Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device manufacturing method.
• pattern forming methods using chemical amplification have been used to compensate for the decrease in sensitivity due to light absorption.
• a photoacid generator contained in an exposed area is decomposed by light irradiation to generate acid.
• the catalytic action of the generated acid converts the alkali-insoluble groups of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition into alkali-soluble groups.
• the solubility in the developer is changed by, for example, changing to a base.
• development is performed using, for example, a basic aqueous solution.
• the exposed portion is removed and a desired pattern is obtained.
• the wavelength of exposure light sources has become shorter and the numerical aperture (NA) of projection lenses has become higher.
• NA numerical aperture
• EUV extreme ultraviolet
• EB electron beams
• Patent Document 1 discloses that the aromatic vinyl monomer for the polymer includes a polymer whose main chain is cleaved by electron beam irradiation to increase its solubility in a developer, a solvent, and an aromatic vinyl monomer. Disclosed is a resist composition having a content of polymers of 10 mass ppm or more and 30,000 mass ppm or less.
• the present inventors prepared an actinic ray-sensitive or radiation-sensitive resin composition with reference to Patent Document 1, and investigated its properties. Specifically, a coating film was formed using the composition, and the coating film was subjected to an exposure treatment and a development treatment to obtain a resist pattern, which was used as a mask to etch a substrate. As a result, the occurrence of defects was confirmed in the substrate after the etching treatment, and it was found that there is room for further improvement.
• the above-mentioned defects refer to parts that differ from the design, such as residues that remain in areas that should be removed by etching when a substrate is etched using a resist pattern as a mask, and chipped parts in areas that should not be removed by etching.
• an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that can form a resist pattern that suppresses the occurrence of defects in an object to be etched when used as a mask during etching processing. shall be.
• the present invention also provides a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and an electronic device. Another objective is to provide a method for manufacturing.
• the present inventor has completed the present invention as a result of intensive studies to solve the above problems. That is, it has been found that the above problem can be solved by the following configuration.
• An actinic ray-sensitive or radiation-sensitive resin composition comprising an aromatic vinyl compound and a dimer of a compound selected from the group consisting of ⁇ -halogenoacrylic acid ester,
• An actinic ray-sensitive or radiation-sensitive resin composition wherein the content of the dimer is 1 to 100,000 ppm by mass based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.
• an actinic ray-sensitive or radiation-sensitive resin composition that can form a resist pattern that suppresses the occurrence of defects in an object to be etched when used as a mask during etching processing. Further, according to the present invention, there is provided a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and A method of manufacturing an electronic device can also be provided.
• organic group refers to a group containing at least one carbon atom.
• active rays or “radiation” include, for example, the bright line spectrum of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet (EUV), X-rays, and electron beams (EB: Electron Beam), etc.
• Light in this specification means actinic rays or radiation.
• exposure refers not only to exposure to the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also to electron beams, unless otherwise specified.
• a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
• the bonding direction of the divalent groups described herein is not limited unless otherwise specified.
• Y in the compound represented by the formula "X-Y-Z" is -COO-, Y may be -CO-O- or -O-CO- Good too. Further, the above compound may be "X-CO-O-Z" or "X-O-CO-Z".
• ppm means “parts-per-million ( 10-6 )
• ppb means “parts-per-billion (10-9)
• ppt means “parts-per-billion ( 10-9 )”. parts-per-trillion (10 ⁇ 12 )”.
• resin means the component whose molecular weight is 1000 or more.
• the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (hereinafter also referred to as "molecular weight distribution") (Mw/Mn) of the resin such as the main chain cleaved resin are as follows: GPC measurement using a GPC (Gel Permeation Chromatography) device (HLC-8120GPC, manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation), column temperature: Defined as a polystyrene equivalent value measured at 40° C., flow rate: 1.0 mL/min, detector: differential refractive index detector. Note that when calculating Mw, Mn, etc., resins with a molecular weight of 1000 or more are to
• the solid content is intended to be a component that forms a resist film, and does not include a solvent. Furthermore, if the component forms a resist film, it is considered to be a solid component even if the component is liquid.
• ClogP values were obtained from Daylight Chemical Information System, Inc. This value was calculated using the program "CLOGP” available from. This program provides the value of "calculated logP” calculated by the fragment approach of Hansch, Leo (see below). The fragment approach is based on the chemical structure of a compound and estimates the logP value of the compound by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments. The details are described in the following documents. In this specification, ClogP values calculated by the program CLOGP v4.82 are used. A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds.
• Log P means the common logarithm of the partition coefficient P, which is a physical property that quantitatively represents how an organic compound is distributed in equilibrium between a two-phase system of oil (generally 1-octanol) and water, and is expressed by the following formula.
• log P log (Coil/Cwater)
• Coil represents the molar concentration of the compound in the oil phase
• Cwater represents the molar concentration of the compound in the water phase.
• boiling point means the boiling point under 1 atmosphere (760 mmHg).
• halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
• the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "resist composition") of the present invention will be explained in detail.
• the resist composition of the present invention comprises a main chain-cleaved resin containing a repeating unit A derived from an aromatic vinyl compound and a repeating unit B derived from an ⁇ -halogenoacrylic acid ester, the aromatic vinyl compound, and the ⁇ - and a dimer of a compound selected from the group consisting of halogenoacrylate esters, wherein the content of the dimer is 1 to 100,000 mass based on the total mass of the resist composition. It is ppm.
• the content of the dimer is 1 to 100,000 ppm by mass based on the total mass of the resist composition. If the dimer content exceeds 100,000 ppm by mass, the resist pattern may be removed by etching when etching is performed using the formed resist pattern as a mask, although the detailed mechanism is unknown. As a result, etching progresses in the region of the object to be etched that was protected by the resist pattern, and is detected as a defect.
• the dimer content is less than 1 ppm by mass, the lack of dimer content in the non-pattern area (exposed area) during the development process when forming a resist pattern may cause the development.
• the solubility of the resist film in the liquid is insufficient, making it difficult to remove the resist film, resulting in defects originating from the resist film in non-pattern areas, which are transferred as they are during etching and detected as defects during etching. becomes. Therefore, when the dimer content is in the range of 1 to 100,000 ppm by mass, it is possible to sufficiently suppress the occurrence of defects.
• the effect of the present invention is more excellent.
• the resist composition of the present invention contains a main chain cleavage type resin that contains repeating units A and B.
• the term "main chain cleavage type resin” refers to a resin in which a depolymerization reaction occurs upon exposure to light, which causes the main chain to be cleaved and improves the solubility in a developer.
• a dissolution contrast is generated, which enables the formation of a resist pattern by development.
• the repeating units contained in the main chain cleavage type resin will be described below.
• the repeating unit A is a repeating unit derived from an aromatic vinyl compound.
• the above-mentioned aromatic vinyl compound represents a compound in which at least one hydrogen atom in ethylene is substituted with a monovalent aromatic group.
• the monovalent aromatic group is not particularly limited, and may be either an aryl group that may have a substituent or a heteroaryl group that may have a substituent. Specific embodiments of the monovalent aromatic group will be described later.
• repeating unit A examples include a repeating unit represented by the following formula (A).
• R 1 represents an alkyl group that may have a substituent.
• the number of substituents that the alkyl group may have is not particularly limited, and is preferably 1 to 4, more preferably 1 or 2.
• the substituent that the alkyl group may have (hereinafter also referred to as "substituent T") is not particularly limited, and includes, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Alkoxy groups such as methoxy, ethoxy and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acetoxy and propionyloxy and acyloxy groups such as benzoyloxy groups; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl
• the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 1.
• the alkyl group mentioned above may be linear, branched, or cyclic, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group.
• linear or branched alkyl groups such as n-hexyl groups, monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, norbornyl groups, tetracyclodecanyl groups, tetracyclododecanyl groups, and adamantyl groups.
• Examples include polycyclic cycloalkyl groups such as groups.
• the alkyl group is preferably a linear alkyl group, more preferably a linear alkyl group having 1 to 5 carbon atoms, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
• the optionally substituted alkyl group represented by R 1 is preferably a linear alkyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
• Ar represents a monovalent aromatic group that may have a substituent.
• the number of substituents that the monovalent aromatic group may have is not particularly limited, and is preferably 1 to 4, and more preferably 1 or 2.
• the substituent that the monovalent aromatic group may have may be the group exemplified as the above-mentioned substituent T.
• the substituent that the monovalent aromatic group may have is preferably an alkyl group that may have a halogen atom, more preferably an alkyl group that may have a fluorine atom. Note that, when the alkyl group has a fluorine atom, it may be a perfluoroalkyl group.
• the alkyl group may be linear, branched, or cyclic.
• the alkyl group is preferably a linear or branched alkyl group, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and further preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or a t-butyl group.
• the monovalent aromatic group is not particularly limited, and may be either monocyclic or polycyclic, or may be either an aryl group or a heteroaryl group.
• the number of ring member atoms in the monovalent aromatic group is preferably 6 to 15, more preferably 6 to 10.
• an aryl group is preferable, a phenyl group, a naphthyl group, or an anthracenyl group is more preferable, and a phenyl group is still more preferable.
• an aryl group which may have a substituent is preferable, and an aryl group which may have a substituent is preferable.
• a phenyl group, a naphthyl group, or an anthracenyl group are more preferred, a phenyl group which may have a t-butyl group or a trifluoromethyl group is even more preferred, and a phenyl group is particularly preferred.
• a phenyl group has a substituent, it is preferable to have a substituent at the para position on the phenyl group.
• the aromatic vinyl compound is preferably ⁇ -methylstyrene or a derivative thereof, and more preferably ⁇ -methylstyrene. That is, in formula (A), R 1 is preferably a methyl group and Ar is a phenyl group which may have a substituent; in formula (A), R 1 is a methyl group, and Ar is more preferably a phenyl group.
• the content of repeating unit A in the main chain cleavage type resin is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and 40 to 60 mol% based on all repeating units in the main chain cleavage type resin. is even more preferable.
• the main chain cleavage type resin may contain two or more types of repeating units A, and in that case, it is preferable that the total content of all repeating units A is within the above range.
• the repeating unit B is a repeating unit derived from an ⁇ -halogenoacrylic acid ester.
• An example of the repeating unit B is a repeating unit represented by the following formula (B).
• X represents a halogen atom.
• the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, with a chlorine atom being preferred.
• R 2 represents a monovalent organic group.
• the monovalent organic group include an alkyl group that may have a substituent, a monovalent aromatic group that may have a substituent, and an aralkyl group that may have a substituent. Examples include groups.
• the number of substituents that the alkyl group may have is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.
• substituents that the alkyl group may have include the groups exemplified for the substituent T described above. Among these, the above-mentioned substituent is preferably a halogen atom, and more preferably a fluorine atom. Note that when the alkyl group has a fluorine atom, it may be a perfluoroalkyl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 to 3, particularly preferably 1 or 2.
• the alkyl group may be linear, branched, or cyclic, and includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group.
• linear or branched alkyl groups such as n-hexyl groups, monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, norbornyl groups, tetracyclodecanyl groups, tetracyclododecanyl groups, and Examples include polycyclic cycloalkyl groups such as adamantyl groups.
• the alkyl group is preferably a linear alkyl group or a polycyclic cycloalkyl group, and more preferably a linear alkyl group or an adamantyl group.
• the number of carbon atoms in the linear alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1.
• the number of substituents that the monovalent aromatic group may have is not particularly limited, and is preferably 1 to 4, more preferably 1 or 2.
• Examples of the substituent that the monovalent aromatic group may have include the groups exemplified for the substituent T described above. Among these, a halogen atom is preferable as the above-mentioned substituent.
• the monovalent aromatic group is not particularly limited, and may be either monocyclic or polycyclic, or may be either an aryl group or a heteroaryl group.
• the number of ring member atoms in the monovalent aromatic group is preferably 6 to 15, more preferably 6 to 10.
• an aryl group is preferable, a phenyl group, a naphthyl group, or an anthracenyl group is more preferable, and a phenyl group is still more preferable.
• the phenyl group has a substituent, it is preferable to have the substituent at the para position of the phenyl group.
• the aralkyl group preferably has a structure in which one of the hydrogen atoms in the alkyl group described above is substituted with the aryl group described above.
• the number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 15.
• the number of substituents is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2.
• examples of the above-mentioned substituent include the groups exemplified for the above-mentioned substituent T, and a halogen atom is preferable.
• the monovalent organic group represented by R 2 is preferably an alkyl group that may have a substituent or a monovalent aromatic group that may have a substituent.
• An optionally alkyl group is more preferred.
• the monovalent organic group represented by R2 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an adamantyl group, a trifluoromethyl group, or a pentafluoroethyl group; , an adamantyl group, or a pentafluoroethyl group, and even more preferably a methyl group.
• ⁇ -halogenoacrylic ester ⁇ -chloroacrylic acid alkyl ester is preferred, and methyl ⁇ -chloroacrylate is more preferred. That is, in formula (B), it is preferable that X is a chlorine atom and R 2 is an alkyl group which may have a substituent; in formula (B), X is a chlorine atom, and R 2 is more preferably a methyl group.
• the content of repeating unit B in the main chain cleavage type resin is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and 40 to 60 mol% based on all repeating units in the main chain cleavage type resin. is even more preferable.
• the main chain cleavage type resin may contain two or more types of repeating units B, and in that case, it is preferable that the total content of all repeating units B is within the above range.
• the main chain cleavage type resin may contain other repeating units that do not fall under either repeating unit A or repeating unit B.
• the content of the other repeating units in the main chain cleavage type resin is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, and 0 to 5 mol%, based on the total repeating units in the main chain cleavage type resin. More preferred is mole %.
• the weight average molecular weight (Mw) of the main chain cleavage type resin is not particularly limited, but in terms of the effects of the present invention being more excellent, it is preferably 15,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more.
• the upper limit is not particularly limited, but is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less.
• the number average molecular weight (Mn) of the main chain cleavage type resin is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 16,000 or more, and particularly preferably 19,000 or more, in terms of the effect of the present invention being more excellent.
• the upper limit is not particularly limited, but is preferably 150,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
• the polydispersity (Mw/Mn) of the main chain-cleaved resin is not particularly limited, but in terms of the effects of the present invention being more excellent, the polydispersity (Mw/Mn) is preferably 2.5 or less, more preferably 2.0 or less, and 1.7 or less. is even more preferable.
• the lower limit is not particularly limited, and examples include 1.0 or more.
• the content of the main chain cleavage type resin is not particularly limited, but it is preferably 0.1 to 30% by mass, and 0.5 to 20% by mass based on the total mass of the resist composition, in order to achieve better effects of the present invention. % is more preferable, and 0.5 to 10% by mass is even more preferable.
• the content of the main chain cleavage type resin is not particularly limited, but it is preferably 5 to 99% by mass, more preferably 10 to 97% by mass, based on the total solid content of the resist composition, in order to achieve better effects of the present invention. , 15 to 97% by mass is more preferable.
• the resist composition of the present invention contains a dimer of a compound selected from the group consisting of an aromatic vinyl compound and an ⁇ -halogenoacrylic acid ester, and the content of the dimer is such that the total weight of the resist composition is 1 to 100,000 ppm by mass.
• a dimer of a compound selected from the group consisting of an aromatic vinyl compound and an ⁇ -halogenoacrylic acid ester and the content of the dimer is such that the total weight of the resist composition is 1 to 100,000 ppm by mass.
• specific embodiments and preferred embodiments of the aromatic vinyl compound and ⁇ -halogenoacrylic acid ester are as described above.
• the above dimer is a dimer having either a structure in which two molecules of an aromatic vinyl compound are bonded or a structure in which two molecules of ⁇ -halogenoacrylate are bonded (hereinafter also referred to as "dimer X".
• dimer Y a dimer having a structure in which one molecule of an aromatic vinyl compound and one molecule of ⁇ -halogenoacrylate ester are bonded.
• aromatic vinyl compounds and the ⁇ -halogenoacrylic acid esters in the dimer X may have the same structure or different structures.
• terminal structure of the dimer is not particularly limited, and may have a structure derived from a polymerization initiator, etc., which will be described later.
• the term "dimer” refers to a form containing both the above-mentioned dimer X and dimer Y.
• the molecular weight of the dimer is often less than 1000, preferably from 50 to 900, more preferably from 150 to 650, even more preferably from 200 to 530.
• the content of the dimer is not particularly limited as long as it is 1 to 100,000 ppm by mass based on the total mass of the resist composition, but it is preferably 1 to 10,000 ppm by mass, and 1 It is more preferably from 1 to 1,000 ppm by mass, and even more preferably from 1 to 1,000 ppm by mass.
• the content of the dimer is the total content of the dimer X and dimer Y.
• products obtained by synthesizing main chain-cleaved resins by radical polymerization may contain dimers as by-products, so this product may be treated to remove low-molecular weight components. By applying this, the content of the dimer in the mixture of the main chain-cleaved resin and the dimer can be adjusted.
• the dimer content can be adjusted within a predetermined range.
• examples of the treatment for removing the low molecular weight components include a molecular weight fractionation method using GPC and a reprecipitation method.
• the content of dimer in the precipitate can be adjusted by selecting the type of reprecipitation solvent used.
• the content of the dimer in the mixture of the main chain-cleaved resin and the dimer is determined by, for example, taking the ratio of the area of the peak corresponding to the molecular weight of the dimer to the total peak area obtained by GPC measurement. It can be calculated by
• the amount of dimer in the product can be adjusted by adjusting the timing of addition of the monomers used. More specifically, after polymerization is performed using a predetermined amount of monomer, the reaction system is opened, and then a post-addition process is performed in which a monomer and a polymerization initiator are separately added to the reaction system. Products containing molecular weight resins and dimers can be easily synthesized. In particular, when the amount of monomer used in the post-addition treatment is large, the amount of dimer produced tends to be large. Further, the amount of dimer produced can also be increased by increasing the amount of polymerization initiator used in the post-addition treatment.
• a resist composition may be prepared using a mixture containing a main chain-cleaved resin and a dimer produced by such a production procedure.
• the resist composition of the present invention may contain a metal element selected from the group consisting of Na, K, Ca, Zn, and Fe.
• the above metal elements may be present in the resist composition due to each component contained in the resist composition, and if the content of the metal elements is within the above range, it will remain when a resist pattern is formed. This is preferable because defects can be reduced.
• the content of the above-mentioned metal element is often 1 to 1000 mass ppb, and in terms of the effects of the present invention being more excellent, the content is preferably 1 to 300 mass ppb, more preferably 1 to 50 mass ppb, and 1 to 20 mass ppb. is more preferable, and 1 to 10 mass ppb is particularly preferable.
• the content of the above metal elements can be adjusted by, for example, adding a metal source such as sodium carbonate to the resist composition. Further, the content of the metal element can be calculated by, for example, an elemental analysis method such as an inductively coupled plasma mass spectrometer (ICP-MS).
• the resist composition may contain a solvent.
• the solvent is not particularly limited as long as it can dissolve the main chain-cleaved resin, and any known solvent can be used.
• the solvent include anisole, acetate (methyl acetate, ethyl acetate, butyl acetate, etc.), tetrahydrofuran (THF), chain ketone (acetone, etc.), cyclic ketone (2-heptanone, cyclohexanone, cyclopentanone, etc.) ), propylene glycol monoalkyl ether carboxylates (propylene glycol monomethyl ether acetate, etc.), propylene glycol monoalkyl ethers (propylene glycol monomethyl ether or propylene glycol monoethyl ether, etc.), lactic acid esters (ethyl lactate, etc.), lactones ( ⁇ -butyrolactone) etc.), alkylene carbonates (such as propylene carbonates (such as propyl
• the content of the solvent is preferably 70 to 99.9% by mass, more preferably 80 to 99.5% by mass, based on the total mass of the resist composition.
• the resist composition may contain only one type of solvent, or may contain two or more types of solvent. When two or more types are included, it is preferable that their total amount falls within the above range.
• the resist composition may include a photoacid generator or a photobase generator.
• the photoacid generator is not particularly limited as long as it is a compound that generates an acid when irradiated with actinic rays or radiation, but in particular, it is a compound having an onium salt structure (photodegradable type) that generates an acid when irradiated with actinic rays or radiation. onium salt compounds) are preferred.
• a photodegradable onium salt compound is a compound that has at least one salt structure site composed of an anion site and a cation site, and that decomposes upon exposure to light to generate an acid (preferably an organic acid).
• the salt structure moiety of the photodegradable onium salt compound is preferably composed of an organic cation moiety and a non-nucleophilic organic anion moiety in terms of ease of decomposition upon exposure and superior production of organic acid.
• photoacid generators include paragraphs [0027] to [0030] of JP2021-026053A, paragraphs [0135] to [0171] of WO2018/193954, and WO2020/066824.
• Compounds described in paragraphs [0077] to [0116] of , and paragraphs [0018] to [0075] and [0334] to [0335] of International Publication No. 2017/154345 can be used.
• the photobase generator is not particularly limited as long as it is a compound that generates a base upon irradiation with actinic rays or radiation.
• the photobase generator for example, the compounds described in paragraph [0031] of JP-A No. 2021-026053 can be used.
• the content of the photoacid generator is preferably 0.5 to 40.0% by mass, and 1.0 to 40.0% by mass, based on the total solid content of the resist composition. 0% by mass is more preferred, and 5.0 to 30.0% by mass is even more preferred.
• the content of the photobase generator is preferably 0.5 to 40.0% by mass, and 1.0 to 40.0% by mass, based on the total solid content of the resist composition. 0% by mass is more preferred, and 5.0 to 30.0% by mass is even more preferred.
• the resist composition may contain only one type of photoacid generator or photobase generator, or may contain two or more types of photoacid generator or photobase generator. When two or more types are included, it is preferable that their total amount falls within the above range.
• the resist composition may further contain a surfactant.
• a surfactant fluorine-based and/or silicon-based surfactants are preferred. Examples of the fluorine-based and/or silicon-based surfactants include the surfactants described in paragraphs [0218] and [0219] of International Publication No. 2018/193954.
• the content of the surfactant is preferably from 0.0001 to 2 mass %, and more preferably from 0.0005 to 1 mass %, based on the total solid content of the resist composition.
• the resist composition may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, it is preferable that the total amount thereof is in the above-mentioned range.
• the resist composition contains, as other additives, a dissolution inhibiting compound (a compound with a molecular weight of 3000 or less that decomposes under the action of an acid and reduces its solubility in an organic developer), a dye, a plasticizer, and a photosensitizer. , a light absorber, and a compound that promotes solubility in a developer (for example, a phenol compound with a molecular weight of 1000 or less, and an alicyclic or aliphatic compound containing a carboxylic acid group). It may contain additives.
• a dissolution inhibiting compound a compound with a molecular weight of 3000 or less that decomposes under the action of an acid and reduces its solubility in an organic developer
• a dye for example, a phenol compound with a molecular weight of 1000 or less, and an alicyclic or aliphatic compound containing a carboxylic acid group. It may contain additives.
• a dissolution inhibiting compound
• the total content of the above-mentioned main chain cleavage resin, dimer, photoacid generator, photobase generator, and surfactant in the resist composition is not particularly limited, but the total content of the resist composition is 99% by mass or more, preferably 99.5% by mass or more, more preferably 99.99% by mass or more, particularly preferably 99.999% by mass or more.
• the upper limit is not particularly limited, but may be 100% by mass.
• the total content of the above-mentioned main chain-cleaved resin and dimer in the resist composition is not particularly limited, but is preferably 99% by mass or more, and 99% by mass or more based on the total solid content of the resist composition.
• the content is more preferably 5% by mass or more, even more preferably 99.99% by mass or more, and particularly preferably 99.999% by mass or more.
• the upper limit is not particularly limited, but may be 100% by mass.
• the mass ratio of the dimer content to the main chain cleavage resin content in the resist composition is not particularly limited, but is preferably 0.00001 to 5, more preferably 0.00001 to 1, and 0.00001. ⁇ 0.01 is more preferred.
• the method for producing the resist composition of the present invention is not particularly limited as long as it contains the above-mentioned components in predetermined amounts.
• a main chain cleavage resin and a dimer may be separately prepared and mixed to produce a resist composition.
• a product obtained by synthesizing a main chain-cleaved resin by radical polymerization or the like may contain a dimer or the like as a by-product.
• a resist composition may be made using a mixture of mold resin and dimer. Furthermore, as mentioned above, when producing main chain-cleaved resins by radical polymerization, etc., the timing of addition of the monomers used can be adjusted to adjust the amount of dimer in the product.
• a resist composition may be manufactured using a mixture of a main chain truncated resin and a dimer.
• the procedure for forming a resist film and a pattern using the resist composition is not particularly limited, but it is preferable for the method to include the following steps. Step 1: Forming a resist film on a substrate using a resist composition; Step 2: Exposing the resist film; Step 3: Developing the exposed resist film using a developer containing an organic solvent to form a resist pattern. The procedure for each step will be described in detail below.
• Step 1 is a step of forming a resist film on a substrate using a resist composition.
• the definition of the resist composition is as described above.
• Examples of methods for forming a resist film on a substrate using a resist composition include a method of applying a resist composition onto a substrate. Note that it is preferable to filter the resist composition before coating, if necessary.
• the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
• the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
• the resist composition can be applied, for example, onto a substrate (eg, silicon, silicon dioxide coated) used in the manufacture of integrated circuit devices using a spinner, coater, or the like.
• a substrate eg, silicon, silicon dioxide coated
• spin coating using a spinner is preferred.
• the rotation speed during spin coating using a spinner is preferably 1000 to 3000 rpm.
• a base film for example, an inorganic film, an organic film, and an antireflection film
• the substrate to be processed for example, in the case of a semiconductor wafer, a silicon wafer can be used.
• Examples of the material for the outermost layer of the substrate to be processed include Si, SiO 2 , SiN, SiON, TiN, WSi, BPSG (Boro-Phospho.Silicate Glass), SOG (Spin On Glass), and organic antireflection film. can be mentioned.
• a drying process may be performed to form a resist film.
• the drying method include a method of drying by heating. Heating can be carried out using a means provided in an ordinary exposure machine and/or developing machine, or may be carried out using a hot plate or the like.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
• the resist film can be formed, for example, by prebaking at 60 to 150° C. for 1 to 20 minutes, preferably at 80 to 120° C. for 1 to 10 minutes.
• the thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the standpoint of forming fine patterns with higher precision. Among these, when performing EUV exposure, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
• a top coat may be formed on the upper layer of the resist film using a top coat composition.
• the top coat composition is preferably a composition that does not mix with the resist film and can be uniformly applied to the upper layer of the resist film.
• the thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm, and even more preferably 40 to 80 nm.
• the composition and formation method of the top coat are not particularly limited, and a known top coat can be formed using a known method. For example, a top coat can be formed based on the description in paragraphs [0072] to [0082] of JP-A-2014-059543.
• a top coat containing a basic compound described in JP-A-2013-061648 on the resist film. It is also preferable that the top coat contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl group, and an ester group.
• Step 2 is a step of exposing the resist film.
• the exposure method include a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask.
• Actinic light or radiation includes infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, particularly preferably 1 Deep ultraviolet light with a wavelength of ⁇ 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams. .
• post-exposure heat treatment PEB: Post Exposure Bake
• the post-exposure heat treatment accelerates the reaction in the exposed area, resulting in better sensitivity and pattern shape.
• Heating can be carried out using a means provided in a normal exposure machine and/or developing machine, and may also be carried out using a hot plate or the like.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, 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.
• Step 3 is a step of developing the exposed resist film using a developer containing an organic solvent to obtain a resist pattern.
• Development methods include, for example, a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and the substrate is left still for a certain period of time for development (paddle method). ), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the rotating substrate (dynamic dispensing method). can be mentioned.
• a step of stopping the development may be performed while replacing the developer with another solvent.
• the development time is not particularly limited as long as the resin in the unexposed areas is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
• the temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
• the organic solvent contained in the developer is preferably at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
• the ClogP value of the organic solvent contained in the developer is not particularly limited, but is preferably 0.00 or more, more preferably 1.00 or more. When two or more types of organic solvents are included, it is preferable that the ClogP value of the mixed solvent falls within the above range.
• ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate.
• ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butane
• Examples include butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
• the alcohol solvent amide solvent, ether solvent, and hydrocarbon solvent
• the solvents described in paragraphs [0715] to [0718] of US Patent Application Publication No. 2016/0070167 can be used. .
• the above solvents may be used alone, or in combination of two or more, or may be mixed with solvents other than the above or with water.
• the water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
• the content of the organic solvent in the developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass. Particularly preferred.
• the developer contains two types, a first organic solvent and a second organic solvent, and the boiling point of the first organic solvent is higher than the boiling point of the second organic solvent, Further, it is more preferable that the ClogP value of the first organic solvent is larger than the ClogP value of the second organic solvent.
• the content ratio of the first organic solvent and the second organic solvent in the developer is not particularly limited, but the mass ratio of the content of the second organic solvent to the content of the first organic solvent is preferably 1 to 50, 3 to 20 is more preferable.
• the first organic solvent in the developer is not particularly limited, but an organic solvent with a ClogP value of 3.00 or more is preferable, and a hydrocarbon solvent is more preferable.
• the second organic solvent in the developer is preferably the ketone solvent or the ester solvent, more preferably an ester solvent, and still more preferably butyl acetate or isoamyl butyrate.
• the pattern forming method may include other steps in addition to those described above. Examples of the other steps include a rinsing step and a heating step.
• the above pattern forming method preferably includes a rinsing step of cleaning the pattern using a rinsing liquid containing an organic solvent after step 3.
• the organic solvent contained in the rinse liquid is preferably at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents.
• Examples and preferred embodiments of the hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents are the same as those of the organic solvent contained in the developer.
• the rinsing liquid preferably contains two types: a first organic solvent and a second organic solvent. Among these, it is more preferable that the boiling point of the first organic solvent is higher than the boiling point of the second organic solvent, and the ClogP value of the first organic solvent is higher than the ClogP value of the second organic solvent.
• the ratio of the contents of the first organic solvent and the second organic solvent in the rinse solution is not particularly limited, but in terms of the effect of the present invention being more excellent, the mass ratio of the content of the second organic solvent to the content of the first organic solvent is preferably 1 to 50, and more preferably 3 to 20.
• the first organic solvent in the rinse liquid is not particularly limited, but an organic solvent with a ClogP value of 3.00 or more is preferable, and a hydrocarbon solvent is more preferable.
• the second organic solvent in the rinse liquid is preferably the ketone solvent or the ester solvent, more preferably an ester solvent, and still more preferably butyl acetate or isoamyl butyrate.
• the above-mentioned cleaning method is not particularly limited, and examples include a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (rotary coating method), a method of immersing a substrate in a tank filled with a rinsing liquid for a certain period of time. (dip method), and a method of spraying a rinsing liquid onto the substrate surface (spray method).
• the developer contains two or more organic solvents
• the pattern forming method includes a rinsing step
• at least one of the developer and the rinsing solution contains two or more organic solvents. It is preferable. Note that as the two or more organic solvents contained in the developer and the rinse solution, a combination of the above-mentioned first organic solvent and second organic solvent is preferred.
• the pattern forming method may include a heating step (Post Bake) after the rinsing step. Through this step, the developer and rinse solution remaining between the patterns and inside the patterns are removed. In addition, this step smoothes the resist pattern and improves surface roughness of the pattern.
• the heating step after the rinsing step is preferably carried out at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
• an etching process may be performed on the substrate, which is the object to be etched. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the lower film and the substrate) to form a pattern on the substrate.
• the method of processing the substrate (or the lower layer film and the substrate) is not particularly limited, but by performing dry etching on the substrate (or the lower layer film and the substrate) using the pattern formed in step 3 as a mask, the substrate can be processed.
• a method of forming a pattern is preferred.
• the dry etching is preferably oxygen plasma etching.
• Various materials other than the resist composition used in the pattern forming method of the present invention may contain impurities such as metals. Preferably, it does not contain.
• the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppt or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
• examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, Examples include W, and Zn.
• An example of a method for removing impurities such as metals from various materials is filtration using a filter. Filtration using a filter can be performed using the method described in paragraph [0321] of WO 2020/004306.
• methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as raw materials constituting various materials, and filtering raw materials constituting various materials. and a method in which distillation is carried out under conditions where contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark).
• impurities may be removed using an adsorbent, or a combination of filtration and an adsorbent may be used.
• adsorbent known adsorbents may be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
• inorganic adsorbents such as silica gel and zeolite
• organic adsorbents such as activated carbon.
• metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment.
• the content of metal components contained in the cleaning solution after use is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less.
• Organic processing solutions such as developing solutions and rinse solutions are made with conductive material to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge.
• Compounds may also be added.
• the conductive compound is not particularly limited, and for example, methanol may be mentioned.
• the amount added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less in terms of maintaining favorable development characteristics or rinsing characteristics.
• chemical liquid piping use various types of piping coated with SUS (stainless steel), polyethylene or polypropylene treated with antistatic treatment, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.), for example. can.
• antistatically treated polyethylene, polypropylene, or fluororesin can be used for the filter and O-ring.
• a method for improving pattern surface roughness may be applied to the pattern formed by the method of the present invention.
• Examples of a method for improving surface roughness of a pattern include a method of treating a pattern with plasma of a gas containing hydrogen, which is disclosed in International Publication No. 2014/002808.
• JP 2004-235468A, US Patent Application Publication No. 2010/0020297, JP 2008-83384A, and Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" Known methods may be used.
• the present invention also relates to an electronic device manufacturing method including the above-described pattern forming method, and an electronic device manufactured by this manufacturing method.
• the electronic device of the present invention is suitably installed in electrical and electronic equipment (home appliances, office automation (OA), media-related equipment, optical equipment, communication equipment, etc.).
• composition ratio (molar ratio), weight average molecular weight (Mw), and polydispersity (Mw/Mn) of each repeating unit in the main chain-cleaved resin are as shown in Table 1.
• the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw/Mn) of the main chain cleaved resin were determined by GPC (Gel Permeation Chromatography) apparatus (Tosoh HLC-8120GPC).
• the content of the dimer relative to the total mass of the mixture is calculated by taking the ratio of the area of the peak corresponding to the molecular weight of the dimer to the total peak area of the mixture obtained in the above (purification treatment method). did. Based on the description of the dimer content in this mixture, the amount of the mixture used was adjusted to adjust the dimer content in the resist composition.
• a lower layer film forming composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied onto a silicon wafer with a diameter of 12 inches, and baked at 205° C. for 60 seconds to form a lower layer film with a thickness of 20 nm.
• Each of the resist compositions shown in Table 1 above was applied thereon, and the coating film was baked at 100° C. for 60 seconds to produce a silicon wafer having a resist film with a thickness of 35 nm.
• the silicon wafer having the resist film obtained by the above procedure was exposed to 30 mJ/cm 2 .
• Pattern exposure was carried out at a certain amount.
• As the reticle a mask with a line width of 30 nm on the wafer and a line:space ratio of 1:1 was used.
• the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 60 nm.
• a silicon wafer having a resist pattern manufactured by the above method is subjected to a dry etching process on the underlying film using the resist pattern as a mask using an etching device (product name "Tactras Vigus", manufactured by Tokyo Electron Ltd.). (oxygen plasma etching).
• a dry etching process was performed until the surface of the silicon wafer was exposed to form a pattern on the underlying film.
• the resist pattern was peeled off using EKC265 (manufactured by DuPont), and the obtained silicon wafer was inspected with a defect evaluation device "UVision 8" (manufactured by Applied Materials) to create a defect map. Thereafter, images of defects were acquired using SEMVision G4 (manufactured by Applied Materials), and the number of defects (pieces/cm 2 ) on the silicon wafer was calculated.
• the evaluation results are shown in Table 1.
• the column “Repeating unit type” shows the structure of repeating unit A and repeating unit B.
• the “composition ratio” column indicates the content (mol%) of repeating unit A (left column) and repeating unit B (right column) with respect to all repeating units of the main chain cleavage type resin.
• the "Main chain cleavage resin content (mass %)” column represents the content of the main chain cleavage resin with respect to the total mass of the resist composition.
• the "dimer content (mass ppm)” column indicates the dimer content relative to the total mass of the resist composition.
• the "metal element content” column indicates the content of the metal element selected from the group consisting of Na, K, Ca, Zn, and Fe with respect to the total mass of the resist composition.
• the content of the above-mentioned metal elements was measured by the following method. Specifically, the content of metal elements was measured using an Agilent 8900 triple quadrupole ICP-MS (for semiconductor analysis, option #200) according to the following measurement conditions.
• the sample introduction system used a quartz torch, a coaxial PFA (perfluoroalkoxyalkane) nebulizer (for self-priming), and a platinum interface cone.
• the measurement parameters under cool plasma conditions are as follows.
• the measurement sample was prepared by diluting the resist composition using the following mixed solvent of N-methyl-2-pyrrolidone (NMP)/nitric acid.
• NMP An electronic industry grade product manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. was purified by distillation and used.
• Nitric acid An ultra-high purity analytical reagent grade product manufactured by Tama Chemical Industry Co., Ltd. was used.
• the resist composition of the present invention suppresses the occurrence of defects on the substrate when used for forming a resist pattern.
• the effect of the present invention is more excellent when the content of the dimer relative to the total mass of the resist composition is 1 to 10,000 ppm by mass (comparison of Examples 1 to 5, etc.).
• the effects of the present invention are more excellent when the content of the metal element selected from the group consisting of Na, K, Ca, Zn, and Fe is 1 to 50 ppb by mass based on the total mass of the resist composition. This was confirmed (comparison of Examples 10 to 14, etc.).
• the effects of the present invention are more excellent when the weight average molecular weight of the main chain-cleaved resin is 30,000 or more (comparison between Example 9 and Example 17, etc.).
• the effect of the present invention is more excellent when the polydispersity of the main chain-cleaved resin is 1.7 or less (comparison between Examples 5 and 19, etc.).

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