Composition, resist film, pattern forming method, and electronic device manufacturing method

Abstract

The present invention provides a composition capable of forming a pattern having excellent resolution. The present invention further provides a resist film, a pattern forming method, and an electronic device manufacturing method related to said composition. The composition according to the present invention comprises a compound A that has a plurality of iodine atoms bonded to a carbon atom, and a compound B that does not have an iodine atom bonded to a carbon atom and has a plurality of specific functional groups selected from the group consisting of: nitrogen-containing aromatic heterocyclic groups; -NH2; NH2 groups protected by a releasable protective group; -NHRN1; -NHRN1 groups protected by a releasable protective group; -NRN2 2; -C≡N; -OH; -ORO; -SH; -SRS; -PRP1 2; and -P(ORP2)2. The composition satisfies at least one of requirement 1 and requirement 2.

Description

Composition, resist film, pattern forming method, and electronic device manufacturing method

[0001] The present invention relates to a composition, a resist film, a pattern forming method, and a method for manufacturing an electronic device.

[0002] Since the development of resists for KrF excimer lasers (248 nm), pattern formation methods utilizing chemical amplification have been used to compensate for the loss of sensitivity due to light absorption. For example, in positive-tone chemical amplification methods, a photoacid generator contained in the exposed area decomposes upon light irradiation to generate acid. Then, during a post-exposure bake (PEB) process, the catalytic action of the generated acid changes the alkali-insoluble groups of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition to alkali-soluble groups, thereby changing the solubility in the developer. Development is then performed, for example, using a basic aqueous solution. This removes the exposed area to obtain the desired pattern. To facilitate the miniaturization of semiconductor devices, the wavelength of exposure light sources has become shorter and the numerical aperture (NA) of projection lenses has become higher. Currently, exposure machines using an ArF excimer laser with a wavelength of 193 nm as a light source have been developed. In recent years, pattern formation methods using extreme ultraviolet (EUV) light and electron beams (EB) as light sources have also been investigated. Under these circumstances, various resist compositions have been proposed.

[0003] For example, Patent Document 1 discloses a resist composition comprising: "a base component whose solubility in a developer changes under the action of an acid; a compound having a specific structure and consisting of an anion moiety and a cation moiety; and a fluorine additive containing a fluorine resin component having specific structural units."

[0004] Japanese Patent Application Laid-Open No. 2021-004993

[0005] The present inventors have studied the resist composition described in Patent Document 1 and found that the patterns formed using the resist composition have poor resolution and require further improvement. Specifically, they investigated the minimum pattern dimensions that could be resolved without collapse while changing the exposure dose during pattern exposure, and found that the dimensions of the patterns formed using the resist composition were not sufficiently small.

[0006] Therefore, an object of the present invention is to provide a composition that can form a pattern with excellent resolution, and a resist film, a pattern forming method, and a method for manufacturing an electronic device, which are related to the composition.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A compound A having a plurality of iodine atoms bonded to a carbon atom, and a nitrogen-containing aromatic heterocyclic group, -NH ２ , NH protected by a removable protecting group ２ group, -NHR Ｎ１ , NHR protected by a removable protecting group Ｎ１ group, -NR Ｎ２ ２ , -C≡N, -OH, -OR Ｏ , -SH, -SR Ｓ , -PR Ｐ１ ２ , and -P(OR Ｐ２ ) ２ and compound B having a plurality of specific functional groups selected from the group consisting of the following and having no iodine atom bonded to a carbon atom, and satisfying at least one of requirement 1 and requirement 2. Requirement 1: Compound A is a polymer having a repeating unit containing an iodine atom bonded to the carbon atom. Requirement 2: Compound B is a polymer having a repeating unit containing the specific functional group. Ｎ１ , R Ｎ２ , R Ｏ , R Ｓ , R Ｐ１ and R Ｐ２R each independently represents a monovalent hydrocarbon group which may have a substituent. Ｎ２ may be bonded to each other to form a ring, and R Ｐ１ may be bonded to each other to form a ring, and R Ｐ２ The monovalent hydrocarbon groups represented by the formula (A1) may be bonded to each other to form a ring. [2] The composition according to [1], wherein the compound A is a compound having a group represented by any one of the formulas (A1) to (A3) described below. [3] The composition according to [2], wherein in the formula (A1), m is 4 or greater. [4] The composition according to [2] or [3], wherein in the formula (A2), all R represent electron-withdrawing groups. [5] The composition according to any one of [2] to [4], wherein in the formula (A1), EWG represents a fluorine atom or a cyano group, and in the formula (A2), at least one of R represents a fluorine atom or a cyano group. [6] The composition according to any one of [2] to [5], wherein the compound A is a compound having a structure represented by the formula (A1). [7] The specific functional group is a nitrogen-containing aromatic heterocyclic group, NH ２ -, NH protected by a removable protecting group ２ Group, NHR Ｎ１ -, NHR protected by a removable protecting group Ｎ１ groups, and NR Ｎ２ ２ - is a functional group selected from the group consisting of. [8] The composition according to any one of [1] to [7], which satisfies Requirement 1 above. [9] The composition according to any one of [1] to [8], which satisfies Requirement 2 above.

[10] A resist film formed using the composition according to any one of [1] to [9].

[11] A pattern formation method comprising the steps of: forming a resist film on a substrate using the composition according to any one of [1] to [9]; exposing the resist film; and developing the exposed resist film with a developer containing an organic solvent.

[12] A method for manufacturing an electronic device, which comprises the pattern formation method according to

[11] .

[0009] According to the present invention, a composition capable of forming a pattern with excellent resolution can be provided. Furthermore, according to the present invention, a resist film, a pattern forming method, and a method for manufacturing an electronic device, which are related to the composition, can be provided.

[0010] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] The meaning of each description in this specification will be explained below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In this specification, a hydrogen atom may be a protist atom (a normal hydrogen atom) or a deuterium atom (for example, a deuterium atom, etc.). In this specification, an "organic group" refers to a group containing at least one carbon atom.

[0012] Unless otherwise specified, the "substituent" in this specification is preferably a monovalent substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxalyl group; thiol group; methylsulfonyl group; Examples of the substituents include alkylsulfanyl groups such as a phenyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; alkyl groups (linear, branched, and cyclic alkyl groups); aryl groups; heteroaryl groups; hydroxyl groups; carboxy groups; formyl groups; sulfo groups; cyano groups; nitro groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups; alkylthio groups; and combinations thereof. In the specification, these substituent groups are also referred to as "substituent K."

[0013] The bonding direction of divalent groups represented in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. In addition, the compound may be "X-CO-O-Z" or "X-O-CO-Z".

[0014] Unless otherwise specified, the compounds described herein may include structural isomers, stereoisomers, and isotopes. Furthermore, the compounds may include one or more structural isomers, stereoisomers, and isotopes.

[0015] In this specification, "(meth)acrylic" is a generic term including acrylic and methacrylic, and means "at least one of acrylic and methacrylic." Similarly, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid."

[0016] As used herein, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam). As used herein, "light" refers to actinic rays or radiation. Unless otherwise specified, "exposure" as used herein includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers (such as ArF excimer lasers), extreme ultraviolet rays, and X-rays, but also drawing using particle beams such as electron beams and ion beams.

[0017] In this specification, unless otherwise specified, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured by Gel Permeation Chromatography (GPC) measurement using a GPC apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL / min, detector: refractive index detector).

[0018] As used herein, "ppm" means "parts per million (10 －６ ) and "ppb" stands for "parts per billion (10 －９ "ppt" means "parts per trillion (10 －１２ )"

[0019] In this specification, the term "total solids" refers to the components that form the resist film and does not include the solvent. Furthermore, any component that forms the resist film is considered to be a solid, even if it is in a liquid state.

[0020] [Composition] The composition of the present invention (hereinafter also referred to as "resist composition") will be described in detail below. The resist composition of the present invention comprises a compound A having a plurality of iodine atoms bonded to a carbon atom, and a nitrogen-containing aromatic heterocyclic group, -NH ２ , NH protected by a removable protecting group ２ group, -NHR Ｎ１ , NHR protected by a removable protecting group Ｎ１ group, -NR Ｎ２ ２ , -C≡N, -OH, -OR Ｏ , -SH, -SR Ｓ , -PR Ｐ１ ２ , and -P(OR Ｐ２ ) ２ and a compound B having a plurality of specific functional groups selected from the group consisting of: and having no iodine atoms bonded to a carbon atom, and satisfying at least one of requirement 1 and requirement 2 described below. The mechanism by which the resist composition of the present invention can solve the problems of the present invention by adopting the above-mentioned configuration is not necessarily clear, but the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effects are obtained. In other words, even if the effects are obtained by a mechanism other than the one described below, it is still included in the scope of the present invention.

[0021] In the resist composition of the present invention, when the resist film is in an unexposed state, Compound A and Compound B contained in the resist composition form strong halogen bonds, resulting in a crosslinked structure throughout the resist film, and therefore the resist film is insoluble in a developer. When the resist film is exposed to light, the sensitivity of iodine atoms is so high that carbon atom-iodine atom bonds are efficiently cleaved, eliminating the crosslinked structure. As a result, the exposed portions of the resist film become soluble in a developer, allowing the formation of a resist pattern. The resist composition disclosed in Patent Document 1 is a so-called chemically amplified resist composition, which suffers from the problem of poor resolution due to the reaction proceeding even in unexposed portions of the resist film that are not exposed to light. On the other hand, with the resist composition of the present invention, as described above, only exposed carbon atom-iodine atom bonds are cleaved, and therefore, it is presumed that the reaction hardly proceeds in unexposed portions, resulting in the resulting resist pattern having superior resolution. Requirements 1 and 2 are described in detail below.

[0022] (Requirements 1 and 2) The resist composition of the present invention satisfies at least one of requirements 1 and 2. Requirement 1: Compound A is a polymer having a repeating unit containing an iodine atom bonded to a carbon atom. Requirement 2: Compound B is a polymer having a repeating unit containing a specific functional group.

[0023] When the resist composition satisfies at least one of requirements 1 and 2, the resist film obtained using the resist composition will be homogeneous. The resist composition may also satisfy both requirements 1 and 2.

[0024] When the resist composition satisfies requirement 1, the weight average molecular weight of compound A is preferably 1,000 to 10,000, and more preferably 1,000 to 5,000. When the resist composition satisfies requirement 1, the number of iodine atoms per repeating unit is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0025] Furthermore, when the resist composition satisfies requirement 2, the weight average molecular weight of compound B is preferably 1,000 to 10,000, and more preferably 1,000 to 5,000. When the resist composition satisfies requirement 2, the number of the specific functional groups per repeating unit is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. Each component contained in the resist composition of the present invention will now be described in detail.

[0026] [Compound A] The resist composition of the present invention contains Compound A. Compound A is a compound having a plurality of iodine atoms bonded to a carbon atom, and the plurality of iodine atoms in Compound A behave as electron acceptors, thereby forming halogen bonds at multiple points with Compound B, which will be described later, to form a resist film. If the resist composition does not satisfy Requirement 1, the molecular weight of Compound A is preferably 300 to 2000, and more preferably 800 to 2000. Furthermore, if the resist composition does not satisfy Requirement 1, Compound A preferably has three or more iodine atoms bonded to the carbon atom, and more preferably four or more iodine atoms. There is no particular upper limit, but it can be, for example, 10 or less.

[0027] It is preferable that compound A has an electron-withdrawing group. When the resist composition satisfies requirement 1, the number of electron-withdrawing groups per repeating unit is preferably 1 to 6, and more preferably 2 to 6. When the resist composition does not satisfy requirement 1, the number of electron-withdrawing groups that compound A has is preferably 2 to 20, more preferably 2 to 16, and even more preferably 4 to 12.

[0028] Examples of electron-withdrawing groups include those having a positive value as the Hammett's rule substituent constant (σp value). The Hammett's rule substituent constant is a numerical representation of the effect of a substituent on the acid dissociation equilibrium constant of a substituted benzoic acid, and is a parameter indicating the strength of the electron-withdrawing and electron-donating properties of the substituent. In this specification, the Hammett's rule substituent constant refers to the substituent constant σ when the substituent is located at the para position of the benzoic acid. The Hammett's rule substituent constant (σp value) can be cited from "Hansch et al., Chemical Reviews, 1991, Vol. 91, No. 2, 165-195". For groups for which the σp value is not shown in the above literature, the σp value can be calculated based on the difference between the pKa of benzoic acid and the pKa of a benzoic acid derivative having a substituent at the para position using the software "ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08)". Examples of electron-withdrawing groups include -F (σp: +0.06), -Cl (σp: +0.23), -Br (σp: +0.23), -CO ２ R ＥＷＧ (σp:R ＥＷＧ is an ethyl group, +0.45), -CONH ２ (σp: +0.36), -COR ＥＷＧ (σp:R ＥＷＧ is a methyl group, +0.50), -CF ３ (σp: +0.54), -SO ２ R ＥＷＧ (σp:R ＥＷＧ is a methyl group, +0.72), and -NO ２ (σp: +0.78). ＥＷＧ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent. Examples of the substituent include the above-mentioned substituent K. The electron-withdrawing group is preferably a fluorine atom, an aryl group having a fluorine atom, a fluorinated alkyl group, or a cyano group.

[0029] Examples of the group having an iodine atom and an electron-withdrawing group include groups represented by any of the following formulas (A1) to (A3). Compound A is preferably a compound having a group represented by any of formulas (A1) to (A3), and more preferably a compound having a group represented by formula (A1).

[0030]

[0031] In formula (A1), EWG represents an electron-withdrawing group. n and m each independently represent an integer of 1 or greater. Ar represents an aromatic hydrocarbon ring which may have a substituent. In formula (A2), R each independently represent a hydrogen atom or a substituent, provided that at least one R represents an electron-withdrawing group. * represents a bonding position.

[0032] In formula (A1), examples of the electron-withdrawing group represented by EWG include the groups exemplified as electron-withdrawing groups. Among these, EWG preferably represents a fluorine atom or a cyano group. n and m each independently represent an integer of 1 or greater. n is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and even more preferably an integer of 1 to 3. m is preferably an integer of 2 to 8, more preferably an integer of 4 to 6, and even more preferably 4. The aromatic hydrocarbon ring represented by Ar, which may have a substituent, may be either monocyclic or polycyclic. Ar corresponds to an m+n+1 valent group. The number of ring atoms in the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6. Examples of the substituent that the aromatic hydrocarbon ring may have include the substituent K described above. Among the aromatic hydrocarbon rings which may have a substituent, a benzene ring which may have a substituent is preferred, and a benzene ring which has no substituents other than an iodine atom and an electron-withdrawing group is more preferred.

[0033] In formula (A2), R each independently represents a hydrogen atom or a substituent. However, at least one of R represents an electron-withdrawing group. R preferably represents a hydrogen atom or an electron-withdrawing group, and it is more preferable that all R in formula (A2) represent electron-withdrawing groups. As described above, examples of the electron-withdrawing group include the groups exemplified as electron-withdrawing groups. Among these, the electron-withdrawing group represented by R is preferably a fluorine atom or a cyano group.

[0034] Specific examples of compound A include compounds represented by formula (X1) or formula (X2). (R Ａ１ -L Ａ ) ｋ -X ｋ ...Formula (X1) R Ａ２ -R Ａ２ ...Formula (X2)

[0035] In formula (X1), R Ａ１ each independently represents a group represented by any one of the above formulas (A1) to (A3). Ａ each independently represents a single bond or a divalent linking group. ｋ represents a k-valent linking group, where k is an integer of 2 or more.

[0036] In formula (X2), R Ａ２ each independently represents a group represented by any one of the above formulas (A1) to (A3).

[0037] In formulae (X1) and (X2), the definitions and preferred embodiments of the groups represented by any of formulae (A1) to (A3) are as described above.

[0038] In formula (X1), L Ａ each independently represents a single bond or a divalent linking group. Ａ Examples of the divalent linking group represented by the formula: ２Examples of the alkylene group and alkenylene group include -, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, and a linking group formed by linking a plurality of these groups. The alkylene group and alkenylene group may be linear, branched, or cyclic, and preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 or 2 carbon atoms. The arylene group preferably has 6 to 10 carbon atoms, more preferably 6 carbon atoms. The heteroarylene group preferably has 4 to 10 carbon atoms, more preferably 4 or 5 carbon atoms. The arylene group and heteroarylene group may be either monocyclic or polycyclic. Examples of groups formed by linking a plurality of divalent linking groups include -COO-, -OCO-, -O-alkylene group-, -COO-alkylene group-, and -OCO-alkylene group-.

[0039] X ｋ In the k-valent linking group represented by the formula: k represents an integer of 2 or more, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4. X ｋ Examples of the divalent linking group represented by the formula: ２ -, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, and a linking group in which a plurality of these groups are linked together (for example, a biphenylene group). Ａ The divalent linking group represented by X is as described in detail above. ｋ The divalent linking group represented by the formula (I) is preferably an alkenylene group having 1 to 3 carbon atoms, a phenylene group, or a biphenylene group.

[0040] X ｋExamples of the trivalent linking group represented by the formula (I) include a trivalent aromatic ring group and a nitrogen atom (-N<). A trivalent aromatic ring group refers to a group obtained by removing three hydrogen atoms from a ring member atom of an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocycle which may have a substituent. For example, a group obtained by removing three hydrogen atoms from a ring member atom of a benzene ring or a biphenyl ring may be mentioned. The aromatic hydrocarbon ring and aromatic heterocycle may be either a monocyclic or polycyclic ring. Examples of the substituent include the above-mentioned substituent K, and among these, an alkyl group or an electron-withdrawing group is preferred, with a fluorine atom being more preferred. The alkyl group preferably has 1 to 3 carbon atoms.

[0041] X ｋ Examples of the tetravalent linking group represented by the formula (I) include a carbon atom (>C<), a silicon atom (>Si<), and a tetravalent aromatic ring group. A tetravalent aromatic ring group refers to a group obtained by removing four hydrogen atoms from a ring member atom of an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocycle which may have a substituent. For example, a group obtained by removing four hydrogen atoms from a ring member atom of a benzene ring or a biphenyl ring may be mentioned. The aromatic hydrocarbon ring and aromatic heterocycle may be either a monocyclic or polycyclic ring. Examples of the substituent include the above-mentioned substituent K, and among these, an alkyl group or an electron-withdrawing group is preferred, and a fluorine atom is more preferred. The alkyl group preferably has 1 to 3 carbon atoms.

[0042] <Repeating Unit A1 (Repeating Unit Having an Iodine Atom Bonded to a Carbon Atom)> When the resist composition satisfies Requirement 1, it is preferable that Compound A has a repeating unit represented by Formula (U1) as a repeating unit having an iodine atom bonded to a carbon atom (hereinafter also referred to as "repeating unit A1").

[0043]

[0044] In formula (U1), R Ｕ１ represents a hydrogen atom or an alkyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms, and more preferably has 1 to 2 carbon atoms.

[0045] L Ｕ１ represents a single bond or a divalent linking group. Examples of the divalent linking group include -O-, -CO-, -S-, -SO-, and -SO ２ Examples of the alkylene group include alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, and linking groups formed by linking a plurality of these groups. The alkylene group, alkenylene group, arylene group, and heteroarylene group may have a substituent. Examples of the substituent include the substituent K.

[0046] The alkylene group and alkenylene group may be linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 or 2 carbon atoms. The arylene group preferably has 6 to 10 carbon atoms, more preferably 6 carbon atoms. The heteroarylene group preferably has 4 to 10 carbon atoms, more preferably 4 or 5 carbon atoms. The arylene group and heteroarylene group may be either monocyclic or polycyclic. Examples of groups formed by linking multiple divalent linking groups include -COO-, -OCO-, -O-alkylene group, -COO-alkylene group-, and -OCO-alkylene group-. L Ｕ１ Among these, —COO— and —COO-alkylene group- are preferred.

[0047] W represents a single bond or a ((t1)+1)-valent linking group. t1 represents an integer of 1 or more. There is no particular limitation on the upper limit, but it is preferably 5 or less, more preferably 2 or less, and even more preferably 1. The ((t1)+1)-valent linking group includes the above-mentioned L Ｕ１ Examples of W include groups obtained by removing ((t1)-1) hydrogen atoms from a divalent linking group represented by the following formula: W is preferably a single bond.

[0048] Each X independently represents a group represented by any one of the above formulas (A1) to (A3). The definition and preferred embodiments of the group represented by any one of the above formulas (A1) to (A3) are as described above. When there are multiple groups represented by X, the multiple groups represented by X may be the same or different.

[0049] The repeating unit A1 may be used singly or in combination of two or more. When compound A has the repeating unit A1, the content of the repeating unit A1 is preferably 50 to 100 mol %, more preferably 70 to 100 mol %, based on the total repeating units.

[0050] <Other Repeating Units> Compound A may have a repeating unit other than the repeating unit A1. Examples of the other repeating unit include a repeating unit having an alkyl group which may have a substituent, a repeating unit having a lactone group, a sultone group, or a carbonate group, and a repeating unit derived from an aromatic vinyl compound.

[0051] Repeating Unit A2 (Repeating Unit Having an Optionally Substituted Alkyl Group) Compound A may have a repeating unit having an optionally substituted alkyl group (hereinafter also referred to as "repeating unit A2"). The alkyl group may be linear, branched, or cyclic. In the case of a cyclic alkyl group, it may have a monocyclic structure or a polycyclic structure. The number of carbon atoms in the alkyl group is not particularly limited, and may be 1 to 20. Examples of the substituent that the alkyl group may have include the above-mentioned substituent K, and more specifically, a hydroxyl group.

[0052] The repeating unit A2 is preferably a repeating unit represented by formula (A).

[0053]

[0054] R １ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group, or an aryl group; L １ represents a divalent linking group, R ２ represents an alkyl group which may have a substituent.

[0055] R １represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group, or an aryl group. The alkyl group and aryl group may have a fluorine atom or an iodine atom as a substituent. The alkyl group may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms that the alkyl group may have is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may have a heteroatom such as an oxygen atom.

[0056] L １ represents a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, and -SO ２ -, divalent hydrocarbon groups (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these groups are linked together. The divalent hydrocarbon groups may have a fluorine atom or an iodine atom as a substituent. Among these, L １ is preferably -CO-, -Rt-, -COO-Rt-, -COO-Rt-CO-, or -Rt-CO-, and more preferably -CO- or -COO-Rt-CO-. Rt is a divalent hydrocarbon group, and is preferably an alkylene group or an arylene group, and more preferably an alkylene group. As the arylene group, a phenylene group is preferable. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0057] R ２represents an alkyl group which may have a substituent. The alkyl group may be linear, branched, or cyclic. In the case of a cyclic alkyl group, it may have a monocyclic structure or a polycyclic structure. The number of carbon atoms in the alkyl group is not particularly limited, and may be 1 to 20. Examples of the cyclic alkyl group include monocyclic alkyl groups (cycloalkyl groups) such as a cyclopentyl group and a cyclohexyl group, as well as polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Examples of the substituent that the alkyl group may have include the substituent K described above, and more specifically, a hydroxyl group.

[0058] The repeating unit A2 may be used singly or in combination of two or more. When compound A has the repeating unit A2, the content of the repeating unit A2 is preferably 1 to 50 mol %, more preferably 10 to 30 mol %, based on the total repeating units.

[0059] Repeating Unit A3 (Repeating Unit Having a Lactone Group, a Sultone Group, or a Carbonate Group) Compound A may have a repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter also referred to as "repeating unit A3"). It is also preferable that the repeating unit A3 does not have an acid group such as a hydroxyl group or a hexafluoropropanol group. The repeating unit A3 may have an iodine atom, but it is preferable that it does not have an iodine atom.

[0060] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure. Among these, a 5- to 7-membered lactone structure to which another ring structure is fused in the form of a bicyclo or spiro structure, or a 5- to 7-membered sultone structure to which another ring structure is fused in the form of a bicyclo or spiro structure, is more preferred. Compound A preferably has a repeating unit having a lactone group or sultone group formed by abstracting one or more hydrogen atoms from a ring member atom of a lactone structure represented by any of the following formulae (LC1-1) to (LC1-21) or a sultone structure represented by any of the following formulae (SL1-1) to (SL1-3). The lactone group or sultone group may be directly bonded to the main chain.

[0061]

[0062] The lactone structure or sultone structure may be formed by the substituent (Rb ２ ) may have a substituent (Rb ２ ) is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, a cyclic alkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxy group, a halogen atom, a cyano group, or an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb ２ may be different, and a plurality of Rb ２ They may be bonded to each other to form a ring.

[0063] Examples of the repeating unit A3 include a repeating unit represented by the following formula (AI).

[0064]

[0065] In formula (AI), Rb ０ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ０Preferred substituents that the alkyl group of Rb may have include a hydroxyl group and a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ０ is preferably a hydrogen atom or a methyl group.

[0066] 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 carboxy group, or a divalent linking group formed by combining these. Ab represents a single bond or -Ab １ -CO ２ A linking group represented by - is preferred. １ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3).

[0067] The carbonate group is preferably a cyclic carbonate group.

[0068] Examples of the repeating unit A3 include the repeating units described in paragraphs

[0104] to

[0110] of WO 2020 / 158467.

[0069] The repeating unit A3 may be used singly or in combination of two or more. When compound A has the repeating unit A3, the content of the repeating unit A3 is preferably 1 to 50 mol %, more preferably 5 to 25 mol %, based on the total repeating units.

[0070] Repeating Unit A4 (Repeating Unit Derived from an Aromatic Vinyl Compound) Compound A may have a repeating unit derived from an aromatic vinyl compound (hereinafter also referred to as "repeating unit A4"). The aromatic vinyl compound is not particularly limited as long as it is an olefin compound having an aromatic ring structure, and may be either a chain olefin compound or a cyclic olefin compound. The monovalent aromatic group is not particularly limited and may be either an optionally substituted aryl group or an optionally substituted heteroaryl group, with an optionally substituted aryl group being preferred. Specific embodiments of the monovalent aromatic group will be described later. Examples of the repeating unit A4 include a repeating unit represented by the following formula (AX):

[0071]

[0072] In formula (AX), R １ represents a hydrogen atom or an alkyl group which may have a substituent. The number of substituents which the alkyl group may have is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2. R １ is preferably a hydrogen atom. Examples of the substituent that the alkyl group may have include the groups exemplified above as the substituent K.

[0073] The number of carbon atoms in the alkyl group (the alkyl group portion excluding the substituent) is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 1. The alkyl group may be linear, branched, or cyclic, and examples thereof include linear or branched alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, and n-hexyl groups, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Of these, the alkyl group is preferably a linear alkyl group, more preferably a linear alkyl group having 1 to 5 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0074] In formula (AX), Ar represents a monovalent aromatic group which may have a substituent.

[0075] The number of substituents that the monovalent aromatic group may have is not particularly limited, and is preferably 1 to 4, and more preferably 1 or 2. Examples of the substituent that the monovalent aromatic group may have include the groups exemplified for the substituent K above. Among these, the substituent that the monovalent aromatic group may have is preferably an alkyl group that may have a halogen atom, and more preferably an alkyl group that may have a fluorine atom. When the alkyl group has a fluorine atom, it may be a perfluoroalkyl group. The alkyl group may be linear, branched, or cyclic. Among these, the alkyl group is preferably a linear or branched alkyl group, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or a t-butyl group.

[0076] The monovalent aromatic group is not particularly limited and may be either a monocyclic or polycyclic group, and may be either an aryl group or a heteroaryl group. The number of ring atoms in the monovalent aromatic group is preferably 6 to 15, more preferably 6 to 10. The monovalent aromatic group is preferably an aryl group, more preferably a phenyl group, a naphthyl group, or an anthracenyl group, and even more preferably a phenyl group.

[0077] Among these, the optionally substituted monovalent aromatic group represented by Ar is preferably an optionally substituted aryl group, more preferably an optionally substituted phenyl group, naphthyl group, or anthracenyl group, still more preferably a phenyl group optionally having a t-butyl group or a trifluoromethyl group, and particularly preferably a phenyl group. When the phenyl group has a substituent, it is preferable that the substituent be at the para-position on the phenyl group.

[0078] The aromatic vinyl compound may be α-methylstyrene or a derivative thereof. １may be a methyl group, and Ar may be a phenyl group which may have a substituent.

[0079] ((Repeating unit represented by formula (V-1) or formula (V-2)) Repeating unit A4 may be a repeating unit represented by the following formula (V-1) or formula (V-2). It is preferable that the repeating unit represented by the following formula (V-1) and the repeating unit represented by the following formula (V-2) are different from the above-mentioned respective repeating units.

[0080]

[0081] In formulas (V-1) and (V-2), R ６ and R ７ each independently represents a hydrogen atom, a hydroxyl group, an alkyl 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 or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. The alkyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. In formula (V-1), n ４ represents an integer of 0 to 4. ４ represents a methylene group, an oxygen atom, or a sulfur atom. ３ represents an integer of 0 to 6. Examples of the repeating unit represented by formula (V-1) or formula (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0082] The repeating unit A4 may be used singly or in combination of two or more. When compound A has the repeating unit A4, the content of the repeating unit A4 is preferably 1 to 50 mol %, more preferably 10 to 45 mol %, based on the total repeating units.

[0083] One type of compound A may be used alone, or two or more types may be used in combination. The content of compound A is preferably from 5 to 80 mass %, more preferably from 15 to 70 mass %, and even more preferably from 15 to 60 mass %, based on the total solid content of the resist composition.

[0084] [Compound B] The resist composition of the present invention contains compound B. When compound B contains multiple specific functional groups, it behaves as an electron donor and forms halogen bonds at multiple points with compound A, thereby forming a resist film. If the resist composition does not satisfy requirement 2, the molecular weight of compound B is preferably 200 to 1,000, and more preferably 400 to 1,000. Furthermore, if the resist composition does not satisfy requirement 2, compound B preferably contains three or more specific functional groups, and more preferably four or more specific functional groups. There is no particular upper limit, but an example is 10 or less.

[0085] Compound B is a nitrogen-containing aromatic heterocyclic group, -NH ２ , NH protected by a removable protecting group ２ Group, NHR Ｎ１ -, NHR protected by a removable protecting group Ｎ１ group, -NR Ｎ２ ２ , -C≡N, -OH, -OR Ｏ , -SH, -SR Ｓ , -PR Ｐ１ ２ , and -P(OR Ｐ２ ) ２ R Ｎ１ , R Ｎ２ , R Ｏ , R Ｓ , R Ｐ１ and R Ｐ２ R each independently represents a monovalent hydrocarbon group which may have a substituent. Ｎ２ may be bonded to each other to form a ring, and R Ｐ１ may be bonded to each other to form a ring, and R Ｐ２ The monovalent hydrocarbon groups represented by the following formula may be bonded to each other to form a ring.

[0086] The nitrogen-containing aromatic heterocyclic group refers to a group formed by removing one hydrogen atom from a nitrogen-containing aromatic heterocycle. The ring structure may be either monocyclic or polycyclic. Examples of the nitrogen-containing aromatic heterocycle in the nitrogen-containing aromatic heterocyclic group include imidazole, pyridine, pyrrole, pyrazole, triazole, triazine, benzimidazole, and benztriazole.

[0087] NHR Ｎ１ -, NHR protected by a removable protecting group Ｎ１ groups, and NR Ｎ２ ２ -In R Ｎ１ and R Ｎ２ R each independently represents a monovalent hydrocarbon group which may have a substituent. Ｎ２ Monovalent hydrocarbon groups represented by the formula (I) may be bonded to each other to form a ring. Examples of monovalent hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The aromatic hydrocarbon group may be either monocyclic or polycyclic. The aromatic hydrocarbon group preferably has 6 to 10 carbon atoms. Among these, alkyl groups having 1 to 3 carbon atoms are preferred as monovalent hydrocarbon groups.

[0088] NH protected with a removable protecting group ２ group, and NHR protected by a removable protecting group Ｎ１ In the group, the term "removable protecting group" refers to a functional group that is removed by the action of heat, acid, base, reducing agent, other reagents, or the like. The protecting group is preferably a protecting group that is removed by heat, and examples thereof include carbamate protecting groups. More specific examples of carbamate protecting groups include a tert-butoxycarbonyl group, a tert-pentoxycarbonyl group, a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, and an allyloxycarbonyl group, with a tert-butoxycarbonyl group or a tert-pentoxycarbonyl group being preferred.

[0089] -OR Ｏ , -SR Ｓ , -PR Ｐ１ ２ , and -P(OR Ｐ２ ) ２ In this case, R Ｏ , R Ｓ , R Ｐ１ and R Ｐ２ each independently represents a monovalent hydrocarbon group which may have a substituent. Examples of the monovalent hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. The aromatic hydrocarbon group may be either monocyclic or polycyclic. The aromatic hydrocarbon group preferably has 6 to 10 carbon atoms. Among these, the monovalent hydrocarbon group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, or a phenyl group.

[0090] The specific functional group is, among others, a nitrogen-containing aromatic heterocyclic group, NH ２ -, NH protected by a removable protecting group ２ Group, NHR Ｎ１ -, NHR protected by a removable protecting group Ｎ１ groups, and NR Ｎ２ ２ Preferred are functional groups selected from the group consisting of:

[0091] Specific examples of compound B include compounds represented by formula (Y1) or formula (Y2). (R Ｂ１ -L Ｂ ) ｊ -X ｊ ...Formula (Y1) R Ｂ２ -R Ｂ２ Formula (Y2)

[0092] In formula (Y1), R Ｂ１ each independently represents the specific functional group. Ｂ each independently represents a single bond or a divalent linking group. ｊ represents a j-valent linking group, and j represents an integer of 2 or more.Ｂ２ each independently represents the specific functional group.

[0093] In formulae (Y1) and (Y2), the definitions and preferred embodiments of the specific functional groups are as described above.

[0094] In formula (Y1), L Ｂ each independently represents a single bond or a divalent linking group. Ｂ Examples of the divalent linking group represented by the formula: ２ Examples of the alkylene group and alkenylene group include alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, and linking groups formed by linking a plurality of these groups. The alkylene group and alkenylene group may be linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 or 2 carbon atoms. The arylene group preferably has 6 to 10 carbon atoms, more preferably 6 carbon atoms. The heteroarylene group preferably has 4 to 10 carbon atoms, more preferably 4 or 5 carbon atoms. The arylene group and heteroarylene group may be either monocyclic or polycyclic. Examples of groups formed by linking a plurality of divalent linking groups include -COO-, -OCO-, -O-alkylene group-, -COO-alkylene group-, -OCO-alkylene group-, and -alkylene group-OCO-alkylene group-.

[0095] X ｊ In the j-valent linking group represented by the formula: j represents an integer of 2 or more, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4. X ｊ Examples of the divalent linking group represented by the formula: ２ -, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, and a linking group in which a plurality of these groups are linked together (for example, a biphenylene group). Ｂ The divalent linking group represented by X is as described in detail above. ｊ The divalent linking group represented by the formula (I) is preferably an alkenylene group having 1 to 3 carbon atoms, a phenylene group, or a biphenylene group.

[0096] X ｊ Examples of the trivalent linking group represented by the formula (I) include a trivalent aromatic ring group and a nitrogen atom (-N<). A trivalent aromatic ring group refers to a group obtained by removing three hydrogen atoms from a ring member atom of an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocycle which may have a substituent. For example, a group obtained by removing three hydrogen atoms from a ring member atom of a benzene ring or a biphenyl ring may be mentioned. The aromatic hydrocarbon ring and aromatic heterocycle may be either a monocyclic or polycyclic ring. Examples of the substituent include the substituent K mentioned above.

[0097] X ｊ Examples of the tetravalent linking group represented by the formula (I) include a carbon atom (>C<), a silicon atom (>Si<), and a tetravalent aromatic ring group. A tetravalent aromatic ring group refers to a group obtained by removing four hydrogen atoms from a ring member atom of an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocycle which may have a substituent. For example, a group obtained by removing four hydrogen atoms from a ring member atom of a benzene ring or a biphenyl ring can be mentioned. The aromatic hydrocarbon ring and aromatic heterocycle may be either a monocyclic or polycyclic ring. Examples of the substituent include the substituent K mentioned above.

[0098] <Repeating Unit B1 (Repeating Unit Containing a Specific Functional Group)> When the resist composition satisfies the above-mentioned requirement 1, it is preferable that compound B has a repeating unit represented by formula (U2) as the repeating unit containing a specific functional group (hereinafter also referred to as "repeating unit B1").

[0099]

[0100] In formula (U2), R Ｕ２ represents a hydrogen atom or an alkyl group. The alkyl group may be either linear or branched. The alkyl group preferably has 1 to 5 carbon atoms, and more preferably has 1 to 2 carbon atoms.

[0101] In formula (U2), L Ｕ２ represents a single bond or a divalent linking group. Examples of the divalent linking group include -O-, -CO-, -S-, -SO-, and -SO ２Examples of the alkylene group include alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, and linking groups formed by linking a plurality of these groups. The alkylene group, alkenylene group, arylene group, and heteroarylene group may have a substituent. Examples of the substituent include the substituent K.

[0102] The alkylene group and alkenylene group may be linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 or 2 carbon atoms. The arylene group preferably has 6 to 10 carbon atoms, more preferably 6 carbon atoms. The heteroarylene group preferably has 4 to 10 carbon atoms, more preferably 4 or 5 carbon atoms. The arylene group and heteroarylene group may be either monocyclic or polycyclic. Examples of groups formed by linking multiple divalent linking groups include -COO-, -OCO-, -O-alkylene group, -COO-alkylene group-, and -OCO-alkylene group-. Among these, L is preferably a single bond, an arylene group, -COO-, or -COO-arylene group-.

[0103] V represents a single bond or a ((t2)+1)-valent linking group. t2 represents an integer of 1 or greater. There is no particular limitation on the upper limit, but it is preferably 5 or less, more preferably 2 or less, and even more preferably 1. Examples of the ((t2)+1)-valent linking group include groups obtained by removing ((t2)-1) hydrogen atoms from the divalent linking group represented by L. V is preferably a single bond.

[0104] Each D independently represents the specific functional group. The definition and preferred embodiments of the specific functional group are as described above. When there are multiple groups represented by D, the multiple groups represented by D may be the same or different.

[0105] The repeating unit B1 may be used singly or in combination of two or more. When compound B has repeating unit B1, the content of repeating unit B1 is preferably 50 to 100 mol %, more preferably 70 to 100 mol %, based on the total repeating units of compound B.

[0106] <Other Repeating Units> Compound B may have a repeating unit other than the repeating unit A1. Examples of other repeating units include a repeating unit having an alkyl group which may have a substituent, a repeating unit having a lactone group, a sultone group, or a carbonate group, and a repeating unit derived from an aromatic vinyl compound. The definition and preferred embodiments of the repeating unit having an alkyl group which may have a substituent are as described above for the repeating unit A2. The repeating unit having a lactone group, a sultone group, or a carbonate group is as described above for the repeating unit A3. The repeating unit derived from an aromatic vinyl compound is as described above for the repeating unit A4.

[0107] In compound B, the repeating unit having an alkyl group which may have a substituent, and the repeating unit having a lactone group, a sultone group, or a carbonate group may be used alone or in combination of two or more. When compound B has repeating units, the content of repeating units having an alkyl group which may have a substituent is preferably 1 to 50 mol%, more preferably 10 to 30 mol%, based on all repeating units. When compound B has repeating units, the content of repeating units having a lactone group, a sultone group, or a carbonate group is preferably 1 to 50 mol%, more preferably 5 to 25 mol%, based on all repeating units. When compound B has repeating units, the content of repeating units derived from an aromatic vinyl compound is preferably 1 to 50 mol%, more preferably 10 to 45 mol%, based on all repeating units.

[0108] One type of compound B may be used alone, or two or more types may be used in combination. The content of compound B is preferably from 5 to 80 mass %, more preferably from 15 to 70 mass %, and even more preferably from 15 to 60 mass %, based on the total solid content of the resist composition.

[0109] [Solvent] The resist composition of the present invention preferably contains a solvent. The solvent preferably contains at least one selected from the group consisting of (M1) propylene glycol monoalkyl ether carboxylate (such as propylene glycol monomethyl ether acetate (PGMEA)) and (M2) propylene glycol monoalkyl ether (such as propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether (PGEE)), lactate esters (such as ethyl lactate), acetate esters, alkoxypropionate esters, chain ketones (such as diacetone alcohol), cyclic ketones (such as 2-heptanone, cyclohexanone, or cyclopentanone), lactones (such as γ-butyrolactone), and alkylene carbonates (such as propylene carbonate). The solvent may further contain solvents other than components (M1) and (M2).

[0110] The solvent preferably contains component (M1). More preferably, the solvent consists essentially of component (M1) alone, or is a mixed solvent of component (M1) and other components. In the latter case, the solvent further preferably contains both component (M1) and component (M2).

[0111] The mass ratio (M1 / M2) of component (M1) to component (M2) is preferably from 100 / 0 to 0 / 100, more preferably from 100 / 0 to 15 / 85, still more preferably from 100 / 0 to 40 / 60, and particularly preferably from 100 / 0 to 60 / 40.

[0112] As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0113] The content of the solvent in the resist composition is preferably determined so that the solids concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass.

[0114] [Other Additives] The resist composition of the present invention may contain other additives in addition to those described above. Examples of other additives include surfactants, polymerization inhibitors, dissolution-inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in a developer.

[0115] <Surfactant> The resist composition of the present invention may further contain a surfactant. The surfactant is preferably a fluorine-based or silicon-based surfactant. Examples of the fluorine-based surfactant and the silicon-based surfactant include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954.

[0116] The surfactant may be used alone or in combination of two or more. When the resist composition contains a surfactant, the content of the surfactant is preferably from 0.001 to 2 mass%, and more preferably from 0.01 to 1 mass%, relative to the total solid content of the resist composition.

[0117] <Polymerization Inhibitor> The resist composition of the present invention may further contain a polymerization inhibitor. The polymerization inhibitor is not particularly limited, but a radical polymerization inhibitor is preferred. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, free radical compounds, amine compounds, phosphine compounds, and thiol ether compounds.

[0118] Examples of phenolic compounds include 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, 4-tert-butylcatechol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-p-cresol, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, 2,4-bis(octylthiomethyl)-6-methylphenol, p-nitrosophenol, and α-nitroso-β-naphthol.

[0119] The quinone compounds include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.

[0120] Free radical compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl), 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2-diphenyl-1-picrylhydrazyl, and triphenylpherdazyl.

[0121] The polymerization inhibitor may be used alone or in combination of two or more. When the resist composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 15 mass %, and more preferably 0.01 to 10 mass %, relative to the total solid content of the resist composition.

[0122] [Method of forming a resist film and a pattern] The procedure of the method of forming a pattern using the resist composition of the present invention is not particularly limited, but preferably includes the following steps. Each step may be performed once or multiple times. Step 1: Forming a resist film on a substrate using the resist composition Step 2: Exposing the resist film Step 3: Developing the exposed resist film using a developer containing an organic solvent to obtain a pattern The procedure of each of the above steps is described in detail below.

[0123] <Step 1: Resist Film Forming Step> Step 1 is a step of forming a resist film on a substrate using a resist composition. The definition of the resist composition is as described above.

[0124] A method for forming a resist film on a substrate using a resist composition includes, for example, applying the resist composition to the substrate. It is preferable to filter the resist composition before application, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0125] The resist composition can be applied onto a substrate (e.g., silicon, silicon dioxide coated) such as those used in the manufacture of integrated circuit elements by an appropriate application method such as a spinner or coater. The application method is preferably spin application using a spinner. The rotation speed when spin application using a spinner is preferably 1000 to 3000 rpm. After application of the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed under the resist film. For example, in the case of a semiconductor wafer, a silicon wafer can be used as the material constituting the substrate to be processed and its outermost layer, and examples of materials for the outermost layer include Si, SiO ２ , SiN, SiON, TiN, WSi, BPSG (Boro-Phospho-Silicate Glass), SOG (Spin On Glass), and organic anti-reflection films.

[0126] An example of a drying method is a method of drying by heating. Heating can be performed using a means provided in a typical exposure machine and / or developing machine, and may also be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds. The resist film can be formed, for example, by pre-baking at 60 to 150°C for 1 to 20 minutes, preferably at 80 to 120°C for 1 to 10 minutes.

[0127] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming a finer pattern with higher precision. In particular, when EUV exposure is used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.

[0128] A top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be uniformly applied to the resist film. The film thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm, and even more preferably 40 to 80 nm. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of JP 2014-059543 A. For example, it is preferable to form a top coat containing a basic compound such as that described in JP 2013-061648 A on the resist film. Specific examples of basic compounds that may be contained in the top coat include basic compounds that may be contained in the resist composition. The top coat also preferably contains a compound containing 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 group, and an ester group.

[0129] <Step 2: Exposure Step> Step 2 is a step of exposing the resist film. Examples of exposure methods include irradiating the formed resist film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Specific examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ These include excimer laser (157 nm), EUV (13 nm), X-ray, and electron beam.

[0130] After exposure, it is preferable to perform post-exposure heat treatment (also referred to as post-exposure baking) before development. Post-exposure heat treatment promotes the reaction of the exposed area, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like.

[0131] <Step 3: Development Step> Step 3 is a step of developing the exposed resist film using a developer containing an organic solvent to form a pattern.

[0132] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of a substrate by surface tension and then left stationary for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispense nozzle is scanned at a constant speed (dynamic dispense method). After the development step, a step of stopping development by replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0133] The organic solvent contained in the developer is preferably at least one selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0134] The ClogP value of the organic solvent contained in the developer is not particularly limited, but is preferably 0.00 or more, and more preferably 1.00 or more. When two or more organic solvents are contained, the ClogP value of the mixed solvent thereof is preferably within the above range.

[0135] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

[0136] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, 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 butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0137] As the alcohol-based solvent, the amide-based solvent, the ether-based solvent, and the hydrocarbon-based solvent, for example, the solvents disclosed in paragraphs

[0715] to

[0718] of the specification of U.S. Patent Application Publication No. 2016 / 0070167 can be used.

[0138] The above solvents may be mixed in combination, or may be mixed with other solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass, based on the total amount of the developer. In order to achieve superior effects of the present invention, the developer preferably contains a first organic solvent and a second organic solvent, and more preferably the boiling point of the first organic solvent is higher than the boiling point of the second organic solvent and the ClogP value of the first organic solvent is higher than the ClogP value of the second organic solvent. Note that the boiling points refer to boiling points at 1 atmosphere (760 mmHg).

[0139] The content ratio of the first organic solvent to the second organic solvent in the developer is not particularly limited, but in terms of better effects of the present invention, the mass ratio of the content of the second organic solvent to the content of the first organic solvent is preferably 1 to 50, and more preferably 3 to 20.

[0140] The second organic solvent in the developer is preferably the ketone solvent or the ester solvent, more preferably an ester solvent, and even more preferably butyl acetate or isoamyl butyrate, in terms of achieving the effects of the present invention more effectively. The first organic solvent is not particularly limited, but is preferably an organic solvent having a ClogP value of 3.00 or more, and more preferably a hydrocarbon solvent.

[0141] <Step 4: Rinse Step> The pattern formation method preferably includes, after step 3, step 4 of rinsing the pattern with a rinse liquid containing an organic solvent.

[0142] The rinse solution contains an organic solvent. The organic solvent contained in the rinse solution is preferably at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Examples of the hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include those described in the developer containing an organic solvent.

[0143] The method for the rinsing step is not particularly limited, and examples thereof include a method in which a rinsing liquid is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with a rinsing liquid for a certain period of time (dip method), and a method in which a rinsing liquid is sprayed onto the surface of the substrate (spray method).

[0144] The pattern formation method of the present invention may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinse solution remaining between and within the pattern due to baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is preferably carried out at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0145] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate to be etched. That is, the pattern formed in step 3 may be used as an etching mask to process the substrate (or the underlayer film and substrate) to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and substrate) using the pattern formed in step 3 as a mask is preferred. Oxygen plasma etching is preferred as the dry etching.

[0146] In terms of achieving better effects of the present invention, it is preferable that the developer contains two or more organic solvents when the pattern formation method does not include step 4, and that at least one of the developer and the rinse solution contains two or more organic solvents when the pattern formation method includes step 4. The two or more organic solvents contained in the developer and the rinse solution are preferably a combination of the first organic solvent and the second organic solvent described above.

[0147] The resist composition and various materials used in the pattern formation method of the present invention (e.g., solvent, developer, rinse, anti-reflective coating composition, top coat composition, etc.) preferably do not contain 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, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0148] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0149] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0150] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less.

[0151] [Method for Manufacturing an Electronic Device] The present invention also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. The electronic device of the present invention is suitable for installation in electrical and electronic equipment (such as home appliances, office automation (OA), media-related equipment, optical equipment, and communication equipment).

[0152] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0153] [Components of Resist Composition] The components used in preparing the resist compositions used in each of the examples and comparative examples, as well as the materials used in the evaluations described below, are listed below.

[0154] [Compound A] The structures of Compound A (A-1 to A-12) used in preparing the resist composition are shown below. For polymers having repeating units, the weight average molecular weight (Mw) is shown to the right of the compound. The number attached to each repeating unit indicates the content (mol %) of that repeating unit relative to all repeating units in the polymer.

[0155]

[0156] [Compound B] The structures of Compounds B (B-1 to B-16) used in preparing the resist compositions are shown below. For polymers having repeating units, the weight average molecular weight (Mw) is shown to the right of the compound. The number attached to each repeating unit indicates the content (mol %) of that repeating unit relative to all repeating units in the polymer.

[0157]

[0158]

[0159] [Additives C] The additives C (C-1 to C-5) used in preparing the resist compositions are shown below. C-1: Megafac F176 (manufactured by DIC Corporation, fluorochemical surfactant) C-2: Megafac R08 (manufactured by DIC Corporation, fluorine and silicon surfactant) C-3: PF656 (manufactured by OMNOVA, fluorochemical surfactant) C-4: 2,6-di-tert-butyl-p-cresol (polymerization inhibitor) C-5: compound having the following structure (polymerization inhibitor)

[0160]

[0161] [Solvent F] The solvents F (F-1 to F-9) used in preparing the resist compositions are as follows: 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

[0162] [Solvent d] The solvents d (d-1 to d-9) used as developers in the evaluation are as follows: d-1: 2-heptanone d-2: isobutyl propionate d-3: diisobutyl ether d-4: n-undecane d-5: 4-methyl-2-pentanol d-6: PGMEA d-7: butyl acetate d-8: N-methyl-2-pyrrolidone d-9: diisobutyl ketone

[0163] [Comparative Compounds] The structures of the comparative compounds (Z-1 to Z-4) used in preparing the comparative resist compositions are shown below. In the structural formulas, the numerical value indicated as Mw indicates the weight average molecular weight. Comparative compounds Z-1 and Z-2 were used as resins, comparative compound Z-3 was used as a photoacid generator, and comparative compound Z-4 was used as a photodegradable base.

[0164]

[0165] [Preparation of Resist Compositions] The components shown in Tables 1 and 2 below were mixed to a solid content (total solid content) concentration of 1.6% by mass. The resulting mixture was passed through a polyethylene filter with a pore size of 0.03 μm and filtered to prepare each resist composition. "Solid content (total solid content)" refers to all components other than the solvent.

[0166] In Tables 1 and 2, the "mass %" column indicates the content (mass %) of each solid component relative to the total solid content. The solid content refers to the components excluding the solvent. In Tables 1 and 2, the entries separated by " / " in the "Type" column indicate that multiple compounds are contained, and the entries separated by " / " in the "Mixing Ratio" column indicate the mixing ratio (mass ratio) of multiple compounds. For example, "Solvent F" in resist composition "Re-14" contains "F-1," "F-2," and "F-8," with the contents being "70," "25," and "5" mass %, respectively.

[0167]

[0168]

[0169] [Pattern Formation and Evaluation] Using the resist compositions of each of the Examples and Comparative Examples, pattern resolution was evaluated using patterns obtained by EUV exposure according to the procedure described below.

[0170] [Pattern Formation] An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer with a diameter of 12 inches and baked at 205°C for 60 seconds to form a 20 nm thick underlayer film. A resist composition shown in Table 2 was applied thereon and baked at 100°C for 60 seconds to form a 30 nm thick resist film. Using an EUV exposure device (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36), the silicon wafer having the resulting resist film was subjected to pattern irradiation so that the average line width of the resulting pattern was 20 nm. A mask with a line size of 20 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90° C. for 60 seconds, then developed for 30 seconds with the developer shown in Table 2, and spin-dried to obtain a positive pattern.

[0171] [Resolution Evaluation (Limiting Resolution, nm)] In the above [Pattern Formation], the exposure was performed at an optimum exposure dose Eop (μC / cm ２ ) (the exposure dose when a pattern formed using the resist composition reproduces the pattern of the mask used for exposure). Next, a test was conducted to form a line and space pattern by gradually changing the exposure dose from the optimum exposure dose Eop. In this case, the minimum dimension of the pattern that could be resolved without collapsing was determined using a critical dimension scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)), and this was taken as the "resolution (nm)." The smaller the resolution value, the better the resolution. The resolution is preferably 15.0 nm or less, more preferably 13.0 nm or less, and most preferably 11.0 nm or less.

[0172] [Results] The evaluation results are shown in Table 3. The compositions of the developers (D-1 to D-9) shown in Table 3 are shown in Table 4. In Table 4, the values ​​in the "mass %" column indicate the content (mass %) of each of the above-mentioned solvents d relative to the total mass of the developer.

[0173]

[0174]

[0175] The results in Table 3 confirm that the resist compositions (actinic ray-sensitive or radiation-sensitive resin compositions) of the present invention have excellent resolution. On the other hand, the resist compositions Re-C1 to Re-C3 used in Comparative Examples 1 to 3 had insufficient resolution.

[0176] Comparison of Examples 5 and 14 with other Examples and the like confirmed that when compound A has a group represented by formula (A1) and in formula (A1), m is 4 or more, the pattern resolution is more excellent. Comparison of Examples 1 to 4, 8, 10 to 12, and 18 with other Examples and the like confirmed that compound B has a specific functional group that is a nitrogen-containing aromatic heterocyclic group, NH ２ -, NH protected by a removable protecting group ２ Group, NHR Ｎ１ -, NHR protected by a removable protecting group Ｎ１ groups, and NR Ｎ２ ２ It has been confirmed that when the functional group is selected from the group consisting of -, the pattern resolution is more excellent.

Claims

1. Compound A has a plurality of iodine atoms bonded to a carbon atom, and a nitrogen-containing aromatic heterocyclic group, -NH ２ , NH protected by a removable protecting group ２ group, -NHR Ｎ１ , NHR protected by a removable protecting group Ｎ１ group, -NR Ｎ２ ２ , -C≡N, -OH, -OR Ｏ , -SH, -SR Ｓ , -PR Ｐ１ ２ , and -P(OR Ｐ２ ) ２ and a compound B having a plurality of specific functional groups selected from the group consisting of the following, and having no iodine atom bonded to a carbon atom, and satisfying at least one of Requirement 1 and Requirement 2. Requirement 1: Compound A is a polymer having a repeating unit containing an iodine atom bonded to the carbon atom. Requirement 2: Compound B is a polymer having a repeating unit containing the specific functional group. Ｎ１ , R Ｎ２ , R Ｏ , R Ｓ , R Ｐ１ and R Ｐ２ R each independently represents a monovalent hydrocarbon group which may have a substituent. Ｎ２ The monovalent hydrocarbon groups represented by R may be bonded to each other to form a ring. Ｐ１ The monovalent hydrocarbon groups represented by R may be bonded to each other to form a ring. Ｐ２ The monovalent hydrocarbon groups represented by the following formula (I) may be bonded to each other to form a ring.

2. The composition according to claim 1, wherein the compound A is a compound having a group represented by any one of formulas (A1) to (A3). In formula (A1), EWG represents an electron-withdrawing group. n and m each independently represent an integer of 1 or more. Ar represents an aromatic hydrocarbon ring which may have a substituent. In formula (A2), R each independently represents a hydrogen atom or a substituent. However, at least one of R represents an electron-withdrawing group. * represents a bonding position.

3. The composition according to claim 2, wherein in formula (A1), m is 4 or more.

4. The composition according to claim 2, wherein in formula (A2), all R's represent electron-withdrawing groups.

5. The composition according to claim 2, wherein in said formula (A1), EWG represents a fluorine atom or a cyano group, and in said formula (A2), at least one of R represents a fluorine atom or a cyano group.

6. The composition according to claim 2, wherein the compound A is a compound having a structure represented by the formula (A1).

7. The specific functional group is a nitrogen-containing aromatic heterocyclic group, NH ２ -, NH protected by a removable protecting group ２ Group, NHR Ｎ１ -, NHR protected by a removable protecting group Ｎ１ Groups, and NR Ｎ２ ２ The composition according to claim 1 or 2, wherein the functional group is selected from the group consisting of -.

8. The composition according to claim 1 or 2, which satisfies requirement 1.

9. The composition according to claim 1 or 2, which satisfies requirement 2.

10. A resist film formed using the composition according to claim 1 or 2.

11. A pattern forming method comprising the steps of: forming a resist film on a substrate using the composition according to claim 1 or 2; exposing the resist film to light; and developing the exposed resist film using a developer containing an organic solvent.

12. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 11.

Images