based and/or silicon-based surfactants described in paragraph [0280] of the specification of U.S. Patent Application Publication No. 2008/0248425 may also be used.

These surfactants may be used singly, or two or more of them may be used.

When the resist composition contains a surfactant, the content of the surfactant is preferably 0.0001% by mass to 2% by mass, and more preferably 0.0005% by mass to 1% by mass relative to the total solid content of the composition.

＜(G) Other additives＞ The resist composition may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (for example, a phenol compound with a molecular weight of 1000 or less, or Alicyclic or aliphatic compounds containing carboxylic acid groups).

The resist composition may further contain a dissolution inhibiting compound. Here, the "dissolution inhibiting compound" refers to a compound having a molecular weight of 3000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[Pattern Formation Method] The order of the pattern formation method using the resist composition is not particularly limited, but it is preferable to have the following steps. Step 1: Step of forming a resist film on a substrate using a resist composition Step 2: The step of exposing the resist film (preferably using EUV light) Step 3: Use a developer to develop the exposed resist film to form a pattern Hereinafter, the order of each step is described in detail.

<Step 1: Resist film formation step> Step 1 is a step of forming a resist film on a substrate using the resist composition. The definition of the resist composition is as described above.

As a method of forming a resist film on a substrate using the resist composition, for example, a method of applying the resist composition on the substrate can be cited. Furthermore, it is preferable to filter the resist composition as necessary before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. In addition, the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

The resist composition can be coated on a substrate (for example, silicon, silicon dioxide coating) used in the manufacture of integrated circuit parts by an appropriate coating method such as a spinner or a coater. The coating method is preferably spin coating using a spinner. The rotation speed when the spinner is used for spin coating is preferably 1000 rpm to 3000 rpm. After coating the resist composition, the substrate may be dried to form a resist film. Furthermore, various base films (inorganic film, organic film, anti-reflection film) may be formed on the lower layer of the resist film as needed.

As a drying method, the method of heating and drying is mentioned, for example. Heating can be performed by a mechanism provided in a normal exposure machine and/or a developing machine, or a hot plate or the like can be used. The heating temperature is preferably 80°C to 150°C, more preferably 80°C to 140°C, and still more preferably 80°C to 130°C. The heating time is preferably 30 seconds to 1000 seconds, more preferably 60 seconds to 800 seconds, and still more preferably 60 seconds to 600 seconds.

The thickness of the resist film is not particularly limited. In terms of forming a finer pattern with higher accuracy, it is preferably 10 nm to 65 nm, and more preferably 15 nm to 50 nm.

Furthermore, a top coat composition may be used on the upper layer of the resist film to form a top coat. The top coat composition is preferably not mixed with the resist film, and can be evenly coated on the upper layer of the resist film. In addition, it is preferable to dry the resist film before forming the top coat layer. Then, on the obtained resist film, the top coat composition is applied by the same method as the formation method of the above-mentioned resist film, and then dried to form the top coat. The film thickness of the top coating layer is preferably 10 nm to 200 nm, more preferably 20 nm to 100 nm, and still more preferably 40 nm to 80 nm. The top coat layer is not particularly limited, and a conventionally known top coat layer can be formed by a conventionally known method. For example, it can be formed based on the description in paragraphs [0072] to [0082] of Japanese Patent Laid-Open No. 2014-059543 Top coat. For example, it is preferable to form a top coat layer containing a basic compound as described in JP 2013-61648 A on the resist film. Specific examples of the basic compound that can be contained in the top coat layer include basic compounds that can be contained in the resist composition described later. In addition, the top coating layer preferably contains a compound having at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

<Step 2: Exposure Step> Step 2 is a step of exposing the resist film (preferably using EUV light). As a method of exposure, for example, a method of irradiating the formed resist film with EUV light through a predetermined mask.

Preferably, baking (heating) is performed after exposure and before development. By baking to promote the reaction of the exposed part, the sensitivity and pattern shape become better. The heating temperature is preferably 80°C to 150°C, more preferably 80°C to 140°C, and still more preferably 80°C to 130°C. The heating time is preferably 10 seconds to 1000 seconds, more preferably 10 seconds to 180 seconds, and still more preferably 30 seconds to 120 seconds. Heating can be performed by a mechanism provided in a normal exposure machine and/or a developing machine, or a hot plate or the like can be used. This step is also called post-exposure baking.

<Step 3: Development Step> Step 3 is a step of developing the exposed resist film using a developing solution to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).

Examples of the development method include: a method of immersing the substrate in a tank filled with a developer solution for a fixed period of time (dipping method); a method of depositing the developer solution on the surface of the substrate using surface tension and resting for a fixed period of time to perform development (coating liquid ( Puddle method); a method of spraying developer on the surface of the substrate (spray method); and a method of continuously spraying developer on a substrate rotating at a fixed speed while scanning the developer spray nozzle at a fixed speed (dynamic distribution method). In addition, after the step of performing the development, a step of stopping the development while being replaced with another solvent may be performed. The development time is not particularly limited as long as the resin in the unexposed part is fully dissolved, and it is preferably 10 seconds to 300 seconds, and more preferably 20 seconds to 120 seconds. The temperature of the developer is preferably 0°C to 50°C, more preferably 15°C to 35°C.

As the alkaline developer, it is preferable to use an alkaline aqueous solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, and examples include quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic bases, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. The alkaline aqueous solution. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by Tetramethyl Ammonium Hydroxide (TMAH). An appropriate amount of alcohols, surfactants, etc. can also be added to the alkaline developer. The alkali concentration of the alkaline developer is usually 0.1% by mass to 20% by mass. In addition, the pH of the alkaline developer is usually 10.0 to 15.0.

The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylpentyl ketone), 4-heptanone, 1- Hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetonyl acetone, purple Protonone, diacetone alcohol, acetoxynol, acetophenone, methyl naphthyl ketone, isophorone and propylene carbonate, etc.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, acetic acid pentyl, isoamyl acetate, acetic acid amyl, and propylene glycol. Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, Propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate and butyl propionate, etc.

As alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents, for example, the solvents disclosed in paragraphs [0715] to [0718] of the specification of U.S. Patent Application Publication No. 2016/0070167A1 can be used.

A plurality of the solvents may be mixed, or may be mixed with solvents or water other than the above. The moisture content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably contains substantially no water. Relative to the total amount of the developer, the content of the organic solvent relative to the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and still more preferably 90% by mass Above and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less.

＜Other steps＞ The pattern forming method preferably includes a step of cleaning with an eluent after step 3.

As the rinsing liquid used in the rinsing step after the step of performing development using an alkaline developer, for example, pure water can be cited. Furthermore, an appropriate amount of surfactant may be added to pure water. It is also possible to add an appropriate amount of surfactant to the eluent.

The rinsing liquid used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. The eluent is preferably an eluent containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents. Examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include the same as those described in the developer containing an organic solvent.

The method of the rinsing step is not particularly limited. For example, a method of continuously spraying a rinsing liquid on a substrate rotating at a fixed speed (spin coating method), and a method of immersing the substrate in a tank filled with the rinsing liquid for a fixed period of time Method (dipping method), and method of spraying eluent on the surface of the substrate (spray method), etc. In addition, the pattern forming method of the present invention may also include a heating step (Post Bake) after the rinsing step. Through this step, baking is used to remove the developer and rinsing liquid remaining between and inside the patterns. In addition, this step also has the effect of forming a resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40°C to 250°C (preferably 90°C to 200°C), usually 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

In addition, the formed pattern may be used as a mask to perform the etching treatment of the substrate. That is, the pattern formed in step 3 may be used as a mask, and the substrate (or the underlying film and the substrate) may be processed to form a pattern on the substrate. The processing method of the substrate (or the underlying film and the substrate) is not particularly limited, and it is preferable to dry-etch the substrate (or the underlying film and the substrate) by using the pattern formed in step 3 as a mask to form a pattern on the substrate. method. Dry etching may be one-stage etching, or may include multiple-stage etching. When the etching includes multiple stages of etching, the etching of each stage may be the same treatment or different treatments. Any known method can be used for etching, and various conditions and the like are appropriately determined according to the type of substrate, use, and the like. For example, the etching can be performed based on "Proceeding of Society of Photo-optical Instrumentation Engineers (Proc. of SPIE)" Vol. 6924, 692420 (2008), Japanese Patent Laid-Open No. 2009-267112, etc. . In addition, the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook 4th Edition 2007 Issued by: SEMI Japan" can also be used. Among them, the dry etching is preferably oxygen plasma etching.

The resist composition and the various materials used in the pattern forming method of the present invention (for example, solvent, developer, rinsing solution, composition for forming anti-reflection film, composition for forming top coat, etc.) are preferably free of Impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, further preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. Here, as metal impurities, for example, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V , W and Zn, etc.

As a method of removing impurities such as metals from various materials, for example, filtration using a filter can be cited. The filter pore size is preferably less than 100 nm, more preferably 10 nm or less, and still more preferably 5 nm or less. The filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. The filter may also be composed of a composite material combining the filter material and the ion exchange medium. The filter can also be a filter that has been cleaned with an organic solvent in advance. In the filter filtration step, multiple filters can also be connected in series or parallel for use. When multiple filters are used, filters with different pore sizes and/or materials can be used in combination. In addition, various materials can also be filtered multiple times, and the step of multiple filtering can be a cyclic filtering step. In the manufacture of a resist composition, it is preferable to perform cyclic filtration using a plurality of filters with different materials after dissolving each component such as a resin and a photoacid generator in a solvent, for example. For example, it is preferable to arrange and connect a polyethylene filter with a pore diameter of 50 nm, a nylon filter with a pore diameter of 10 nm, and a polyethylene filter with a pore diameter of 3 nm, and to perform the filtration cycle 10 times or more. The pressure difference between the filters is as small as possible, usually 0.1 MPa or less, preferably 0.05 MPa or less, and more preferably 0.01 MPa or less. The pressure difference between the filter and the filling nozzle is also as small as possible, usually 0.5 MPa or less, preferably 0.2 MPa or less, and more preferably 0.1 MPa or less. The inside of the manufacturing apparatus of the resist composition is preferably replaced with an inert gas such as nitrogen. This can prevent active gases such as oxygen from being dissolved in the resist composition. The resist composition is filtered through a filter and then filled into a clean container. The resist composition filled in the container is preferably stored under refrigeration. Thereby, performance degradation caused by time can be suppressed. The shorter the time from the completion of the filling of the composition into the container to the start of refrigerated storage, the better, and it is usually within 24 hours, preferably within 16 hours, more preferably within 12 hours, and more preferably within 10 hours. The storage temperature is preferably 0°C to 15°C, more preferably 0°C to 10°C, and still more preferably 0°C to 5°C.

In addition, as a method of reducing impurities such as metals contained in various materials, for example, the following methods can be cited: a method of selecting a raw material with a small metal content as a raw material constituting various materials, a method of filtering a raw material constituting various materials with a filter , And the method of using Teflon (registered trademark) to lining the device, etc., and distilling under the condition of suppressing pollution as much as possible.

In addition to filter filtration, adsorption materials can also be used to remove impurities, and filter filtration and adsorption materials can also be used in combination. As the adsorbent, a well-known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the mixing of metal impurities in the manufacturing process. It is possible to measure the content of the metal components contained in the cleaning liquid used for cleaning the manufacturing equipment to confirm whether the metal impurities are sufficiently removed from the manufacturing equipment. The content of the metal component contained in the cleaning solution after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and still more preferably 1 mass ppt or less.

In order to prevent malfunctions of the chemical liquid piping and various components (filters, O-rings, tubes, etc.) caused by static electricity and subsequent electrostatic discharge, it is also possible to add conductivity to organic treatment liquids such as eluents Sexual compounds. The conductive compound is not particularly limited, and for example, methanol can be mentioned. The addition amount is not particularly limited, but it is preferably 10% by mass or less, and more preferably 5% by mass or less in terms of maintaining better development characteristics or rinsing characteristics. As the chemical solution piping, for example, various piping coated with SUS (stainless steel) or antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used. Regarding the filter and O-ring, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) that has been subjected to antistatic treatment can also be used in the same way.

For the pattern formed by the method of the present invention, a method of improving the surface roughness of the pattern can be applied. As a method of improving the surface roughness of a pattern, for example, a method of processing a pattern using plasma of a hydrogen-containing gas disclosed in International Publication No. 2014/002808 can be cited. In addition, Japanese Patent Laid-Open No. 2004-235468, U.S. Patent Application Publication No. 2010/0020297, Japanese Patent Laid-Open No. 2008-83384, and Proc. of SPIE ) Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement for reducing line width roughness and enhancing etching selectivity" is a well-known method described in.

When the formed pattern is linear, the aspect ratio calculated by dividing the pattern height by the line width is preferably 2.5 or less, more preferably 2.1 or less, and still more preferably 1.7 or less. When the pattern to be formed is a groove (groove) pattern or a contact hole pattern, the aspect ratio calculated by dividing the pattern height by the groove width or hole diameter is preferably 4.0 or less, more preferably 3.5 or less , And more preferably 3.0 or less.

The pattern forming method of the present invention can also be used for guiding pattern formation in Directed Self-Assembly (DSA) (for example, refer to "ASC Nano (ACS Nano)" Vol. 4 No. 8 4815-4823).

In addition, the pattern formed by the method described above can be used as a core of the spacer process disclosed in Japanese Patent Laid-Open No. 3-270227 and Japanese Patent Laid-Open No. 2013-164509, for example.

In addition, the present invention also relates to a manufacturing method of an electronic component including the pattern forming method, and an electronic component manufactured by the manufacturing method. The electronic component of the present invention can be preferably mounted in electrical and electronic equipment (home appliances, office automation (OA), media-related equipment, optical equipment, communication equipment, etc.). [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amount, ratio, processing content, processing order, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.

[Components of resist composition (sensitized radiation-sensitive or radiation-sensitive resin composition)] [Resin] Hereinafter, the repeating unit each resin (A-1 to A-26, A'-1 to A'-6) used in the manufacture of the resist composition has is shown. Furthermore, resins A-1～A-26, A'-1～A’-2 and A’-4～A’-6 are acid-decomposable resins, and resin A’-3 is resins other than acid-decomposable resins. .

[化60]

[化61]

[化62]

The following table shows the content of each repeating unit in each resin, the weight average molecular weight (Mw), and the degree of dispersion (Mw/Mn). In addition, the repeating molar ratio in the table is the content (molar ratio) occupied by each repeating unit constituting each resin shown in the upper paragraph in order from the left. In addition, the content of each repeating unit ^{was measured by 13} C-nuclear magnetic resonance (NMR). The weight average molecular weight and the degree of dispersion are based on the polystyrene conversion value measured by GPC (carrier: tetrahydrofuran (THF)).

[Table 1] Table 1 Repeated molar ratio Mw Mw/Mn A-1 20 30 50 - - 6500 1.52 A-2 10 10 60 20 - 8300 1.65 A-3 40 60 - - - 7800 1.55 A-4 20 20 60 - - 12000 1.68 A-5 60 10 30 - - 5500 1.49 A-6 70 15 5 10 - 8600 1.63 A-7 55 25 20 - - 9600 1.72 A-8 60 30 10 - - 10200 1.64 A-9 65 15 10 10 - 7500 1.54 A-10 70 10 20 - - 7000 1.61 A-11 65 15 20 - - 6500 1.63 A-12 40 30 20 10 - 5900 1.59 A-13 65 25 10 - - 5200 1.53 A-14 10 50 35 5 - 6200 1.48 A-15 60 40 - - - 7000 1.73 A-16 70 10 20 - - 11500 1.56 A-17 70 10 20 - - 8400 1.58 A-18 60 15 10 15 - 9200 1.66 A-19 55 25 20 - - 5700 1.75 A-20 65 20 15 - - 7600 1.56 A-21 60 20 20 - - 8000 1.45 A-22 70 25 5 - - 4900 1.43 A-23 65 15 20 - - 5200 1.65 A-24 20 30 50 - - 7700 1.55 A-25 40 20 20 20 - 6000 1.73 A-26 30 10 60 - - 12000 1.66 A'-1 40 60 - - - 8000 1.65 A'-2 50 50 - - - 9000 1.57 A'-3 50 50 - - - 11000 1.78 A'-4 40 60 - - - 8000 1.65 A'-5 40 60 - - - 8000 1.65 A'-6 26 47 12 5 10 8000 1.65

<Synthesis Example 1: Synthesis of Resin A-1> Cyclohexanone (226 g) was heated to 80°C under a stream of nitrogen. While stirring for 6 hours, the monomer represented by the following formula M-1 (21.5 g), the monomer represented by the following formula M-2 (21.6 g), and the monomer represented by the following formula M-3 (58.3 g), cyclohexanone (420 g) and dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by Wako Pure Chemical Industries Co., Ltd.) (12.42 g) are added dropwise Into the cyclohexanone, a reaction liquid is obtained. After completion of the dropwise addition, the reaction solution was further stirred at 80°C for 2 hours. After the obtained reaction liquid was left to cool, it was reprecipitated with a large amount of methanol/water (mass ratio 9:1) and then filtered, and the obtained solid was vacuum dried to obtain resin A-1 (89 g).

[化63]

The weight average molecular weight (Mw: polystyrene conversion) of the obtained resin A-1 determined by GPC (carrier: tetrahydrofuran (THF)) was 6,500, and the degree of dispersion (Mw/Mn) was 1.52. The composition ratio determined by ¹³ C-NMR (nuclear magnetic resonance) is M-1 based unit/M-2 based unit/M-3 based unit=20/30/50 (mole ratio).

The other resins are also synthesized in the same way.

[Photo Acid Generator] Use the photoacid generator shown below. Photo acid generator B-1 ~ photo acid generator B-3 are compounds represented by general formula (PB), and photo acid generator C-1 ~ photo acid generator C-12 are represented by general formula (PB) Photo acid generators other than compounds. Photo acid generator C-9 to photo acid generator C-12 are compounds represented by general formula (PA-1).

[化64]

[化65]

[化66]

[Acid Diffusion Control Agent] Use the acid diffusion control agent shown below.

[化67]

[Surfactant] Use the surfactant shown below. H-1: Megafac F176 (manufactured by DIC (Stock), fluorine-based surfactant) H-2: Megafac R08 (manufactured by DIC (stock), fluorine-based and silicon-based surfactants) H-3: PF656 (manufactured by OMNOVA, fluorine-based surfactant)

[Solvent] Use the solvents shown below. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6: 2-Heptanone F-7: Ethyl lactate F-8: γ-butyrolactone F-9: propylene carbonate

[Preparation of resist composition] The components shown in Table 2 were mixed so that the solid content concentration became 2.0% by mass. Then, the obtained mixed solution was circulated and filtered in the order of a polyethylene filter with a pore size of 50 nm, a nylon filter with a pore size of 10 nm, and a polyethylene filter with a pore size of 5 nm. Resist composition (Re-1 to Re-50, Re'-1 to Re'-6). In addition, the term "solid content" refers to all components other than the solvent. The obtained resist composition was used in Examples and Comparative Examples. In addition, in the table, the "amount" column indicates the content (mass %) of each component with respect to the total solid content in the resist composition.

[Table 2] Table 2 Solid content Solvent Resin Photoacid generator Acid diffusion control agent Surfactant species the amount species the amount species the amount species the amount species the amount species Mixing ratio (mass ratio) Re-1 A-1 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-2 A-2 79.3 - - C-2 13.8 D-1 6.9 - - F-1/F-8 85/15 Re-3 A-3 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-4 A-4 76.5 - - C-3 14.8 D-4 8.7 - - F-1/F-5 85/15 Re-5 A-5 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-6 A-6 82.1 - - C-4 13.1 D-3 4.8 - - F-1/F-9 85/15 Re-7 A-7 84.3 - - C-5/C-7 5.5/5.0 D-4 5 H-2 0.2 F-1/F-3 70/30 Re-8 A-8 82.9 - - C-6 14.2 D-3 2.9 - - F-1/F-7 90/10 Re-9 A-9 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-10 A-10 85.3 - - C-7 9.8 D-5 4.9 - - F-1/F-2/F-6 70/20/10 Re-11 A-11 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-12 A-12 79.9 - - C-8 13.8 D-5 6.3 - - F-1/F-4 80/20 Re-13 A-13 81.2 - - C-2 14.1 D-1 4.7 - - F-1/F-2/F-5 60/30/10 Re-14 A-14 83.5 - - C-3 10.2 D-4 6.2 H-1 0.1 F-4 100 Re-15 A-15 84.2 - - C-8 10.2 D-3 5.6 - - F-1/F-5 85/15 Re-16 A-16 80.2 - - C-2 13.4 D-1/D-2 4.4/2.0 - - F-1/F-3 75/25 Re-17 A-17 80.9 - - C-1/C-4 8.7/4.0 D-5 6.4 - - F-1/F-2 80/20 Re-18 A-18 84.5 - - C-3 10.5 D-3 5 - - F-1/F-8 85/15 Re-19 A-19 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-20 A-20 86.1 - - C-7 9.4 D-3 4.5 - - F-1/F-6 80/20 Re-21 A-21 85.0 - - C-4 10.5 D-4 4.4 H-3 0.1 F-1/F-8 85/15 Re-22 A-22 84.9 - - C-4 10.9 D-2 4.2 - - F-1/F-2/F-8 80/15/5 Re-23 A-23 83.2 - - C-8 11.9 D-1 4.9 - - F-1/F-2 80/20 Re-24 A-24 82.9 - - C-6 14.2 D-3 2.9 - - F-1/F-7 90/10 Re-25 A-25 79.3 - - C-2 13.8 D-1 6.9 - - F-1/F-4 85/15 Re-26 A-26 82.1 - - C-4 13.1 D-3 4.8 - - F-1/F-8 85/15 Re-27 A-1 82.0 - - C-9 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-28 A-5 82.0 - - C-10 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-29 A-9 82.0 - - C-11 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-30 A-11 82.0 - - C-12 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-31 A-19 82.0 - - C-10 13.0 D-1 5.0 - - F-1/F-2 80/20 Re-32 A-22 84.5 - - C-9/C-10 8.0/2.5 D-3 5.0 - - F-1/F-4 80/20 Re-33 A-1 82.0 B-1 13.9 C-6 4.1 - - - - F-1/F-2 80/20 Re-34 A-5 82.0 B-2 13.9 C-6 4.1 - - - - F-1/F-2 80/20 Re-35 A-9 82.0 B-3 13.9 C-6 4.1 - - - - F-1/F-2 80/20 Re-36 A-11 82.0 B-1 13.9 C-6 4.1 - - - - F-1/F-2 80/20 Re-37 A-19 82.0 B-2 13.9 C-6 4.1 - - - - F-1/F-2 80/20 Re-38 A-20 84.7 B-1 14.1 C-4 0.8 D-4 0.3 H-3 0.1 F-1/F-6 80/20 Re-39 A-21 84.9 B-2 10.9 - - D-2 4.2 - - F-1/F-8 85/15 Re-40 A-22 83.2 B-3 11.9 C-8 3.8 D-1 1.1 - - F-1/F-2/F-8 80/15/5 Re-41 A-22 87.3 B-3 12.7 - - - - - - F-1/F-2 80/20 Re-42 A-1 82.0 - - C-1 15.1 D-1 2.9 - - F-1/F-2 80/20 Re-43 A-5 80.1 - - C-1 17.6 D-1 2.3 - - F-1/F-2 80/20 Re-44 A-9 76.6 - - C-1 18.4 D-1 5.0 - - F-1/F-2 80/20 Re-45 A-11 82.0 - - C-1 16.0 D-1 2.0 - - F-1/F-2 80/20 Re-46 A-19 73.0 - - C-1 22.2 D-1 4.8 - - F-1/F-2 80/20 Re-47 A-21 72.5 B-2 20.1 C-9 0.4 D-2 7.0 - - F-1/F-2 80/20 Re-48 A-20 70.9 B-1 18.5 C-2 5.5 D-3 5.1 - - F-1/F-2 80/20 Re-49 A-22 80.5 B-3 19.5 - - - - - - F-1/F-2 80/20 Re-50 A-19 73.0 B-1 23.1 C-4 3.9 - - - - F-1/F-2 80/20 Re'-1 A'-1 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re'-2 A'-2 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re'-3 A'-3 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re'-4 A'-4 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re'-5 A'-5 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20 Re'-6 A'-6 82.0 - - C-1 13.0 D-1 5.0 - - F-1/F-2 80/20

[Pattern Formation] [EUV exposure, organic solvent development] A 12-inch diameter silicon wafer was coated with an underlayer film forming composition AL412 (manufactured by Brewer Science), and baked at 205°C for 60 seconds to form a base film with a thickness of 20 nm. The resist composition shown in Table 3 was coated thereon, and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Using EUV exposure equipment (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupole, Out Sigma 0.68, Ne Sigma 0.36), the resist film obtained The silicon wafer is patterned so that the average line width of the resulting pattern becomes 20 nm. Furthermore, as a reticle, a mask with line size=20 nm and line:space=1:1 is used. After the exposed resist film was baked at 90°C for 60 seconds, it was developed with n-butyl acetate for 30 seconds, and it was spin-dried to obtain a negative pattern.

[Evaluation] ＜Defect evaluation (defect suppression)＞ Regarding the patterns obtained by the above method, using UVision5 (manufactured by AMAT) and SEMVisionG4 (manufactured by AMAT), the number of defects per silicon wafer was calculated and evaluated according to the following evaluation criteria. The fewer the number of defects, the better the defect suppression. In addition, in the evaluation of defect suppression properties, the resist composition immediately after preparation was used to form a pattern and used for evaluation. "A": The number of defects is less than 50 "B": The number of defects exceeds 50 and is less than 100 "C": The number of defects exceeds 100 and is less than 200 "D": The number of defects exceeds 200 and is less than 300 "E": The number of defects exceeds 300 and is less than 400 "F": The number of defects exceeds 400 and is less than 500 "G": The number of defects exceeds 500

<Line width roughness after time (LWR performance after time, nm)> The pattern obtained by the method was observed from the upper part of the pattern using a length-measuring scanning electron microscope (scanning electron microscope (SEM) (S-9380II of Hitachi, Ltd.)). The line width of the pattern was observed at 100 places, the measurement deviation was evaluated by 3σ, and it was set as LWR (nm). The smaller the value of LWR, the better the LWR performance over time. In addition, in the evaluation of LWR performance over time, a resist composition stored in a dark room at room temperature (25° C.) for 180 days after preparation was used to form a pattern and used for evaluation. In addition, the LWR (nm) after time is preferably 4.7 nm or less, 4.4 nm or less, 4.1 nm or less, 3.8 nm or less, 3.5 nm, and 3.2 nm or less in this order.

The characteristics and evaluation results of the resist composition used are shown in Table 3 below. The "content" column in the table indicates whether the content of the photoacid generator relative to the total solid content in the resist composition of the example is 15% by mass. If this requirement is met, it is recorded as "A", and if it is not met, it is recorded as "B". The "Formula PA1" column indicates whether the resist composition of the example contains the compound represented by the general formula (PA-1) as a photoacid generator. If this requirement is met, it is recorded as "A", and if it is not met, it is recorded as "B. The "Formula PB" column indicates whether the resist composition of the example contains the compound represented by the general formula (PB) as a photoacid generator. If this requirement is met, it is recorded as "A", and if it is not met, it is recorded as "B". The columns "a2", "a3", "a4", "a5", "a6", "b5", and "b6" respectively indicate whether the resin (acid-decomposable resin) contained in the resist composition of the example is It has repeating unit a2, repeating unit a3, repeating unit a4, repeating unit a5, repeating unit a6, repeating unit b5, and repeating unit b6. If this requirement is met, it is recorded as "A", and if it is not met, it is recorded as "B".

[table 3] table 3 Resist composition Photoacid generator Resin Defect inhibition LWR performance after time content Formula PA1 Formula PB a2 a3 a4 a5 a6 b5 b6 Example 1-1 Re-1 B B B B B B B B B B F 4.5 Example 1-2 Re-2 B B B B B B B B B B F 4.6 Example 1-3 Re-3 B B B A B B B B B B E 4.4 Example 1-4 Re-4 B B B A B B B B B B E 4.2 Example 1-5 Re-5 B B B A A B B B B B D 4.1 Example 1-6 Re-6 B B B A A B B B B B D 3.9 Example 1-7 Re-7 B B B A A B B B B B D 4.0 Example 1-8 Re-8 B B B A A B B B B B D 3.9 Example 1-9 Re-9 B B B B B A B B B B C 3.8 Example 1-10 Re-10 B B B B B A B B B B C 3.7 Example 1-11 Re-11 B B B B B A A B B B B 3.5 Example 1-12 Re-12 B B B B B A B B B B C 3.8 Example 1-13 Re-13 B B B A A A B B B B C 3.6 Example 1-14 Re-14 B B B A A A B B B B C 3.6 Example 1-15 Re-15 B B B A A A B B B B C 3.7 Example 1-16 Re-16 B B B A A A B B B B C 3.7 Example 1-17 Re-17 B B B A A B B B B B D 3.9 Example 1-18 Re-18 B B B A A A B B B B C 3.7 Examples 1-19 Re-19 B B B B B A B B A A A 3.2 Example 1-20 Re-20 B B B A B A B B A A A 3.1 Example 1-21 Re-21 B B B A A A A A B B A 3.1 Example 1-22 Re-22 B B B A B A A A B B A 3.1 Example 1-23 Re-23 B B B A B A B B A B B 3.3 Example 1-24 Re-24 B B B A A B B B B B D 3.9 Example 1-25 Re-25 B B B A B A B B B B C 3.7 Examples 1-26 Re-26 B B B A A B B B B B D 3.9 Example 1-27 Re-27 B A B B B B B B B B E 4.2 Example 1-28 Re-28 B A B A A B B B B B C 3.7 Example 1-29 Re-29 B A B B B A B B B B B 3.4 Example 1-30 Re-30 B A B B B A A B B B A 3.2 Example 1-31 Re-31 B A B B B A B B A A A 3.1 Example 1-32 Re-32 B A B A B A A A B B A 3.0 Example 1-33 Re-33 A B A B B B B B B B E 4.2 Example 1-34 Re-34 A B A A A B B B B B C 3.6 Example 1-35 Re-35 A B A B B A B B B B B 3.4 Example 1-36 Re-36 A B A B B A A B B B A 3.1 Example 1-37 Re-37 A B A B B A B B A A A 2.9 Example 1-38 Re-38 B B A A B A B B A A A 3.0 Examples 1-39 Re-39 B B A A A A A A B B A 3.0 Example 1-40 Re-40 A B A A B A A A B B A 2.9 Example 1-41 Re-41 B B A A B A A A B B A 3.0 Examples 1-42 Re-42 A B B B B B B B B B E 4.4 Examples 1-43 Re-43 A B B A A B B B B B C 3.7 Example 1-44 Re-44 A B B B B A B B B B B 3.5 Examples 1-45 Re-45 A B B B B A A B B B A 3.2 Example 1-46 Re-46 A B B B B A B B A A A 3.1 Examples 1-47 Re-47 A A A A A A A A B B A 2.9 Examples 1-48 Re-48 A B A A B A B B A A A 2.9 Examples 1-49 Re-49 A B A A B A A A B B A 2.9 Examples 1-50 Re-50 A B A B B A B B A A A 3.0 Comparative example 1-1 Re'-1 B B B - - - - - - - G 4.6 Comparative example 1-2 Re'-2 B B B - - - - - - - G 5.2 Comparative example 1-3 Re'-3 B B B - - - - - - - - - Comparative example 1-4 Re'-4 B B B - - - - - - - D 5.2 Comparative example 1-5 Re'-5 B B B - - - - - - - G 5.8 Comparative example 1-6 Re'-6 B B B - - - - - - - G 4.9

As shown in the table, it was confirmed that the resist composition of the present invention has excellent defect suppression properties and LWR performance over time when the pattern is formed by organic solvent development. On the other hand, in the resist composition of the comparative example, at least one of defect suppression properties and LWR performance over time is insufficient. In the resist composition of Comparative Example 1-1, in the acid-decomposable resin, the repeating unit (repeating unit a1) having an F atom at the α position is not used, but only the repeating unit having no F atom at the α position is used. It is believed that the reason is the large shot noise of EUV light. In the resist composition of Comparative Example 1-2, the acid-decomposable resin does not use a repeating unit having an F atom at the α-position, but uses _{a resin having a CF 3} group at the α-position. It is considered that the reason is that the organic solvent The solubility in the developer is too high. In the resist composition of Comparative Example 1-3, an acid-decomposable resin was not used but only a non-acid-decomposable resin was used, and the pattern could not be formed under these conditions. In the resist composition of Comparative Example 1-4, in the acid-decomposable resin, a repeating unit having an F atom at the α-position is not used, but a resin having an I atom at the α-position is used. Over time, LWR performance becomes insufficient. In the resist composition of Comparative Example 1-5, the acid-decomposable resin does not use a repeating unit having an F atom at the α-position, but only uses a resin that does not have an F atom at the α-position. The reason is considered to be EUV light. The shot noise is large. In the resist composition of Comparative Example 1-6, the acid-decomposable resin does not use a repeating unit having an F atom at the α position, but only uses a resin that does not have an F atom at the α position. The reason is considered to be EUV light. The shot noise is large.

In addition, in terms of more excellent effects of the present invention, it was confirmed that the resin contained in the resist composition preferably has repeating unit a2, more preferably has repeating unit a3, and still more preferably has repeating unit a4, It is especially preferable to have a repeating unit a5 or a repeating unit b5, and it is most preferable to have a repeating unit a6 or a repeating unit b6 (refer to the results of Examples 1-1 to 1-26, etc.).

In terms of the more excellent effects of the present invention, it was confirmed that the resist composition preferably contains the compound represented by the general formula (PA-1) (refer to the comparison between Example 1-1 and Example 1-27, Comparison of Examples 1-5 and Examples 1-28, Comparison of Examples 1-9 and Examples 1-29, Comparison of Examples 1-11 and Examples 1-30, Examples 1-19 and Examples 1-31 comparison, etc.).

In terms of the more excellent effects of the present invention, it was confirmed that the resist composition preferably contains the compound represented by the general formula (PB) (refer to the comparison between Example 1-1 and Example 1-33, Example 1-5 and Example 1-34, Example 1-9 and Example 1-35, Example 1-11 and Example 1-36, Example 1-19, Example 1- 37 Comparison with Examples 1-50, Examples 1-20, Examples 1-38 and Examples 1-48, Examples 1-21, Examples 1-39 and Examples 1-47, Comparison of Examples 1-22, Examples 1-40, Examples 1-41 and Examples 1-49).

In terms of the more excellent effects of the present invention, it was confirmed that the resist composition preferably contains 15% by mass or more of the photoacid generator with respect to the total solid content (refer to Example 1-1 and Example 1 -42, Example 1-5 and Example 1-43, Example 1-9 and Example 1-44, Example 1-11 and Example 1-45, Example 1 -19 and Example 1-46, Example 1-39 and Example 1-47, Example 1-41 and Example 1-49, etc.).

[EUV exposure, alkaline aqueous solution development] A 12-inch diameter silicon wafer was coated with an underlayer film forming composition AL412 (manufactured by Brewer Science), and baked at 205°C for 60 seconds to form a base film with a thickness of 20 nm. The resist composition shown in Table 4 was applied thereon, and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Using EUV exposure equipment (manufactured by Exitech, Micro Exposure Tool, NA 0.3, quadrupole, outer sigma 0.68, inner sigma 0.36), the silicon wafer with the obtained resist film The pattern irradiation is performed so that the average line width of the resulting pattern becomes 20 nm. Furthermore, as a reticle, a mask with line size=20 nm and line:space=1:1 is used. After the exposed resist film was baked at 90°C for 60 seconds, it was developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. Then, it was spin-dried to obtain a positive pattern. Using the obtained positive pattern, the defect suppression properties and the LWR performance after time were evaluated in the same manner as described above.

The evaluation results are shown in the following table. The meaning of each column in Table 4 is the same as the meaning of the corresponding column in Table 3.

[Table 4] Table 4 Resist composition Photoacid generator Resin Defect inhibition LWR performance after time content Formula PA1 Formula PB a2 a3 a4 a5 a6 b5 b6 Example 2-1 Re-1 B B B B B B B B B B F 4.6 Example 2-2 Re-2 B B B B B B B B B B F 4.5 Example 2-3 Re-3 B B B A B B B B B B E 4.3 Example 2-4 Re-4 B B B A B B B B B B E 4.2 Example 2-5 Re-5 B B B A A B B B B B D 4.0 Example 2-6 Re-6 B B B A A B B B B B D 3.9 Example 2-7 Re-7 B B B A A B B B B B D 4.0 Example 2-8 Re-8 B B B A A B B B B B D 4.1 Example 2-9 Re-9 B B B B B A B B B B C 3.8 Example 2-10 Re-10 B B B B B A B B B B C 3.7 Example 2-11 Re-11 B B B B B A A B B B B 3.5 Example 2-12 Re-12 B B B B B A B B B B C 3.7 Example 2-13 Re-13 B B B A A A B B B B C 3.7 Example 2-14 Re-14 B B B A A A B B B B C 3.6 Example 2-15 Re-15 B B B A A A B B B B C 3.7 Example 2-16 Re-16 B B B A A A B B B B C 3.6 Example 2-17 Re-17 B B B A A B B B B B D 4.0 Example 2-18 Re-18 B B B A A A B B B B C 3.7 Example 2-19 Re-19 B B B B B A B B A A A 3.2 Example 2-20 Re-20 B B B A B A B B A A A 3.2 Example 2-21 Re-21 B B B A A A A A B B A 3.1 Example 2-22 Re-22 B B B A B A A A B B A 3.1 Example 2-23 Re-23 B B B A B A B B A B B 3.3 Example 2-24 Re-24 B B B A A B B B B B D 3.9 Example 2-25 Re-25 B B B A B A B B B B C 3.7 Example 2-26 Re-26 B B B A A B B B B B D 3.9 Example 2-27 Re-27 B A B B B B B B B B E 4.3 Example 2-28 Re-28 B A B A A B B B B B C 3.7 Example 2-29 Re-29 B A B B B A B B B B B 3.3 Example 2-30 Re-30 B A B B B A A B B B A 3.2 Example 2-31 Re-31 B A B B B A B B A A A 3.0 Example 2-32 Re-32 B A B A B A A A B B A 3.0 Example 2-33 Re-33 A B A B B B B B B B E 4.2 Example 2-34 Re-34 A B A A A B B B B B C 3.7 Example 2-35 Re-35 A B A B B A B B B B B 3.3 Example 2-36 Re-36 A B A B B A A B B B A 3.0 Example 2-37 Re-37 A B A B B A B B A A A 2.9 Example 2-38 Re-38 B B A A B A B B A A A 3.0 Example 2-39 Re-39 B B A A A A A A B B A 3.0 Example 2-40 Re-40 A B A A B A A A B B A 2.9 Example 2-41 Re-41 B B A A B A A A B B A 3.0 Example 2-42 Re-42 A B B B B B B B B B E 4.3 Example 2-43 Re-43 A B B A A B B B B B C 3.8 Example 2-44 Re-44 A B B B B A B B B B B 3.4 Example 2-45 Re-45 A B B B B A A B B B A 3.2 Example 2-46 Re-46 A B B B B A B B A A A 3.0 Example 2-47 Re-47 A A A A A A A A B B A 2.9 Example 2-48 Re-48 A B A A B A B B A A A 2.9 Example 2-49 Re-49 A B A A B A A A B B A 2.9 Example 2-50 Re-50 A B A B B A B B A A A 2.9 Comparative example 2-1 Re'-1 B B B - - - - - - - G 4.9 Comparative example 2-2 Re'-2 B B B - - - - - - - G 5.2 Comparative example 2-3 Re'-3 B B B - - - - - - - - - Comparative example 2-4 Re'-4 B B B - - - - - - - D 5.3 Comparative example 2-5 Re'-5 B B B - - - - - - - G 5.8 Comparative example 2-6 Re'-6 B B B - - - - - - - G 5.1

As shown in the table, it was confirmed that the resist composition of the present invention has excellent defect suppression properties and LWR performance over time even when the pattern is formed by alkali development. On the other hand, in the resist composition of the comparative example, at least one of defect suppression properties and LWR performance over time is insufficient. In the resist composition of Comparative Example 2-1, in the acid-decomposable resin, the repeating unit having an F atom at the α position (repeating unit a1) is not used, but only the repeating unit having no F atom at the α position is used. It is believed that the reason is the large shot noise of EUV light. In the resist composition of Comparative Example 2-2, in the acid-decomposable resin, a repeating unit having an F atom at the α-position is not used, but _{a resin having a CF 3} group at the α-position is used. The solubility in the developer is too low. In the resist composition of Comparative Example 2-3, an acid-decomposable resin was not used but only a non-acid-decomposable resin was used, and the pattern could not be formed under these conditions. In the resist composition of Comparative Example 2-4, in the acid-decomposable resin, a repeating unit having an F atom at the α-position is not used, but a resin having an I atom at the α-position is used. Over time, LWR performance becomes insufficient. In the resist composition of Comparative Example 2-5, in the acid-decomposable resin, a repeating unit having an F atom at the α-position is not used, and only a resin having no F atom at the α-position is used, which is believed to be due to EUV light. The shot noise is large. In the resist composition of Comparative Example 2-6, in the acid-decomposable resin, the repeating unit having an F atom at the α-position is not used, and only the resin having no F atom at the α-position is used, which is believed to be due to EUV light. The shot noise is large.

In addition, in the comparison between the examples, the same tendency as when the pattern was formed by development with an organic solvent was also confirmed.

Claims (13)

A photosensitive ray-sensitive or radiation-sensitive resin composition, comprising: an acid-decomposable resin and a compound that generates acid by irradiation with actinic rays or radiation, the acid-decomposable resin having the general formula (A1) The repeating unit a1;

In the general formula (A1), R ^Q represents a hydrogen atom or an organic group. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit a1 includes a repeating unit a2 having an acid-decomposable group. The sensitized radiation-sensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit a2 includes the repeating unit a3 represented by the general formula (A2);

In the general formula (A2), R ^Q1 to R ^Q3 each independently represent an alkyl group; two of R ^Q1 to R ^Q3 may be bonded to each other to form a ring. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the repeating unit a1 includes ^{a repeating unit a4 in which R Q} represents a hydrogen atom or a group X, and the group X is A group having one or more specific groups selected from the group consisting of a lactone group, a sultone group, a carbonate group, a hydroxyl group, a sulfonamide group, an amide group, a carboxylic acid group, and a photoacid generating group, and It's not to break away from the base. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to claim 4, wherein the repeating unit a4 includes a repeating unit a5, and the repeating unit a5 includes the group X having a fluorine atom. The sensitizing radiation-sensitive or radiation-sensitive resin composition according to claim 5, wherein the repeating unit a5 includes a repeating unit a6, and the repeating unit a6 includes the group X having a hexafluoropropanol group. The sensitized radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the acid-decomposable resin has a repeating unit b5 represented by the general formula (B1);

In the general formula (B1), X represents a halogen atom other than a hydrogen atom, an alkyl group or a fluorine atom; L ^B represents a single bond or -COO-; R ^B1 represents a group Z, the group Z is a radical selected from the group consisting of a lactone, One or more specific groups in the group consisting of a sultone group, a carbonate group, a hydroxyl group, a sulfonamide group, a amide group, a carboxylic acid group, and a photoacid generating group, and has a fluorine atom and is not a leaving group . The sensitizing radiation-sensitive or radiation-sensitive resin composition according to claim 7, wherein the repeating unit b5 includes a repeating unit b6, and the repeating unit b6 includes the group Z having a hexafluoropropanol group. The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the compound that generates acid by irradiation with actinic rays or radiation comprises the general formula (PA-1) The compound represented;

Formula (PA-1) in, A ¹ and A ² each independently represent -SO ₂ -R ^P or -CO-R ^P; R ^P represents an organic group; M ⁺ represents a cation. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the compound that generates an acid by irradiation with actinic rays or radiation comprises a compound represented by the general formula (PB) The compound of; M ₁ ⁺ A ^-- LB ^- M ₂ ⁺ (PB) In the general formula (PB), M ₁ ⁺ and M ₂ ⁺ each independently represent an organic cation; L represents a divalent organic group; A ^- represents an acid radical anion _{Group; wherein, in the compound represented by HA-L-BH in which M 1} ⁺ and M ₂ ⁺ of the compound represented by the general formula (PB) are replaced by hydrogen atoms, respectively, the pKa of the group represented by HA is higher than that of BH The pKa of the group is low; B ^- represents a group represented by any one of the general formulas (B-1) to (B-4);

In the general formula (B-1) ~ (B -4), * represents a bonding position; in the general formula (B-1) ~ (B -4), R B represents an organic group. The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the content of the compound that generates acid by irradiation with actinic rays or radiation relative to the total solid content It is 15% by mass or more. A pattern forming method includes: A step of forming a resist film on a substrate using the sensitized radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11; A step of exposing the resist film; and A step of developing the exposed resist film using a developing solution to form a pattern. A manufacturing method of an electronic component includes the pattern forming method as described in claim 12.