A light-sensitive or radiation-sensitive resin composition, and a method for manufacturing a resist pattern

Abstract

The present invention aims to provide a photosensitive or radiation-sensitive resin composition that is resistant to defects when an etching treatment is performed using a formed resist pattern as a mask, and also has excellent storage stability. The present invention also aims to provide a method for manufacturing a resist pattern. The sensitizing light-reducing or radiation-reducing resin composition of the present invention comprises a resin whose polarity is increased by the action of an acid, a photogenerator, at least one compound Y selected from the group consisting of a compound represented by formula (1) and a compound represented by formula (2), and a sensitizing light-reducing or radiation-reducing resin composition containing a metal atom, wherein the mass ratio of the content of the compound Y to the content of the metal atom is 1.0×10 to 1.0×109.

Description

Technology Field

[0001] The present invention relates to a light-sensitive or radiation-sensitive resin composition and a method for manufacturing a resist pattern. Background Technology

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), microfabrication by lithography using a photosensitive or radiation-sensitive composition (hereinafter also referred to as a "resist composition") is performed. Recently, with the high integration of integrated circuits, the formation of ultra-fine patterns in the sub-micron or quarter-micron region is required.

[0003] Accordingly, in order to miniaturize semiconductor devices, the wavelength of the exposure light source and the numerical aperture (high NA) of the projection lens are being increased, and exposure machines using a KrF excimer laser with a wavelength of 248 nm or an ArF excimer laser with a wavelength of 193 nm as a light source have been developed. In addition, recently, pattern formation methods using extreme ultraviolet (EUV) light or electron beam (EB) as a light source are also being considered.

[0004] For example, Patent Document 1 discloses a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, wherein the photosensitive resin composition comprises an alkali-soluble polymer, a compound having an ethylenically unsaturated double bond, a photopolymerization initiator, and a metal atom, and the content of the metal atom in the photosensitive resin composition layer is 0.005 ppm or more and 70 ppm or less based on the photosensitive resin composition layer. Prior art literature

[0005] Patent Document 1: International Publication No. 2019 / 142786 The problem to be solved

[0006] The inventors, referring to the technology described in Patent Document 1, further examined a resist pattern of a finer size formed using a resist composition containing metal atoms and found that pattern defects presumed to be of metal atom origin are prone to occur in a pattern formed by etching using the resist pattern as a mask and formed on a target layer lower than the resist pattern. In addition, stability of quality after storing the resist composition for a predetermined period was also required.

[0007] The present invention aims to provide a light-sensitive or radiation-sensitive resin composition that, in light of the above circumstances, is unlikely to cause defects in the formed pattern when an etching treatment is performed using a formed resist pattern as a mask, and also has excellent storage stability.

[0008] In addition, the present invention also has the objective of providing a method for manufacturing a resist pattern. means of solving the problem

[0009] The inventors have found that the above problem can be solved by the following configuration.

[0010] [1] At least one compound Y selected from the group consisting of a resin whose polarity is increased by the action of an acid, a photogenerator, a compound represented by Formula (1) described below, and a compound represented by Formula (2) described below, and a desensitizing photo- or radiation-desensitizing resin composition containing a metal atom, wherein the mass ratio of the content of compound Y to the content of the metal atom is 1.0×10 to 1.0×10 9 Phosphorus, photosensitive or radiation-sensitive resin composition.

[0011] [2] A light-sensitive or radiation-sensitive resin composition described in [1] that satisfies the requirement 1 described below.

[0012] [3] A desensitizing photoreactive or radiation-reducing resin composition as described in [1] or [2], wherein the resin has repeating units represented by the formula (Y) described below.

[0013] [4] A photosensitive or radiation-sensitive resin composition described in any one of [1] to [3], further containing propylene glycol methyl ether acetate.

[0014] [5] A photosensitive or radiation-sensitive resin composition described in any one of [1] to [4], further containing a peroxide, wherein the content of the peroxide is 100 mass ppm or less with respect to the total mass of the photosensitive or radiation-sensitive resin composition.

[0015] [6] A desensitizing photoreceptor or radiation-reducing resin composition for EUV exposure as described in any one of [1] to [5].

[0016] [7] A method for manufacturing a resist pattern comprising: a resist film forming process in which a resist film is formed on a substrate using a photosensitive or radiation-sensitive resin composition described in any one of [1] to [6]; an exposure process in which the resist film is exposed to light; and a development process in which the exposed resist film is developed using a developer.

[0017] [8] A method for manufacturing a resist pattern as described in [7], wherein the above-described developer comprises an ester-based solvent and a hydrocarbon-based solvent.

[0018] [9] A method for manufacturing a resist pattern as described in [7] or [8], wherein the above-mentioned developer comprises butyl acetate and undecaein. Effects of the invention

[0019] According to the present invention, when an etching treatment is performed using a formed resist pattern as a mask, a pattern formed is less likely to have defects, and a desensitizing light- or radiation-sensitive resin composition with excellent storage stability can be provided.

[0020] In addition, according to the present invention, a method for manufacturing a resist pattern can be provided. Specific details for implementing the invention

[0021] The present invention will be described in detail below.

[0022] The description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0023] Regarding the notation of groups (atomic groups) in this specification, unless contrary to the spirit of the present invention, notations that do not specify substitution or non-substitution include groups having substituents along with groups not having substituents. For example, the term "alkyl group" includes not only alkyl groups not having substituents (non-substituted alkyl groups) but also alkyl groups having substituents (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group comprising at least one carbon atom.

[0024] Unless otherwise specified, monovalent substituents are preferred.

[0025] In this specification, "active light" or "radiation" means, for example, emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam), etc. In this specification, "light" means active light or radiation.

[0026] Unless otherwise specifically explained, the term "exposure" in this specification includes not only exposure by emission spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also drawing by particle beams such as electron beams and ion beams.

[0027] In this specification, "~" is used to mean including the values ​​described before and after it as lower and upper limits.

[0028] The bonding direction of the divalent groups indicated in this specification is not limited unless specifically explained. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may be -CO-O- or -O-CO-. Also, the compound may be "X-CO-OZ" or "XO-CO-Z".

[0029] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic.

[0030] 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 polystyrene equivalent values ​​by GPC measurement using a GPC (Gel Permeation Chromatography) device (Dosoh HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: Dosoh TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0031] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, it is a value obtained by calculation based on the database of Hamette's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification represent values ​​obtained by calculation using this software package.

[0032] Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris(1994-2007 ACD / Labs).

[0033] Meanwhile, pKa is also determined by molecular orbital calculations. Specifically, this method involves H₂ in an aqueous solution based on thermodynamic cycles. + One method is to calculate it by calculating the dissociation free energy. H + Regarding the method for calculating the dissociation free energy, it can be calculated, for example, by the Density Functional Path (DFT); however, various other methods have been reported in the literature and are not limited to this. Furthermore, while there are multiple software programs capable of performing DFT, Gaussian 16 can be cited as an example.

[0034] In this specification, pKa refers to a value obtained by calculation based on a database of Hammett's substituent constants and known literature values ​​using software package 1 as described above. However, if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on the DFT (density functional method) is adopted.

[0035] Additionally, as described above, pKa in this specification refers to "pKa in an aqueous solution," but if pKa in an aqueous solution cannot be calculated, "pKa in a dimethyl sulfoxide (DMSO) solution" shall be adopted.

[0036] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0037] In this specification, the term "solid content" refers to all components capable of constituting a resist film other than the solvent and the compound represented by Formula (1) described below. Furthermore, even if the nature of the above components is liquid, they are calculated as solid content.

[0038] In the present specification, for example, where it is stated that "Composition A substantially comprises only component B," it is intended that the content of component B is 95 mass% or more with respect to the total mass of composition A. Also, in the present specification, for example, where it is stated that "Composition A does not substantially comprise component C," it is intended that the content of component C is 5 mass% or less with respect to the total mass of composition A.

[0039] [Sensitive light-sensitive or radiation-sensitive resin composition]

[0040] The photosensitive or radiation-sensitive resin composition (resist composition) of the present invention comprises a resin whose polarity is increased by the action of an acid, a photogenerator, at least one compound Y selected from the group consisting of a compound represented by Formula (1) and a compound represented by Formula (2) described below, and a metal atom.

[0041] The resist composition of the present invention has a mass ratio of the content of compound Y to the content of metal atoms of 1.0×10 to 1.0×10 9 It is characterized by being.

[0042] In addition, in this specification, "content of compound Y" means the total content of the compound represented by formula (1) and the compound represented by formula (2) described below.

[0043] The mass ratio of the content of compound Y to the content of metal atoms is 1.0×10 to 1.0×10 9Thus, although the detailed mechanism by which a resist composition with excellent effects of the present invention is obtained has not been clarified, the inventors speculate that if the content of metal atoms is relatively excessive, when an etching treatment is performed on a target layer below the resist pattern using a resist pattern formed using the resist composition as a mask, many defects originating from metal atoms occur in the formed pattern, whereas if the content of compound Y is relatively excessive, the resin is prone to decomposition during storage of the resist composition, and defects are prone to occur in the resist pattern formed using the resist composition after storage.

[0044] Accordingly, according to the resist composition of the present invention, when an etching treatment is performed using a formed resist pattern as a mask, it is difficult for defects to occur in the formed pattern, and the storage stability is excellent.

[0045] In this specification, "effect of the present invention" means at least one of the effect of suppressing the occurrence of defects in the pattern and preservation stability.

[0046] [Each component of the resist composition]

[0047] The resist composition according to the present invention contains at least a resin whose polarity increases by the action of an acid (hereinafter also referred to as "acid-degradable resin (A)" or "resin (A)"), a photocatalytic agent, a compound Y, and a metal atom.

[0048] As each component included in the resist composition, components included in a known resist composition capable of forming a resist pattern by performing photolithography and development using a developer can be used.

[0049] The resist composition may be a positive-type resist composition or a negative-type resist composition. The resist composition may be a resist composition for alkali development or a resist composition for organic solvent development.

[0050] The resist composition may be a chemically amplified type resist composition or a non-chemically amplified type resist composition. Typically, the resist composition is a chemically amplified type resist composition.

[0051] The above exposure treatment preferably includes EUV exposure, KrF exposure, ArF exposure, or EB exposure, and EUV exposure is more preferable. That is, the resist composition is preferably for EUV exposure, KrF exposure, ArF exposure, or EB exposure, and is more preferable for EUV exposure.

[0052] Hereinafter, various components included in the resist composition will be described in detail.

[0053] <Acid-degradable resin (A)>

[0054] The resist composition includes an acid-degradable resin (A).

[0055] The resin (A) often contains a group that decomposes upon the action of acid and increases polarity (hereinafter also referred to as an "acid-degradable group"), and it is preferable to include repeating units having the acid-degradable group.

[0056] In a method for forming a resist pattern using a resist composition in which the resin (A) includes acid-degradable groups, typically, a positive type pattern is formed by employing an alkaline developer as the developer, and a negative type pattern is formed by employing an organic developer as the developer.

[0057] As for the repeating unit having an acid-degradable group, in addition to the repeating unit having an acid-degradable group described below, a repeating unit having an acid-degradable group including an unsaturated bond is preferred.

[0058] ≪Repeating unit having an acid-degrading group (Aa)≫

[0059] It is preferable that the resin (A) has a repeating unit (Aa) having an acid-degradable group (hereinafter also referred to as "repeating unit (Aa)").

[0060] An acid-degradable group is a group that decomposes by the action of an acid to generate a polar group, and it is desirable to have a structure in which the polar group is protected by a detachable group that is detached by the action of an acid. That is, it is desirable for the resin (A) to have a repeating unit (Aa) having a group that decomposes by the action of an acid to generate a polar group. A resin having a repeating unit (Aa) has increased polarity by the action of an acid, solubility in an alkaline developer increases, and solubility in an organic solvent decreases.

[0061] As for the polar group, an alkali-soluble group is preferred, and examples include an acidic group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, a (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylsulfonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, and an alcoholic hydroxyl group.

[0062] Among these, as polar groups, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is more preferred.

[0063] Examples of groups that are removed by the action of acid include the groups represented by equations (Y1) to (Y4).

[0064] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0065] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0066] Equation (Y3): -C(R 36 )(R 37 )(OR 38 )

[0067] Equation (Y4): -C(Rn)(H)(Ar)

[0068] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), an alkeneyl group (straight or branched), or an aryl group (monocyclic or polycyclic). Additionally, when all of Rx1 to Rx3 are alkyl groups (straight or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups.

[0069] Among these, it is preferable that Rx1 to Rx3 each independently represent a straight-chain or branched-chain alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a straight-chain alkyl group.

[0070] Two of Rx1 to Rx3 may combine to form a monocyclic or polycyclic ring.

[0071] As for the alkyl groups of Rx1 to Rx3, alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred.

[0072] As for the cycloalkyl groups of Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0073] As for the aryl groups of Rx1 to Rx3, aryl groups having 6 to 10 carbon atoms are preferred, and examples include phenyl groups, naphthyl groups, and anthryl groups.

[0074] As for the alkene groups of Rx1~Rx3, a vinyl group is preferred.

[0075] As for the ring formed by combining two of Rx1 to Rx3, a cycloalkyl group is preferred. As for the cycloalkyl group formed by combining two of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, or an adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.

[0076] The cycloalkyl group formed by the combination of two of Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring substituted with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. In addition, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

[0077] The group represented by formula (Y1) or formula (Y2) is preferably, for example, in which Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are combined to form the cycloalkyl group described above.

[0078] In the case where the resist composition is, for example, a resist composition for EUV exposure, the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx1 to Rx3, and the ring formed by combining two of Rx1 to Rx3, may additionally have a fluorine atom or an iodine atom as a substituent.

[0079] In equation (Y3), R 36 ~R 38 Each independently represents a hydrogen atom or a monovalent organic group. R 37 and R 38Silver may combine with each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. R 36 It is also desirable that it be a hydrogen atom.

[0080] In addition, the above alkyl group, cycloalkyl group, aryl group, and aralkyl group may include a group having a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. For example, the above alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with, for example, one or more methylene groups having a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group.

[0081] In addition, regarding the repeating unit having an acid-degradable group described later, R 38 It may combine with other substituents on the main chain of the repeating unit to form a ring. R 38 The group formed by the bonding of other substituents on the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0082] In the case where the resist composition is, for example, a resist composition for EUV exposure, R 36 ~R 38 A monovalent organic group represented by, and, R 37 and R 38 It is also desirable for the ring formed by these mutual bonding to additionally have a fluorine atom or an iodine atom as a substituent.

[0083] As for Equation (Y3), it is preferable to have a group represented by the following Equation (Y3-1).

[0084] [Chemical Formula 1]

[0085]

[0086] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof (e.g., a combination of an alkyl group and an aryl group).

[0087] M represents a single bond or a divalent linker.

[0088] Q represents an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (e.g., a combination of an alkyl group and a cycloalkyl group).

[0089] The alkyl group and the cycloalkyl group may, for example, be substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.

[0090] In addition, it is preferable that one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group combining an alkylene group and an aryl group.

[0091] At least two of Q, M, and L1 may be combined to form a ring (preferably, a 5-membered or 6-membered ring).

[0092] In terms of pattern refinement, it is preferable that L2 be a secondary or tertiary alkyl group, and more preferable that it be a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl groups, cyclohexyl groups, or norbornyl groups, and examples of tertiary alkyl groups include tert-butyl groups or adamantane groups. In these embodiments, the Tg (glass transition temperature) and activation energy of the resin (A) are increased in the repeating unit having the acid-degradable group described later, so in addition to ensuring film strength, fogging can be suppressed.

[0093] In the case where the resist composition is, for example, a resist composition for EUV exposure, it is also preferable that the alkyl group, cycloalkyl group, aryl group, and a combination thereof represented by L1 and L2 further have a fluorine atom or an iodine atom as a substituent. In addition, it is also preferable that the alkyl group, cycloalkyl group, aryl group, and aralkyl group contain heteroatoms such as oxygen atoms in addition to fluorine atoms and iodine atoms (i.e., the alkyl group, cycloalkyl group, aryl group, and aralkyl group are, for example, one of the methylene groups is substituted with a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group).

[0094] In addition, when the resist composition is, for example, a resist composition for EUV exposure, among the alkyl group that may contain a heteroatom represented by Q, the cycloalkyl group that may contain a heteroatom, the aryl group that may contain a heteroatom, the amino group, the ammonium group, the mercapto group, the cyano group, the aldehyde group, and the groups combined thereof, it is also preferable that the heteroatom is a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom.

[0095] In formula (Y4), Ar represents an aromatic group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. More preferably, Ar is an aryl group.

[0096] In the case where the resist composition is, for example, a resist composition for EUV exposure, it is also preferable that the aromatic group represented by Ar, and the alkyl group, cycloalkyl group, and aryl group represented by Rn have fluorine atoms and iodine atoms as substituents.

[0097] In terms of further improving acid decompositionability, when a non-aromatic ring is directly bonded to a polar group (or its residue) in a detacher protecting a polar group, it is also desirable that the reducing atom adjacent to the reducing atom directly bonded to the polar group (or its residue) among the non-aromatic rings does not have a halogen atom, such as a fluorine atom, as a substituent.

[0098] The detachable group that is removed by the action of acid may also be a 2-cyclopentenyl group having a substituent (alkyl group, etc.) such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (alkyl group, etc.) such as a 1,1,4,4-tetramethylcyclohexyl group.

[0099] As for the repeating unit (Aa), the repeating unit represented by Equation (A) is also desirable.

[0100] [Chemical Formula 2]

[0101]

[0102] L1 represents a divalent linker that may have a fluorine atom or an iodine atom, R1 represents an alkyl group that may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom, or an iodine atom, or an aryl group that may have a fluorine atom or an iodine atom, and R2 represents a detaching group that may have a fluorine atom or an iodine atom after being detached by the action of an acid.

[0103] In addition, as a suitable embodiment of the repeating unit represented by formula (A), an embodiment in which at least one of L1, R1, and R2 has a fluorine atom or an iodine atom may also be cited.

[0104] L1 represents a divalent linker that may have a fluorine atom or an iodine atom. Examples of divalent linkers that may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that may have a fluorine atom or an iodine atom (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linkers formed by connecting multiple of these. Among these, as L1, -CO-, an arylene group, or -arylene group-alkylene group that may have a fluorine atom or an iodine atom is preferred, and -CO-, an arylene group, or -arylene group-alkylene group that may have a fluorine atom or an iodine atom is more preferred.

[0105] As for the arylene group, a phenylene group is preferred.

[0106] The alkylene group may be in a straight chain or a branched chain. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred.

[0107] When the alkylene group has a fluorine atom or an iodine atom, the total number of fluorine atoms and iodine atoms included in the alkylene group is not particularly limited, but 2 or more is preferred, 2 to 10 is more preferred, and 3 to 6 is more preferred.

[0108] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine atom or an iodine atom, or an aryl group that may have a fluorine atom or an iodine atom.

[0109] The alkyl group may be in a straight chain or a branched chain. 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.

[0110] The total number of fluorine atoms and iodine atoms included in an alkyl group having a fluorine atom or an iodine atom is not particularly limited, but 1 or more is preferred, 1 to 5 is more preferred, and 1 to 3 is more preferred.

[0111] The above alkyl group may include heteroatoms such as oxygen atoms other than halogen atoms.

[0112] R2 represents a deluminater that may have a fluorine atom or an iodine atom after being deluminated by the action of an acid. Examples of deluminaters that may have a fluorine atom or an iodine atom include those represented by the above-described formulas (Y1) to (Y4) and those having a fluorine atom or an iodine atom, and the suitability mode is the same.

[0113] As for the repeating unit (Aa), the repeating unit represented by the general formula (AI) is also desirable.

[0114] [Chemical Formula 3]

[0115]

[0116] In the general formula (AI),

[0117] Xa1 represents a hydrogen atom, or an alkyl group that may have a substituent.

[0118] T represents a single bond, or a divalent linker.

[0119] Rx1 to Rx3 each independently represent an alkyl group (straight or branched), a cycloalkyl group (single or polycyclic), an aryl group, or an alkeneyl group. However, if all of Rx1 to Rx3 are alkyl groups (straight or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups.

[0120] Two of Rx1 to Rx3 may be combined to form a cycloalkyl group (monocyclic or polycyclic).

[0121] The alkyl group that may have a substituent, represented by Xa1, is, for example, a methyl group or -CH2-R 11 One example is the energy manifested as. R 11 It represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples include an alkyl group having 5 or fewer carbon atoms that may be substituted with a halogen atom, an acyl group having 5 or fewer carbon atoms that may be substituted with a halogen atom, and an alkoxy group having 5 or fewer carbon atoms that may be substituted with a halogen atom, wherein an alkyl group having 3 or fewer carbon atoms is preferred, and a methyl group is more preferred. As Xa1, a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferred.

[0122] Examples of the divalent linking groups of T include alkylene groups, aromatic groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0123] T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0124] As for the alkyl groups of Rx1 to Rx3, alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred.

[0125] As for the cycloalkyl groups of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, and an adamantyl group is preferred.

[0126] As for the cycloalkyl group formed by the combination of two of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group is preferred, and additionally, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, and an adamantyl group is preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.

[0127] The cycloalkyl group formed by the combination of two of Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring substituted with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group.

[0128] As for the alkene devices of Rx1~Rx3, vinyl devices can be cited.

[0129] Phenyl groups can be used as aryl groups of Rx1~Rx3.

[0130] The repeating unit represented by the general formula (AI) is preferably, for example, in which Rx1 is a methyl or ethyl group and Rx2 and Rx3 are combined to form the cycloalkyl group described above.

[0131] When each of the above groups has a substituent, examples of the substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituents is preferably 8 or less.

[0132] The repeating unit represented by the general formula (AI) is preferably an acid-degradable (meth)acrylic acid tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group and T represents a single bond).

[0133] The resin (A) may have only one type of repeating unit (Aa) or two or more types.

[0134] The content of repeating units (Aa) (total content in cases where two or more types of repeating units (Aa) exist) is preferably 15 to 80 mol% with respect to the total repeating units in the resin (A), and more preferably 20 to 70 mol%.

[0135] Preferably, resin (A) has at least one repeating unit selected from the group consisting of repeating units represented by the following general formulas (A-VIII) to (A-XII), as a repeating unit (Aa).

[0136] [Chemical Formula 4]

[0137]

[0138] In general formula (A-VIII), R5 represents a tert-butyl group, -CO-O-(tert-butyl) group.

[0139] In general formula (A-IX), R6 and R7 each independently represent a monovalent organic group. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups.

[0140] In the general formula (AX), p represents 1 or 2.

[0141] In general formulas (AX) to (A-XII), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R9 represents an alkyl group having 1 to 3 carbon atoms.

[0142] Among the general formula (A-XII), R 10 It represents a carbon alkyl group having 1 to 3 carbon atoms or an adamantyl group.

[0143] ≪Repetitive unit with a variability (A-1)≫

[0144] The resin (A) may have a repeating unit (A-1) having an acid group.

[0145] As for the acid group, an acid group with a pKa of 13 or less is preferred. As for the acid dissociation constant of the acid group, 13 or less is preferred, 3 to 13 is more preferred, and 5 to 10 is more preferred.

[0146] When the resin (A) has acid groups with a pKa of 13 or less, the content of acid groups in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is more preferred. If the content of acid groups is within the above range, the development proceeds well, the formed pattern shape is superior, and the resolution is also superior.

[0147] As for the acid group, for example, a carboxyl group, a hydroxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group is preferred.

[0148] In addition, one or more (preferably 1 to 2) of the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The -C(CF3)(OH)-CF2- formed in this way is also preferred as an acid group. In addition, one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-.

[0149] A repeating unit (A-1) having an acid group is preferably a repeating unit having a structure in which a polar group is protected by a detaching group that is detached by the action of the acid described above, and a repeating unit (A-2) having a lactone group, a sulfonate group, or a carbonate group described later.

[0150] Repeating units having acid groups may have fluorine atoms or iodine atoms.

[0151] As a repeating unit having a dispersive function, the repeating unit represented by Equation (Y) is preferred in that it has superior sensitivity.

[0152] [Chemical Formula 5]

[0153]

[0154] In formula (Y), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.

[0155] L represents a divalent linker having a single bond or an oxygen atom. It is preferable that L be a single bond.

[0156] R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. If multiple Rs are present, they may be identical or different. If multiple Rs are present, they may be bonded to each other to form a ring. As R, a hydrogen atom is preferred.

[0157] a represents an integer from 1 to 3.

[0158] b represents an integer from 0 to (5-a).

[0159] Hereinafter, repeating units having a number are exemplified. In the formulas, a represents 1 or 2.

[0160] [Chemical Formula 6]

[0161]

[0162] [Chemical Formula 7]

[0163]

[0164] [Chemical Formula 8]

[0165]

[0166] As a repeating unit having an acid group, for example, a repeating unit having a phenolic hydroxyl group described in paragraphs 0089 to 0100 of Japanese Patent Publication No. 2018-189758 can be suitably used.

[0167] When the resin (A) comprises repeating units (A-1) having acid groups, the resist composition comprising the resin (A) is preferred for KrF exposure, EB exposure, or EUV exposure. In such an embodiment, the content of repeating units having acid groups in the resin (A) is preferably 30 to 100 mol% with respect to the total repeating units in the resin (A), more preferably 40 to 100 mol%, and even more preferably 50 to 100 mol%.

[0168] ≪Repeating unit (A-2) having at least one selected from the group consisting of lactone structure, sulfone structure, carbonate structure, and hydroxyadamantane structure≫

[0169] The resin (A) may have a repeating unit (A-2) having at least one selected from the group consisting of a lactone structure, a carbonate structure, a sulfone structure, and a hydroxyadamantane structure.

[0170] The lactone structure or selton structure in the repeating unit having a lactone structure or a selton structure is not particularly limited, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring selton structure is preferred, and it is more preferable that another ring structure is condensed in a form that forms a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure, or that another ring structure is condensed in a form that forms a bicyclo structure or a spiro structure in the 5- to 7-membered ring selton structure.

[0171] Examples of repeating units having a lactone structure or a sulfone structure include the repeating units described in paragraphs 0094 to 0107 of International Publication No. 2016 / 136354.

[0172] The resin (A) may have repeating units having a carbonate structure. The carbonate structure is preferably a cyclic carbonate ester structure.

[0173] Examples of repeating units having a carbonate structure include the repeating units described in paragraphs 0106 to 0108 of International Publication No. 2019 / 054311.

[0174] Resin (A) may have repeating units having a hydroxyadamantane structure. Examples of repeating units having a hydroxyadamantane structure include repeating units represented by the following general formula (AIIa).

[0175] [Chemical Formula 9]

[0176]

[0177] In general formula (AIIa), R1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R2c to R4c each independently represent a hydrogen atom or a hydroxyl group. However, at least one of R2c to R4c represents a hydroxyl group. It is preferable that one or two of R2c to R4c are hydroxyl groups and the remainder are hydrogen atoms.

[0178] ≪Repeating unit having a fluorine atom or an iodine atom≫

[0179] Resin (A) may have repeating units having fluorine atoms or iodine atoms.

[0180] Examples of repeating units having a fluorine atom or an iodine atom include the repeating units described in paragraphs 0080 to 0081 of Japanese Patent Publication No. 2019-045864.

[0181] ≪Repeating unit having a mine generator≫

[0182] Resin (A) may have a repeating unit other than the above that has a group that generates acid upon irradiation with radiation.

[0183] Examples of repeating units having a fluorine atom or an iodine atom include the repeating units described in paragraphs 0092 to 0096 of Japanese Patent Publication No. 2019-045864.

[0184] ≪Repeating unit having alkali-soluble groups≫

[0185] The resin (A) may have repeating units having alkali-soluble groups.

[0186] Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohols in which the α-position is substituted with an electron-withdrawing group (e.g., hexafluoroisopropanol groups), and carboxyl groups are preferred. As the resin (A) has repeating units having alkali-soluble groups, the resolution for contact hole applications is increased.

[0187] Examples of repeating units having alkali-soluble groups include repeating units in which the alkali-soluble group is directly bonded to the main chain of the resin, such as repeating units made of acrylic acid and methacrylic acid, or repeating units in which the alkali-soluble group is bonded to the main chain of the resin through a linker. Additionally, the linker may have a monocyclic or polycyclic cyclic hydrocarbon structure.

[0188] As a repeating unit having an alkali-soluble group, a repeating unit made of acrylic acid or methacrylic acid is preferred.

[0189] ≪Repeating unit having neither an acid-degrading group nor a polar group≫

[0190] The resin (A) may also have repeating units that do not have either acid-degradable groups or polar groups. The repeating units that do not have either acid-degradable groups or polar groups preferably have a cycloaliphatic hydrocarbon structure.

[0191] Examples of repeating units that do not have either an acid-degrading group or a polar group include, for instance, the repeating unit described in paragraphs 0236–0237 of U.S. Patent Application Publication No. 2016 / 0026083, and the repeating unit described in paragraph 0433 of U.S. Patent Application Publication No. 2016 / 0070167.

[0192] In addition to the repeating structure unit described above, the resin (A) may have various repeating structure units for the purpose of controlling dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0193] ≪Characteristics of Suji (A)≫

[0194] As for the resin (A), it is preferable that all repeating units consist of repeating units derived from (meth)acrylate monomers. In this case, any resin may be used in which all repeating units are derived from methacrylate monomers, all repeating units are derived from acrylate monomers, or all repeating units are derived from methacrylate monomers and acrylate monomers. It is preferable that the repeating units derived from acrylate monomers are 50 mol% or less of the total repeating units in the resin (A).

[0195] When the resist composition is for fluorinated argon (ArF) exposure, it is preferable that the resin (A) substantially does not have aromatic groups for the sake of the transmittance of ArF light. More specifically, it is preferable that the repeating units having aromatic groups be 5 mol% or less with respect to the total repeating units of the resin (A), more preferable that they be 3 mol% or less, and ideally 0 mol%, that is, it is more preferable that there are no repeating units having aromatic groups.

[0196] Also, when the resist composition is for ArF exposure, it is preferable that the resin (A) has a monocyclic or polycyclic alicyclic hydrocarbon structure, and also preferable that it does not contain either fluorine atoms or silicon atoms.

[0197] When the resist composition is for krypton fluoride (KrF) exposure, EB exposure, or EUV exposure, it is preferable that the resin (A) has repeating units having aromatic hydrocarbon groups, and more preferable that it has repeating units having phenolic hydroxyl groups.

[0198] Examples of repeating units having a phenolic hydroxyl group include the repeating unit (A-1) exemplified above having an acid group, and repeating units derived from hydroxystyrene (meth)acrylate.

[0199] In addition, when the resist composition is for KrF exposure, EB exposure, or EUV exposure, it is also preferable that the resin (A) has repeating units having a structure protected by a group (detacher) in which a hydrogen atom of a phenolic hydroxyl group is decomposed and detached by the action of an acid.

[0200] When the resist composition is for KrF exposure, EB exposure, or EUV exposure, the content of repeating units having aromatic hydrocarbon groups included in the resin (A) is preferably 30 to 100 mol% with respect to the total repeating units in the resin (A), more preferably 40 to 100 mol%, and more preferably 50 to 100 mol%.

[0201] Resin (A) can be synthesized by a conventional method (e.g., radical polymerization).

[0202] The weight average molecular weight (Mw) of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and more preferably 5,000 to 15,000. By setting the weight average molecular weight (Mw) of the resin (A) to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and also deterioration of developability and deterioration of film-forming ability due to increased viscosity can be prevented. In addition, the weight average molecular weight (Mw) of the resin (A) is a polystyrene equivalent value measured by the GPC method described above.

[0203] The degree of dispersion (molecular weight distribution) of the resin (A) is typically 1 to 5, 1 to 3 is preferred, and 1.1 to 2.0 is more preferred. The smaller the degree of dispersion, the better the resolution and resist shape, and the smoother the sidewalls of the pattern, the better the roughness.

[0204] In the resist composition, the content of resin (A) is preferably 50 to 99.9 mass% with respect to the total solid content of the resist composition, and more preferably 60 to 99.0 mass%.

[0205] Also, resin (A) may be used as a single type or in combination with two or more types.

[0206] <Mining Agent (B)>

[0207] The resist composition comprises a photogenerator (B). The photogenerator (B) is not particularly limited as long as it is a compound that generates acid upon irradiation with radiation.

[0208] The photogenerator (B) may be in the form of a low-molecular-weight compound or introduced into a part of the polymer. In addition, the form of a low-molecular-weight compound and the form introduced into a part of the polymer may be used in combination.

[0209] When the photogenerator (B) is in the form of a low molecular weight compound, it is preferable that the weight average molecular weight (Mw) is 3000 or less, more preferable that it is 2000 or less, and more preferable that it is 1000 or less.

[0210] When the photogenerator (B) is in a form introduced into a part of the polymer, it may be introduced into a part of the resin (A), or it may be introduced into a resin different from the resin (A).

[0211] The photogenerator (B) is preferably in the form of a low-molecular-weight compound.

[0212] As for the photogenerator (B), it is not particularly limited as long as it is a known one, but a compound that generates an organic acid upon irradiation with radiation is preferred, and a photogenerator having a fluorine atom or an iodine atom in its molecule is more preferred.

[0213] Examples of the above organic acids include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, and camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, and aralkylcarboxylic acid, etc.), carbonylsulfonylimide, bis(alkylsulfonyl)imide, and tris(alkylsulfonyl)methide.

[0214] The volume of acid generated from the photogenerative agent (B) is not particularly limited, but in terms of suppressing the diffusion of acid generated by exposure to the non-exposed area and improving resolution, 240 Å 3 The above is desirable, and 305Å 3 The above is more preferable, and 350Å 3 The above is more desirable, and 400Å 3 The above is particularly desirable. In addition, in terms of sensitivity or solubility as a coating solvent, the volume of acid generated from the photogenerator (B) is 1500 Å. 3 The following is preferable, and 1000 Å 3 The following is more preferable, and 700Å 3 The following is more desirable.

[0215] The above volume values ​​are obtained using "WinMOPAC" manufactured by Fujitsu Corporation. In calculating the above volume values, first, the chemical structure of the acid for each example is input, and next, the most stable stereochemical position of each acid is determined by calculating the molecular force field using the MM (Molecular Mechanics) 3 method with this structure as the initial structure, and then, the "accessible volume" of each acid can be calculated by performing molecular orbital calculations using the PM (Parameterized Model Number) 3 method for these most stable stereochemical positions.

[0216] The structure of the acid generated from the photogenerator (B) is not particularly limited, but it is desirable that the interaction between the acid generated from the photogenerator (B) and the resin (A) be strong in order to suppress the diffusion of the acid and improve the resolution. In this regard, when the acid generated from the photogenerator (B) is an organic acid, for example, it is desirable to have additional polar groups in addition to organic acid groups such as sulfonic acid groups, carboxylic acid groups, carbonylsulfonylimide acid groups, bissulfonylimide acid groups, and trissulfonylmedide acid groups.

[0217] Examples of polar groups include, for instance, ether groups, ester groups, amide groups, acyl groups, sulfo groups, sulfonyloxy groups, sulfonamide groups, thioether groups, thioester groups, urea groups, carbonate groups, carbamate groups, hydroxyl groups, and mercapto groups.

[0218] The number of polar groups of the acid generated is not particularly limited, but it is preferable to have one or more, and more preferable to have two or more. However, from the perspective of suppressing excessive phenomena, it is preferable that the number of polar groups be less than 6, and more preferable to have less than 4.

[0219] Among them, it is preferable that the photogenerator (B) be a photogenerator composed of an anionic part and a cation part.

[0220] As for the photocatalytic agent (B), the photocatalytic agent described in paragraphs 0144 to 0173 of Japanese Patent Publication No. 2019-045864 can be cited.

[0221] The content of the photocatalytic agent (B) is not particularly limited, but with respect to the total solid content of the resist composition, 5 to 50 mass% is preferred, 5 to 40 mass% is more preferred, and 5 to 35 mass% is more preferred.

[0222] The photocatalytic agent (B) may be used as a single type or in combination of two or more types. When two or more types of photocatalytic agents (B) are used in combination, it is preferable that the total amount be within the above range.

[0223] <Compound Y>

[0224] The resist composition of the present invention comprises at least one compound Y selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).

[0225] [Chemical Formula 10]

[0226]

[0227] In formula (1), R1 to R3 each independently represent an alkyl group having 1 to 5 carbon atoms.

[0228] In formula (2), R4 and R5 each independently represent an alkyl group having 1 to 5 carbon atoms.

[0229] All alkyl groups represented by R1 to R5 may be straight-chain, branched-chain, or cyclic, and straight-chain is preferred.

[0230] In formula (1), the alkyl group represented by R1 to R3 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0231] Examples of compounds represented by formula (1) include 2-methoxypropyl acetic acid, 2-ethoxypropyl acetic acid, and 2-methoxypropyl propionic acid, and 2-methoxypropyl acetic acid is preferred.

[0232] In formula (2), the alkyl groups represented by R4 and R5 are preferably methyl or ethyl groups, and more preferably methyl groups.

[0233] Examples of compounds represented by formula (2) include 2-methoxy-1-propanol and 2-ethoxy-1-propanol, and 2-methoxy-1-propanol is preferred.

[0234] As compound Y, 2-methoxypropyl acetic acid, 2-methoxy-1-propanol, 2-ethoxypropyl acetic acid, 2-ethoxy-1-propanol, or 2-methoxypropyl propionic acid is preferred, and 2-methoxypropyl acetic acid or 2-methoxy-1-propanol is more preferred.

[0235] The content of compound Y is not particularly limited as long as the ratio with respect to the content of metal atoms falls within a predetermined range, but for superior effects of the present invention, it is preferable to have 200 mass ppm or less and 100 mass ppm or less with respect to the total mass of the resist composition. The lower limit is not particularly limited, but it is preferable to have 0.1 mass ppm or more and 1 mass ppm or more with respect to the total mass of the resist composition.

[0236] In particular, when the resist composition contains propylene glycol methyl ether acetate (2-methoxy-1-methyl ethyl acetate) as the solvent (F) described below, the content of 2-methoxypropyl acetate is preferably 0.1 to 200 ppm by mass and more preferably 1 to 100 ppm by mass with respect to the total mass of the resist composition.

[0237] In addition, when the resist composition contains propylene glycol monomethyl ether (1-methoxy-2-propanol) as the solvent (F) described later, the content of 2-methoxy-1-propanol is preferably 0.1 to 200 ppm by mass with respect to the total mass of the resist composition, and more preferably 1 to 100 ppm by mass.

[0238] Compound Y may be added to the resist composition, or unintentionally mixed into the resist composition during the manufacturing process of the resist composition. Examples of cases where compound Y is unintentionally mixed during the manufacturing process of the resist composition include, but are not limited to, cases where compound Y is contained in the raw materials (e.g., organic solvents) used to manufacture the resist composition, and cases where it is mixed during the manufacturing process of the resist composition.

[0239] As a method for adjusting the content of compound Y included in a resist composition, examples include preparing multiple raw materials used in the manufacture of the resist composition, measuring the content of compound Y included in each raw material in advance, using a mixture containing multiple types of raw materials and adjusting the amount of each raw material, and manufacturing the resist composition under conditions in which contamination is suppressed as much as possible by lining or coating the inside of the device with a fluoropolymer resin, etc.

[0240] Metal atoms

[0241] The resist composition of the present invention contains metal atoms.

[0242] Additionally, in this specification, the "metal atoms" contained in the resist composition are Na, K, Ca, Fe, Cu, Mn, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Mo, Zr, Pb, Ti, V, W, and Zn. These metal atoms are metal atoms that can be included in the resist composition under normal operation.

[0243] In addition, in this specification, "content of metal atoms" means the total content of the above metals. The form of the metal atoms contained in the resist composition is not particularly limited and may be in the form of a compound such as a salt, may be in the form of a single element, or may be in the form of an ion.

[0244] In the resist composition of the present invention, the mass ratio of the content of compound Y to the content of metal atoms (content of compound Y / content of metal atoms) is 1.0×10 to 1.0×10 9 am.

[0245] The mass ratio of the content of compound Y to the content of metal atoms is 1.0×10 to 1.0×10, in that the effect of the present invention is more superior. 9 is desirable, and 1.0×10 2 ~5.0×10 8 This is more desirable, and 1.0×10 2 ~1.0×10 7 This is more desirable.

[0246] The content of metal atoms in the resist composition is preferably 0.1 to 10,000 mass ppt with respect to the total mass of the resist composition, more preferably 1 to 1,000 mass ppt, and even more preferably 1 to 100 mass ppt, in order to provide a more superior effect of the present invention.

[0247] The content of metal atoms in the resist composition and the resist film can be measured, for example, using ICP-MS (Inductively coupled plasma mass spectrometry).

[0248] Metal atoms may be added to the resist composition, or may be unintentionally mixed into the resist composition during the manufacturing process of the resist composition. Examples of cases where metal atoms are unintentionally mixed during the manufacturing process of the resist composition include, but are not limited to, cases where metal atoms are contained in the raw materials used to manufacture the resist composition (e.g., organic solvents) and cases where they are mixed during the manufacturing process of the resist composition.

[0249] In addition, the content of metal atoms contained in the resist composition may be reduced by known methods, such as a method of filtering raw materials, such as a resist composition or organic solvent, using a filter; a method of selecting raw materials with a low content of metal atoms; or a method of distilling raw materials under conditions that suppress contamination, such as by lining the inside of the device with Teflon (registered trademark). Regarding the filter and the reduction method used for reducing the content of metal atoms, including their preferred forms, they may be the same as those described in the method for removing metal impurities from various materials described below.

[0250] <Acid Diffusion Control Agent (C)>

[0251] The resist composition may include an acid diffusion control agent (C).

[0252] The acid diffusion control agent (C) acts as a quencher that traps the acid generated from the photogenerative agent (B) during exposure and suppresses the reaction of the acid-degradable resin in the unexposed area caused by the excess generated acid. As for the acid diffusion control agent (C), examples may be used, such as a basic compound (CA), a basic compound (CB) whose basicity is reduced or lost due to radiation irradiation, an onium salt (CC) that becomes a relatively weak acid with respect to the photogenerative agent (B), a low-molecular-weight compound (CD) having a nitrogen atom and a group that is detached by the action of the acid, and an onium salt compound (CE) having a nitrogen atom in the cation portion.

[0253] In the resist composition, known acid diffusion control agents may be appropriately used. For example, known compounds disclosed in paragraphs

[0627] –

[0664] of U.S. Patent Application Publication No. 2016 / 0070167, paragraphs

[0095] –

[0187] of U.S. Patent Application Publication No. 2015 / 0004544, paragraphs

[0403] –

[0423] of U.S. Patent Application Publication No. 2016 / 0237190, and paragraphs

[0259] –

[0328] of U.S. Patent Application Publication No. 2016 / 0274458 may be suitably used as acid diffusion control agents (C).

[0254] As basic compounds (CA), the repeating units described in paragraphs 0188 to 0208 of Japanese Patent Publication No. 2019-045864 can be cited.

[0255] In the resist composition, an onium salt (CC) that is relatively weak acid to the photogenerative agent (B) can be used as an acid diffusion control agent (C).

[0256] When a photogenerative agent (B) and an onium salt that generates an acid that is relatively weak compared to the acid generated from the photogenerative agent (B) are mixed and used, if the acid generated from the photogenerative agent (B) collides with the onium salt having unreacted weak acid anions due to irradiation with active photogenicity or radiation, the weak acid is released through salt exchange to generate an onium salt having strong acid anions. In this process, since the strong acid is exchanged for a weak acid with lower catalytic activity, the acid is apparently deactivated and acid diffusion can be controlled.

[0257] Examples of onium salts that are relatively weak acids to the photogenerative agent (B) include the onium salts described in paragraphs 0226 to 0233 of Japanese Patent Publication No. 2019-070676.

[0258] When an acid diffusion control agent (C) is included in the resist composition, the content of the acid diffusion control agent (C) (the total amount if multiple types exist) is preferably 0.1 to 10.0 mass% with respect to the total solid content of the resist composition, and more preferably 0.1 to 5.0 mass%.

[0259] In the resist composition, the acid diffusion control agent (C) may be used alone or in combination with two or more types.

[0260] <Hypohydrophobic resin (E)>

[0261] The resist composition may include a hydrophobic resin (E) that is different from the resin (A) as the hydrophobic resin.

[0262] The hydrophobic resin (E) is preferably designed to be localized on the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups within its molecule and does not need to contribute to the uniform mixing of polar and non-polar substances.

[0263] Effects of adding a hydrophobic resin (E) include control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of out-gas.

[0264] The hydrophobic resin (E) preferably has at least one of a fluorine atom, a silicon atom, and a CH3 part structure included in the side chain portion of the resin, with respect to localization into the film surface layer, and more preferably has at least two of these. In addition, the hydrophobic resin (E) preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted in the side chain.

[0265] When the hydrophobic resin (E) 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 in the side chain.

[0266] When the hydrophobic resin (E) has fluorine atoms, the partial structure having fluorine atoms is preferably an alkyl group having fluorine atoms, a cycloalkyl group having fluorine atoms, or an aryl group having fluorine atoms.

[0267] The alkyl group having a fluorine atom (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a straight-chain or branched-chain alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may additionally have substituents other than fluorine atoms.

[0268] 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 additionally have substituents other than the fluorine atom.

[0269] Examples of aryl groups having a fluorine atom include phenyl groups and naphthyl groups in which at least one hydrogen atom is substituted with a fluorine atom, and may also have substituents other than fluorine atoms.

[0270] Examples of repeating units having fluorine atoms or silicon atoms include those exemplified in paragraph 0519 of U.S. Patent Application Publication No. 2012 / 0251948.

[0271] In addition, as described above, it is also desirable that the hydrophobic resin (E) has a CH3 part structure in the side chain portion.

[0272] Here, the CH3 part structure having a side chain portion in the hydrophobic resin includes a CH3 part structure having an ethyl group and a propyl group, etc.

[0273] Meanwhile, methyl groups directly bonded to the main chain of the hydrophobic resin (E) (e.g., α-methyl groups of repeating units having a methacrylic acid structure) are not included in the CH3 substructure of the present invention because they contribute little to the surface localization of the hydrophobic resin (E) due to the influence of the main chain.

[0274] Regarding hydrophobic resins (E), reference may be made to paragraphs

[0348] to

[0415] of Japanese Patent Publication No. 2014-010245, and the contents thereof are incorporated herein by reference.

[0275] As for the hydrophobic resin (E), the resins described in Japanese Patent Publication No. 2011-248019, Japanese Patent Publication No. 2010-175859, and Japanese Patent Publication No. 2012-032544 may also be preferably used.

[0276] When the resist composition includes a hydrophobic resin (E), the content of the hydrophobic resin (E) is preferably 0.01 to 20 mass% with respect to the total solid content of the resist composition, and more preferably 0.1 to 15 mass%.

[0277] <Solvent (F)>

[0278] The resist composition may include a solvent (F). Additionally, the compound Y is not included in the solvent (F).

[0279] When the resist composition is a radioactive resin composition for EUV exposure, the solvent (F) preferably comprises at least one selected from the group consisting of (F1) propylene glycol monoalkyl ether carboxylate and (F2) propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. In this case, the solvent may further comprise components other than components (F1) and (F2).

[0280] A solvent containing at least one of components (F1) and (F2) is preferred because, when used in combination with the resin (A) described above, the applicability of the resist composition is improved and a pattern with a low number of development defects can be formed.

[0281] As for the component (F1), for example, a compound represented by the following formula (3) can be used.

[0282] [Chemical Formula 11]

[0283]

[0284] In formula (3), R6 and R7 each independently represent an alkyl group having 1 to 5 carbon atoms. As the alkyl group represented by R6, a methyl group or an ethyl group is preferred, and a methyl group is more preferred. As the alkyl group represented by R7, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0285] As for component (F1), propylene glycol methyl ether acetate (2-methoxy-1-methyl ethyl acetate) is preferred.

[0286] As for the propylene glycol monoalkyl ether included in component (F2), for example, a compound represented by the following formula (4) can be used.

[0287] [Chemical Formula 12]

[0288]

[0289] In formula (4), R8 represents an alkyl group having 1 to 5 carbon atoms. As for the alkyl group represented by R8, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0290] As a compound represented by the above formula (4), 1-methoxy-2-propanol is preferred.

[0291] The content of component (F1) is preferably 20 to 99 mass% with respect to the total content of solvent (F), and more preferably 30 to 90 mass%.

[0292] The content of component (F2) is preferably 5 to 90 mass% with respect to the total content of solvent (F), and more preferably 10 to 80 mass%.

[0293] In addition, when the resist composition is a radioactive resin composition for ArF, the solvent (F) may be an organic solvent such as, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound that may contain a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

[0294] It is preferable to set the content of the solvent (F) in the resist composition such that the solid content concentration is 0.5 to 40 mass%.

[0295] In one embodiment of the resist composition, it is also desirable that the solid content concentration be 10 mass% or more.

[0296] (peroxide)

[0297] When the solvent (F) has an oxygen-containing functional group, in particular, when the solvent (F) is the solvent (F1), there is a possibility that peroxides may be formed in the resist composition. If the amount of peroxides contained in the resist composition is excessive, other components may be oxidized during storage of the resist composition, and consequently, there is a concern that this may lead to a deterioration in the quality of the resist film or resist pattern formed using the resist composition after storage.

[0298] In light of the above, the content of peroxide in the resist composition is preferably 100 mass ppm or less with respect to the total mass of the resist composition, and more preferably 10 mass ppm or less, in order to provide a more superior effect of the present invention. The lower limit is not particularly restricted and may be below the detection limit, and is preferably 3 mass ppm or more with respect to the total mass of the resist composition.

[0299] Likewise, the content of peroxide in the solvent (F) is preferably 100 mass ppm or less with respect to the total mass of the solvent (F) for superior effects of the present invention, and more preferably 10 mass ppm or less. The lower limit is not particularly limited and may be below the detection limit, and is preferably 3 mass ppm or more with respect to the total mass of the solvent (F).

[0300] The content of peroxide in the resist composition and solvent (F) can be quantified by known methods such as GC, HPLC, and NMR.

[0301] <Surfactant (H)>

[0302] The resist composition may include a surfactant (H). By including a surfactant (H), a pattern with better adhesion and fewer development defects can be formed.

[0303] As for the surfactant (H), fluorine-based and / or silicone-based surfactants are preferred.

[0304] As for fluorine-based and / or silicone-based surfactants, examples include the surfactant described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425.

[0305] In addition, the surfactant (H) may be synthesized using a fluoroaliphatic compound prepared by the telomerization method (also called the telomer method) or the oligomerization method (also called the oligomer method), in addition to the known surfactant as described above. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as the surfactant (H). This fluoroaliphatic compound may be synthesized, for example, by the method described in Japanese Patent Publication No. 2002-090991.

[0306] These surfactants (H) may be used as a single type, or two or more types may be used in combination.

[0307] The content of surfactant (H) is preferably 0.0001 to 2 mass% with respect to the total solid content of the resist composition, and more preferably 0.0005 to 1 mass%.

[0308] Other Additives

[0309] The resist composition may further include a crosslinking agent, an alkali-soluble resin, a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer.

[0310] The content of each component (excluding metal atoms) included in the resist composition, etc., can be measured by known methods such as gas chromatography-mass spectrometry (GC-MS).

[0311] [Requirement 1]

[0312] It is preferable that the resist composition satisfies the following requirement 1 in order to have a more superior effect of the present invention.

[0313] Requirement 1: A resist composition is applied to the surface of a silicon wafer with a diameter of 12 inches, and the resulting film is baked at 120°C for 60 seconds to produce a silicon wafer having a resist film with a thickness of 50 nm. The silicon wafer having the obtained resist film is immersed in a mixed solution containing butyl acetate and undecae, wherein the mass ratio of butyl acetate to undecae is 9:1, to remove the resist film from the silicon wafer. Subsequently, defects on the surface of the silicon wafer from which the resist film has been removed are measured using a defect evaluation device. The number of measured defects per silicon wafer is 1 to 1000.

[0314] The number of defects on the surface of the silicon wafer from which the above-mentioned resist film has been removed can be adjusted by changing the method of manufacturing the resist composition described below. More specifically, in a process of filtration using a filter, it can be adjusted by changing manufacturing conditions such as the type and pore diameter of the filter, filtration pressure and the number of filtrations, and the method of pre-cleaning the filter.

[0315] [Method for preparing a resist composition]

[0316] The method for manufacturing the resist composition is not particularly limited, but it is preferable to have a process of mixing various components, such as an acid-degradable resin and a photocatalytic agent, and then dissolving each component in a solvent and filtering it using a filter.

[0317] In filter filtration, it is preferable to use multiple filters made of different materials (circulating filtration may also be used). More specifically, it is preferable to perform filtration by connecting 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 to 5 nm in a permutation. It is also preferable to perform filtration by circulating filtration two or more times. Through the above filtration process, the content of metal atoms in the resist composition can be reduced. The pressure difference between filters is preferably smaller, preferably 0.1 MPa or less, more preferably 0.05 MPa or less, and even more preferably 0.01 MPa or less.

[0318] In addition, as a method for performing circulation filtration using a filter in the preparation of a resist composition, for example, a method of performing circulation filtration two or more times using a polytetrafluoroethylene filter with a pore diameter of 50 nm is also preferred.

[0319] [Method for manufacturing a resist pattern]

[0320] The resist composition according to the present invention is used for forming a resist pattern. The method of forming a resist film using the resist composition is not particularly limited, and for example, a method having a process of forming a resist film on a substrate using the resist composition may be cited.

[0321] The method for manufacturing a resist pattern according to the present invention comprises the following processes 1 to 3.

[0322] · Process 1: A resist film formation process for forming a resist film on a substrate using a resist composition.

[0323] · Process 2: Photolithography process for exposing the resist film

[0324] · Process 3: A development process in which the exposed resist film is developed using a developer and a pattern is formed.

[0325] Explain the steps of each process in detail.

[0326] [Process 1: Resist Film Formation Process]

[0327] Process 1 is a process of applying a resist composition onto a substrate and forming a resist film.

[0328] As a method for forming a resist film using a resist composition, for example, a method of applying the resist composition onto a substrate may be used. The resist composition is as previously described.

[0329] As a method for applying a resist composition onto a substrate, for example, a method of applying the resist composition onto a substrate (e.g., silicon, etc.) used for manufacturing semiconductor devices such as integrated circuits using devices such as a spinner and a coater may be cited.

[0330] As for the coating method, spin coating using a spinner is preferred. The rotational speed when performing spin coating is preferably 1,000 to 3,000 rpm.

[0331] As for the substrate, any substrate used for manufacturing integrated circuit devices is not particularly limited and may include a silicon wafer and a silicon wafer coated with silicon dioxide, and a silicon wafer is preferred.

[0332] A resist film may be formed by drying a substrate coated with a resist composition.

[0333] As a drying method, for example, a heating method may be used. The heating may be performed using means provided in a known exposure machine and / or a known developer, and a hot plate.

[0334] 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 1000 seconds, more preferably 30 to 800 seconds, and even more preferably 40 to 600 seconds. Heating may be performed once or two or more times.

[0335] The film thickness of the resist film is preferably 10 to 90 nm, more preferably 10 to 65 nm, and more preferably 15 to 50 nm, in that it can form a fine pattern with higher precision.

[0336] In addition, an underlayer (e.g., an inorganic film, an organic film, and an anti-reflective film) may be formed between the substrate and the resist film.

[0337] The resist composition for forming a lower film preferably includes a known organic material or a known inorganic material.

[0338] The thickness of the lower membrane is preferably 10 to 90 nm, more preferably 10 to 50 nm, and more preferably 10 to 30 nm.

[0339] Examples of resist compositions for forming a film include AL412 (manufactured by Brewer Science) and the SHB series (e.g., SHB-A940, manufactured by Shin-Etsu Kagaku Kogyo).

[0340] A top coat may be formed on the side opposite to the substrate of the resist film using a top coat resist composition.

[0341] It is desirable that the top coat resist composition is not mixed with the resist film and can also be uniformly applied to the side opposite to the substrate of the resist film.

[0342] The top coat resist composition preferably comprises a resin, an additive, and a solvent.

[0343] As for a method of forming a top coat, for example, a known method of forming a top coat can be cited, and specifically, a method of forming a top coat described in paragraphs

[0072] to

[0082] of Japanese Patent Publication No. 2014-059543 can be cited.

[0344] As a method for forming a top coat, it is preferable to form a top coat containing a basic compound described in Japanese Patent Publication No. 2013-061648 on the side opposite to the substrate of the resist film. Examples of the basic compound include, for instance, the basic compound described in International Publication No. 2017 / 002737.

[0345] In addition, the top coat may also include a compound having at least one selected from the group consisting of -O-, -S-, hydroxyl groups, thiol groups, -CO-, and -COO-.

[0346] [Process 2: Photolithography Process]

[0347] Process 2 is a process of exposing the resist film formed in Process 1.

[0348] Process 2 is preferably a process of exposing a pattern through a photomask.

[0349] As for the photomask, for example, a known photomask can be used. In addition, the photomask may be in contact with the resist film.

[0350] Examples of exposure light for exposing the resist film include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams.

[0351] The wavelength of the exposure light is preferably 250 nm or less, more preferably 220 nm or less, and more preferably 1 to 200 nm. Specifically, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), X-rays, EUV (wavelength 13 nm), or electron beams are preferred, a KrF excimer laser, an ArF excimer laser, EUV, or electron beams are more preferred, and EUV or electron beams are more preferred.

[0352] The exposure amount can be appropriately adjusted to match the target pattern shape.

[0353] The exposure method of the photolithography process may be immersion exposure.

[0354] The photolithography process may be performed once or two or more times.

[0355] After the photolithography process and before the development process described later, a post-exposure bake (PEB) may be performed.

[0356] The heating temperature of the bake after exposure 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 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.

[0357] Baking after exposure may be performed using means provided in a known exposure machine and / or developer, and a hot plate. In addition, baking after exposure may be performed once or two or more times.

[0358] [Process 3: Development Process]

[0359] Process 3 is a process of developing the exposed resist film using a developer and forming a pattern.

[0360] Examples of development methods include, for instance, a method of immersing a substrate in a tank filled with a developer solution for a certain period of time (dip method), a method of developing by puddle-forming the developer solution onto the substrate surface by surface tension and allowing it to stand for a certain period of time (puddle method), a method of spraying the developer solution onto the substrate surface (spray method), and a method of continuously dispensing the developer solution while scanning a discharge nozzle at a certain speed onto a substrate rotating at a certain speed (dynamic dispensing method), but are not limited to these.

[0361] In addition, after the developing process, a process of stopping the developing process may be performed while replacing it with another solvent.

[0362] The development time is not particularly limited as long as it is a time during which the non-exposed or exposed part to be dissolved is sufficiently dissolved, and is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds.

[0363] The temperature of the developer solution is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0364] <Developer>

[0365] The developer is not particularly limited as long as it can dissolve the resist film formed using the above-mentioned resist composition, and a developer suitable for the resist composition can be appropriately selected from known developers.

[0366] In addition, the notation "resist film formed using the resist composition" or simply "resist film" in this specification includes both an unexposed film formed using the resist composition that has not been exposed, and a film formed using the resist composition that has been exposed. That is, the developer may be a negative-type developer that removes the unexposed portion of the resist film to form a resist pattern, or a positive-type developer that removes the exposed portion of the resist film to form a resist pattern.

[0367] Examples of developers include alkaline developers and organic solvent developers, and organic solvent developers are preferred.

[0368] As an alkaline developer, an alkaline aqueous solution containing alkali is preferred. The type of alkaline aqueous solution is not particularly limited, but examples include an alkaline aqueous solution containing at least one selected from the group consisting of a quaternary ammonium salt represented by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcoholamine, and a cyclic amine. Among these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohols or surfactants may be added to the alkaline developer.

[0369] The alkali concentration of alkaline developers is often 0.1 to 20 mass%. Also, the pH of alkaline developers is often 10.0 to 15.0.

[0370] An organic solvent developer is a developer containing an organic solvent.

[0371] The vapor pressure of the organic solvent included in the organic solvent developer (the total vapor pressure in the case of a mixed solvent) is preferably 5 kPa or less at 20°C, more preferably 3 kPa or less, and more preferably 2 kPa or less. By making the vapor pressure of the organic solvent 5 kPa or less, the evaporation of the developer on the substrate or within the developing cup is suppressed, thereby improving the temperature uniformity within the wafer surface, and consequently, the dimensional uniformity within the wafer surface is improved.

[0372] Examples of organic solvents used in organic solvent developers include known organic solvents, ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0373] As for the ester-based solvent, for example, an ester-based solvent having 3 to 12 carbon atoms can be used, an ester-based solvent having 4 to 10 carbon atoms is preferred, and an ester-based solvent having 5 to 8 carbon atoms is more preferred.

[0374] The ester-based solvent may have an alkyl group. The alkyl group may be any of a straight chain, a branched chain, or a cyclic chain, and a straight chain is preferred.

[0375] As heteroatoms of the ester-based solvent, oxygen atoms are preferred, and it is more preferable to have only oxygen atoms as heteroatoms. The ester-based solvent may have one or more -COO- groups, and it is preferable to have only one -COO- group.

[0376] More specifically, ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, t-butyl acetate, pentyl acetate (amyl acetate), isopentyl acetate (isoamyl 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, amyl formate, isoamyl formate, ethyl lactate, butyl lactate, propyl lactate, propyl propionic acid, isopropyl propionic acid, Examples include butyl propionate, isobutyl propionate, ethyl butyl butyl, propyl butyl butyl, isopropyl butyl butyl, butyl butanate (butyl butyl butyl), methyl 2-hydroxyisobutyrate, ethyl isobutyrate, propyl isobutyrate, and isobutyl isobutyl isobutyl.

[0377] Among these, butyl acetate, isobutyl acetate, t-butyl acetate, amyl acetate, isoamyl acetate, amyl formate, isoamyl formate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, ethyl butyrate, propyl butyrate, isopropyl butyrate, ethyl isobutyrate, or propyl isobutyrate is preferred, butyl acetate, isobutyl acetate, or isoamyl acetate is more preferred, and butyl acetate is even more preferred.

[0378] Examples of ketone-based solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone monoacetone, ionone, diacetone monoalcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate.

[0379] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. The number of carbon atoms in the hydrocarbon solvent is preferably 3 to 20, more preferably 8 to 12, and even more preferably 9 to 11.

[0380] The aliphatic hydrocarbon solvent may be a saturated aliphatic hydrocarbon solvent or an unsaturated aliphatic hydrocarbon solvent, and a saturated aliphatic hydrocarbon solvent is preferred. The aliphatic hydrocarbon solvent may be straight-chain, branched-chain, or cyclic, and a straight-chain is preferred. The aromatic hydrocarbon solvent may be either monocyclic or polycyclic.

[0381] As for the hydrocarbon solvent, a saturated aliphatic hydrocarbon solvent is preferred, a saturated aliphatic hydrocarbon solvent having the above number of carbon atoms is more preferred, octane, nonene, decane, undecane, or dodecane is more preferred, and nonene, decane, or undecane is particularly preferred.

[0382] As for alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents, the solvents disclosed in paragraphs

[0715] –

[0718] of U.S. Patent Application Publication No. 2016 / 0070167 may be used, and this description is incorporated herein by reference.

[0383] As for the developer, an organic solvent developer is preferred, and it is more preferable to include at least one selected from the group consisting of ester-based solvents and hydrocarbon-based solvents, and a mixed solvent including ester-based solvents and hydrocarbon-based solvents is more preferable.

[0384] Among these, it is preferable to use the above-mentioned preferred ester-based solvent as the ester-based solvent, and it is more preferable to use butyl acetate. That is, as a developer, it is particularly preferable to include the above-mentioned preferred ester-based solvent (more preferably butyl acetate) and a hydrocarbon-based solvent.

[0385] Furthermore, as for the developer, an embodiment containing multiple of the above-mentioned preferred ester-based solvents is more preferable, and an embodiment containing multiple of the above-mentioned preferred ester-based solvents and also containing at least one hydrocarbon-based solvent is more preferable. In the embodiment containing multiple of these preferred ester-based solvents, an embodiment in which one of the ester-based solvents is butyl acetate is particularly preferred.

[0386] As for hydrocarbon solvents combined with ester solvents, the above-mentioned preferred saturated aliphatic hydrocarbon solvents can be cited in terms of adjusting the solubility of the resist film, and noneneine, decane, or undecane are preferred, and undecane is more preferred.

[0387] The developer may contain one type of organic solvent alone, or a combination of two or more types. When the developer contains two or more types of organic solvents, the content of each is not particularly limited and can be determined appropriately, as it depends on the solvent solubility of the resist film.

[0388] When the developer includes an ester-based solvent and a hydrocarbon-based solvent, the content of the ester-based solvent is preferably 10 to 95 mass% with respect to the total mass of the developer, more preferably 25 to 93 mass%, and even more preferably 40 to 91 mass%. In addition, the content of the hydrocarbon-based solvent is preferably 5 to 90 mass% with respect to the total mass of the developer, more preferably 7 to 75 mass%, and even more preferably 9 to 60 mass%. As for the developer, it is particularly preferable to include only the ester-based solvent and the hydrocarbon-based solvent within the above content ranges.

[0389] Regarding the content of organic solvent (total in cases where multiple types are mixed) in the developer, it is preferable to have 80 mass% or more and 90 mass% or more with respect to the total mass of the developer. Among these, it is more preferable that the developer substantially contains only organic solvent, and the content of organic solvent is particularly preferable to have 98 mass% or more with respect to the total mass of the developer. The upper limit is not particularly restricted and may be 100 mass%.

[0390] The developer may contain water, but it is preferable that it substantially does not contain water, it is more preferable that the water content is 2 mass% or less of the total mass of the developer, and it is even more preferable that it does not contain water.

[0391] [Other processes]

[0392] The pattern forming method preferably includes a cleaning process using a rinse solution after process 3.

[0393] As a rinsing solution used in the rinsing process after the developing process using a developer, pure water can be used, for example. In addition, an appropriate amount of surfactant may be added to the pure water.

[0394] An appropriate amount of surfactant may be added to the rinse solution.

[0395] The resist pattern formed in process 3 above is used as a mask to form a pattern by processing the target layer by performing an etching treatment on the target layer below the resist pattern.

[0396] Examples of target layers include bulk layers and silicon oxide layers. The pattern formed on the target layer functions as, for example, part of a circuit board (metal wiring and barrier layers, etc.).

[0397] The method of processing the target layer is not particularly limited, but a method of forming a pattern on the target layer by using the resist pattern formed in process 3 as a mask and performing dry etching on the target layer is preferred.

[0398] Dry etching may be a single-stage etching or a multi-stage etching. In the case of a multi-stage etching, the etching of each stage may be the same treatment or different treatment. Also, as the etching gas, for example, a mixed gas such as Ar gas and a fluorinated carbon gas such as CF4, C2F8, CHF3, CH3F, and CH2F2, and a mixed gas of HBr and CO2 may be used.

[0399] Etching can be performed using any known method, and various conditions are appropriately determined according to the type or use of the target layer. For example, etching can be performed in accordance with the International Society for Photonics and Optics (Proc. of SPIE) Vol. 6924, 692420 (2008), Japanese Patent Publication No. 2009-267112, etc. In addition, it may be performed in accordance with the method described in "Chapter 4 Etching" of the "Semiconductor Process Manual, 4th Edition, 2007, Publisher: SEMI Japan".

[0400] Among them, oxygen plasma etching is preferred as a dry etching method.

[0401] Various materials used in the method for manufacturing a resist pattern and the method for manufacturing a pattern using the resist pattern (e.g., solvent, developer, rinse solution, composition for forming an anti-reflective film, composition for forming a top coat, 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, more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. Here, metal impurities may include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Mo, Zr, Pb, Ti, V, W, and Zn.

[0402] As a method for removing impurities such as metal from the above various materials, filtration using a filter can be cited, for example. As for the filter hole diameter, 0.20 μm or less is preferred, 0.05 μm or less is more preferred, and 0.01 μm or less is even more preferred.

[0403] As for the filter material, fluoropolymer resins such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA), polyolefin resins such as polypropylene and polyethylene, and polyamide resins such as nylon 6 and nylon 66 are preferred. The filter may be used after being pre-cleaned with an organic solvent. In the filter filtration process, multiple or multiple types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore diameters and / or materials may be combined. Furthermore, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulating filtration process. As for the circulating filtration process, for example, the method disclosed in Japanese Patent Publication No. 2002-062667 is preferred.

[0404] As for the filter, it is preferable that the leaching product be reduced as disclosed in Japanese Patent Publication No. 2016-201426.

[0405] In addition to filter filtration, the removal of impurities may be performed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. As for the adsorbent, known adsorbents may be used, for example, inorganic adsorbents such as silica gel or zeolite, or organic adsorbents such as activated carbon. As for metal adsorbents, for example, those disclosed in Japanese Patent Publication No. 2016-206500 may be cited.

[0406] In addition, methods for reducing impurities such as metals contained in the various materials mentioned above may include selecting raw materials with a low metal content as the raw materials constituting the various materials, performing filter filtration on the raw materials constituting the various materials, or performing distillation under conditions in which contamination is suppressed as much as possible by lining or coating the inside of the device with fluoropolymer resin, etc. The preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as the conditions mentioned above.

[0407] In order to prevent the incorporation of impurities, it is preferable that the above various materials be stored in containers described in U.S. Patent Application Publication No. 2015 / 0227049, Japanese Patent Publication No. 2015-123351, and Japanese Patent Publication No. 2017-013804, etc.

[0408] Various materials may be used after being diluted with the solvent used in the resist composition.

[0409] [Electronic Devices]

[0410] The resist film and resist pattern formed using the resist composition may be used in the manufacture of electronic devices.

[0411] The electronic device is not particularly limited and, for example, can be an electronic device installed in electrical and electronic devices (home appliances, OA (Office Automation), media-related devices, optical devices and communication devices, etc.).

[0412] Examples

[0413] The present invention will be described in more detail below based on the examples. The materials, usage amounts, ratios, processing details, and processing procedures shown in the following examples may be appropriately modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0414] [Each component of the resist composition]

[0415] The following components were used to prepare the resist composition. Each component, and the raw material for synthesizing each component, were selected from high-purity grade materials for semiconductor manufacturing or equivalent compounds.

[0416] [Synthesis of Resin (A)]

[0417] In the examples and comparative examples, the following resins A-1 to A-6 were used as resin (A). All of the resins A-1 to A-6 were synthesized based on known technology.

[0418] Table 1 shows the composition ratio (molar ratio; corresponding in order from left), weight average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit in resin (A).

[0419] [Table 1]

[0420]

[0421] [Chemical Formula 13]

[0422]

[0423] [Chemical Formula 14]

[0424]

[0425] [Ore-generating agent (B)]

[0426] In the examples and comparative examples, the structures of compounds B-1 to B-6 used as photogenerators (B) are shown below.

[0427] [Chemical Formula 15]

[0428]

[0429] [Chemical Formula 16]

[0430]

[0431] [Acid Diffusion Control Agent (C)]

[0432] The structures of compounds C-1 to C-4 used as acid diffusion control agents (C) in the examples and comparative examples are shown below.

[0433] [Chemical Formula 17]

[0434]

[0435] [Hydrophobic resin (E)]

[0436] In the examples and comparative examples, resin E-1 having the following structure was used as the hydrophobic resin (E). Resin E-1 was used that was synthesized based on known technology.

[0437] The compositional ratio (molar ratio) of each repeating unit in resin E-1 was "85 / 10 / 5" from left to right. Also, the weight average molecular weight (Mw) of resin E-1 was 11,000, and the degree of dispersion (Mw / Mn) was 1.55.

[0438] [Chemical Formula 18]

[0439]

[0440] [Solvent (F)]

[0441] In the examples and comparative examples, the following solvents F-1 to F-6 were used as the solvent (F).

[0442] F-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0443] F-2: Propylene glycol monomethyl ether (PGME)

[0444] F-3: γ-beautyllactone

[0445] F-4: Ethyl lactate

[0446] F-5: Cyclohexanone

[0447] F-6: 2-heptanone

[0448] [Compound Y]

[0449] In the examples and comparative examples, 2-methoxypropyl acetic acid (compound Y1), 2-methoxy-1-propanol (compound Y2), 2-ethoxypropyl acetic acid (compound Y3), 2-ethoxy-1-propanol (compound Y4), and 2-methoxypropyl propionic acid (compound Y5) were used as compound Y.

[0450] [Preparation of Resist Composition]

[0451] A resin (A), a photocatalytic agent (B), an acid diffusion control agent (C), a hydrophobic resin (E), and a solvent (F) were mixed to form the composition shown in Table 2 below. Next, the obtained mixture was filtered in the following order: first through a polyethylene filter with a pore diameter of 50 nm, then through a nylon filter with a pore diameter of 10 nm, and finally through a polyethylene filter with a pore diameter of 5 nm to prepare the composition.

[0452] The content of metal atoms was adjusted to the content listed in Table 2 by repeating the filtration treatment of passing the prepared composition through the filter, or by adding a metal-containing liquid in which a trace amount of metal or a trace amount of metal is dissolved or dispersed in the solvent.

[0453] In addition, the content of compounds Y1 and Y2 included in resist compositions Re-1 to Re-7 was adjusted to the content listed in Table 2 by using a mixture obtained by mixing two or more products with different content of compounds Y1 or Y2 as the solvent (F) when preparing the resist composition, after measuring the content of compounds Y1 and Y2 included in products with different lots, grades, and manufacturers, and / or by adding a diluted solution of compounds Y1 and / or Y2 diluted with said solvent to the solvent (F). In addition, when preparing resist compositions Re-1 to Re-4, Re-6, and Re-7, the content of compounds Y other than compounds Y1 was adjusted to be significantly lower (at least two to three orders of magnitude lower) compared to the content of compounds Y1. In addition, when preparing the resist composition Re-5, the content of compound Y other than compounds Y1 and Y2 was adjusted to be significantly lower (at least two to three orders of magnitude lower) compared to the content of compounds Y1 and Y2.

[0454] Likewise, the content of compounds Y1 to Y5 included in the resist compositions Re-8 to Re-15 was adjusted to the content listed in Table 2 by using a mixture obtained by mixing two or more products with different content of compounds Y1 to Y5 as the solvent (F) when preparing the resist composition, after measuring the content of compounds Y1 to Y5 included in products with different lots, grades, and manufacturers, and / or by adding a diluted solution obtained by diluting any one of compounds Y1 to Y5 with the said solvent to the solvent (F). In addition, regarding the resist compositions Re-8 to Re-15, a compound with a content (mass ppm) indicated as "0" in Table 2 described below means that the content is significantly lower (at least two to three orders of magnitude lower) compared to a compound with a content other than "0".

[0455] As described above, the resist compositions Re-1 to Re-15, Re-C1, and Re-C2 shown in Table 2 were prepared.

[0456] In the table below, the "Amount (%)" column for each component of resin (A), photocatalytic agent (B), acid diffusion control agent (C), and hydrophobic resin (E) represents the "content (mass%)" relative to the total solid content.

[0457] The "Solid Content (%)" column refers to the total content (mass%) of each component other than the solvent and compound Y relative to the total mass of the resist composition.

[0458] The "mixing ratio" column of "solvents" indicates the mass ratio of each solvent.

[0459] The "Compound Y" column indicates the content of Compound Y (total content of Compounds Y1 to Y5) (mass ppm) relative to the total mass of the resist composition. Additionally, the "Compound Y1" to "Compound Y5" columns indicate the respective content of Compounds Y1 to Y5 (mass ppm) relative to the total mass of the resist composition.

[0460] The column "Metal X" indicates the content of metal atoms (mass ppm) relative to the total mass of the resist composition. Additionally, the metal atoms detected in the resist composition were Na, K, Ca, Fe, Cu, Mn, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Mo, Zr, Pb, Ti, V, W, and Zn.

[0461] The "Y / X" column represents the mass ratio of the total content of compound Y (mass ppm) to the content of metal atoms (mass ppm) (content of compound Y / content of metal atoms).

[0462] The "peroxide" column indicates the content of peroxide (mass ppm) relative to the total mass of the resist composition.

[0463] In each column of the table, "E+n" is "×10 nRepresents ", and "En" is "×10 -n It represents ". n represents an integer greater than or equal to 0. Specifically, "1.00E-7" is "1.00×10 -7 Represents ", and "5.00E+8" is "5.00×10 8 It represents ".

[0464] In addition, the content of each component was calculated from the amount introduced, or measured using the measurement method for the content of each component described above.

[0465] [Table 2]

[0466]

[0467] [Table 3]

[0468]

[0469] [Table 4]

[0470]

[0471] [Table 5]

[0472]

[0473] [Measurement and Evaluation of Resist Composition]

[0474] [Determination of Requirement 1]

[0475] Each of the resist compositions listed in Table 2 was applied to a 12-inch diameter silicon wafer, and the film was baked at 120°C for 60 seconds to form a resist film with a thickness of 50 nm. The silicon wafer having the resist film was immersed in a mixed solution containing butyl acetate and undecae, with a mass ratio of butyl acetate to undecae of 9:1, to remove the resist film from the silicon wafer. The silicon wafer from which the resist film was removed was removed from the mixed solution and spin-dried.

[0476] The surface of the obtained silicon wafer was inspected using a defect evaluation device "UVision 8" (Applied Materials) to create a defect map showing the location of detected defects on the surface of the silicon wafer. Then, images of the defects were acquired using SEMVision G4 (Applied Materials), and the number of defects per silicon wafer was calculated by comparing the defect images with the defect map.

[0477] It was determined that a resist composition having a number of defects per silicon wafer in the range of 1 to 1000 satisfies requirement 1, and a resist composition having less than 1 or more than 1000 satisfies requirement 1.

[0478] In the column "Requirement 1" of Table 3 described below, "A" means satisfying Requirement 1, and "B" means not satisfying Requirement 1.

[0479] [Formation of resist pattern and measurement of defect number (1)]

[0480] A composition AL412 (manufactured by Brewer Science) for forming a sublayer was applied to a silicon wafer with a diameter of 12 inches, and baked at 205°C for 60 seconds to form a sublayer consisting of an organic film with a thickness of 20 nm. On top of this, each of the resist compositions listed in Table 2 was applied, and the film was baked at 120°C for 60 seconds to form a resist film with a thickness of 50 nm.

[0481] Using an EUV lithography apparatus (ASML NXE3400, NA 0.33, Quadruple, outer sigma 0.885, inner sigma 0.381), for a silicon wafer having a resist film obtained by the above-described procedure, 30 mJ / cm² 2 Pattern exposure was performed with an exposure amount. In addition, as a reticle, a mask was used with a line width of 25 nm on the wafer and a line:space ratio of 1:1.

[0482] After baking (PEB) the pattern-exposed resist film at 110°C for 60 seconds, the silicon wafer having the resist film was immersed in the developer shown in Table 3 below and developed for 30 seconds. By removing the silicon wafer having the resist film from the developer and spin-drying it, a silicon wafer having a resist pattern formed of a line and space pattern with a pitch of 50 nm was obtained.

[0483] A silicon wafer with a resist pattern formed thereon was inspected using a defect evaluation device "UVision8" (Applied Materials) to create a defect map. Then, images of the defects were acquired using SEMVision G4 (Applied Materials), and the number of pattern defects per silicon wafer (number of pattern defects) was calculated.

[0484] [Silicon Wafer Pattern Formation and Defect Count Measurement (2)]

[0485] For a silicon wafer having a resist pattern manufactured by the above method, dry etching treatment (oxygen plasma etching) was performed on the lower film using an etching device (product name "Tactras Vigus", manufactured by Tokyo Electron Co., Ltd.) with the resist pattern as a mask. The dry etching treatment was performed until the surface of the silicon wafer was exposed, thereby forming a pattern on the lower film.

[0486] After that, the number of defects (total number of defects) of the pattern formed on the lower film and the resist pattern was measured by measuring the number of defects in the same way as the method for measuring the number of defects of the resist pattern above. Subsequently, the number of defects of the pattern formed on the lower film was calculated by subtracting the number of defects of the resist pattern from the total number of defects obtained.

[0487] [Evaluation of Conservation Stability]

[0488] Each of the resist compositions prepared in each example and each comparative example was placed in a container and subjected to a storage test by storing them in a constant temperature bath at 35°C for 3 months. After the storage period had elapsed, a resist pattern was formed in the same manner as the method for measuring the number of defects in the resist pattern described above, and the number of defects in the formed resist pattern was measured.

[0489] The storage stability of the resist composition was evaluated based on the following evaluation criteria from the ratio of the number of defects in the resist pattern formed using the resist composition after storage to the number of defects in the resist pattern formed using the resist composition immediately after manufacturing (before storage) {(number of defects after storage) / (number of defects before storage), also referred to as the "defect increase rate before and after storage test").

[0490] (metewand)

[0491] A: The defect increase rate before and after storage testing is less than 1.1 times.

[0492] B: The defect increase rate before and after storage testing is 1.1 times or more and less than 2 times.

[0493] C: The defect increase rate before and after storage testing is more than double.

[0494] Table 3 below shows the resist composition, developer, measurement results, and evaluation results used in each example.

[0495] In the table, "nBA / UD" in the "Developer" column represents a mixture of butyl acetate and undecae (butyl acetate:undecae = 90:10 (mass ratio)).

[0496] Also, in the table, the column “Number of defects in resist pattern (1)” indicates the number of defects in the resist pattern per silicon wafer, the column “Number of defects after etching (2)” indicates the sum of the number of defects in the pattern formed on the lower layer and the number of defects in the resist pattern per silicon wafer, and the column “(2)-(1)” indicates the number of defects in the pattern formed on the lower layer per silicon wafer.

[0497] [Table 6]

[0498]

[0499] [Examples 15–124]

[0500] Except for using a developer containing an organic solvent as shown in Table 4 below, a resist pattern was formed using the resist composition described in Table 2 according to the method described in [Formation of resist pattern and measurement of number of defects (1)] above, and the number of pattern defects per silicon wafer was determined, and a dry etching treatment was performed on the silicon wafer having the resist pattern manufactured according to the method described in [Formation of silicon wafer pattern and measurement of number of defects (2)] above to determine the number of defects in the pattern formed on the lower layer.

[0501] As a developer, the following organic solvents S-1 to S-18 were used.

[0502] S-1: Undecane (Manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0503] S-2: Decane (Manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0504] S-3: Dodecane (Manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0505] S-4: 2-Methyldecane (Manufactured by Fujifilm Wako Junyaku Co., Ltd.)

[0506] S-5: Nonein (Manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0507] S-6: Butyl acetate (manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0508] S-7: Isobutyl acetate (manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0509] S-8: t-butyl acetate (manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0510] S-9: Amyl acetate (Manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0511] S-10: Isoamyl acetate (Manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0512] S-11: Propyl propionic acid (Manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0513] S-12: Butyl propionate (Manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0514] S-13: Isobutyl propionate (Manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0515] S-14: Ethyl butyrate (Manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0516] S-15: Isoamyl formic acid (manufactured by Fujifilm Wako Junyaku Co., Ltd., "Wako Express")

[0517] S-16: Butyric Acid Profile (Tokyo Kasei High School Co., Ltd.)

[0518] S-17: Isopropyl butyric acid (manufactured by Fujifilm Wako Junyaku Co., Ltd.)

[0519] S-18: Isobutyric acid profile (manufactured by Tokyo Kasei High School Co., Ltd.)

[0520] In Table 4, the "Type" column of "Developer" indicates the type of organic solvent included in the developer of each example, and the "Amount (%)" column of "Developer" indicates the content (mass%) of each organic solvent relative to the total amount of developer.

[0521] The notations for "number of resist pattern defects (1)", "number of defects after etching (2)", and "(2)-(1)" in Table 4 are each the same as the notations for each column in Table 3.

[0522] [Table 7]

[0523]

[0524] [Table 8]

[0525]

[0526] [Table 9]

[0527]

[0528] [Table 10]

[0529]

[0530] From the evaluation results shown in the table above, it was confirmed that the resist composition of the present invention is less likely to have defects in the formed pattern when an etching treatment is performed using a resist pattern formed using the resist composition as a mask, and also has excellent storage stability.

Claims

Claim 1 A resin whose polarity is increased by the action of an acid, a photogenerator, at least one compound Y selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), and a desensitizing photo- or radiation-reducing resin composition containing a metal atom, wherein the content of the metal atom is 0.1 to 10,000 mass ppt with respect to the total mass of the composition, and the mass ratio of the content of the compound Y to the content of the metal atom is 1.0×10 to 1.0×10 9 Phosphorus, photosensitive or radioactive resin composition.[Chemical Formula 1] In Formula (1), R1 to R3 each independently represent an alkyl group having 1 to 5 carbon atoms. In Formula (2), R4 and R5 each independently represent an alkyl group having 1 to 5 carbon atoms. Claim 2 A photosensitive or radiation-sensitive resin composition according to claim 1, satisfying the following requirement 1. Requirement 1: A photosensitive or radiation-sensitive resin composition is applied to the surface of a silicon wafer with a diameter of 12 inches, and the resulting film is baked at 120°C for 60 seconds to produce a silicon wafer having a resist film with a thickness of 50 nm. The silicon wafer having the resulting resist film is immersed in a mixed solution comprising butyl acetate and undecae, wherein the mass ratio of butyl acetate to undecae is 9:1, to remove the resist film from the silicon wafer. Subsequently, defects on the surface of the silicon wafer from which the resist film has been removed are measured using a defect evaluation device. The number of measured defects per silicon wafer is 1 to 1000. Claim 3 A photosensitive or radiation-sensitive resin composition according to claim 1 or claim 2, wherein the resin has repeating units represented by the following formula (Y). [Chemical Formula 2] In formula (Y), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. L represents a divalent linker having a single bond or an oxygen atom. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. If multiple Rs are present, the multiple Rs may be the same or different. If multiple Rs are present, the multiple Rs may combine with each other to form a ring. a represents an integer from 1 to 3. b represents an integer from 0 to (5-a). Claim 4 A photosensitive or radiation-sensitive resin composition according to claim 1 or claim 2, further containing propylene glycol methyl ether acetate. Claim 5 A desensitizing photosensitive or radiation-sensitive resin composition according to claim 1 or claim 2, further comprising a peroxide, wherein the content of the peroxide is 100 mass ppm or less with respect to the total mass of the desensitizing photosensitive or radiation-sensitive resin composition. Claim 6 The desensitizing photoreceptive or radiation-reducing resin composition of claim 1 or claim 2, which is for EUV exposure. Claim 7 A method for manufacturing a resist pattern comprising: a resist film forming process for forming a resist film on a substrate using a photosensitive or radiation-sensitive resin composition described in claim 1 or claim 2; an exposure process for exposing the resist film to light; and a development process for developing the exposed resist film using a developer. Claim 8 A method for manufacturing a resist pattern according to claim 7, wherein the developer comprises an ester-based solvent and a hydrocarbon-based solvent. Claim 9 A method for manufacturing a resist pattern according to claim 7, wherein the developer comprises butyl acetate and undecaein. Claim 10 delete

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