Classifications

• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
• • 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
• • 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
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • 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

Definitions

• the present invention relates to an actinic ray- or radiation-sensitive resin composition.
• a pattern formation method using chemical amplification has been used to compensate for the decrease in sensitivity due to light absorption.
• a photoacid generator contained in the exposed portion is decomposed by light irradiation to generate an acid.
• the catalytic action of the generated acid changes the alkali-insoluble group of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition to an alkali-soluble group, thereby changing the solubility in the developer.
• development is performed using, for example, a basic aqueous solution.
• the exposed portion is removed to obtain a desired pattern.
• the wavelength of the exposure light source has become shorter and the numerical aperture (NA) of the projection lens has become higher, and currently, an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed.
• pattern formation methods using extreme ultraviolet (EUV light: Extreme Ultraviolet) and electron beam (EB: Electron Beam) as light sources are also being considered in recent years.
• compositions capable of achieving ultrafine patterns have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions, and recently, resin compositions containing a resin whose main chain is decomposed or cleaved by exposure to light have become known as compositions capable of achieving ultrafine patterns.
• Patent Document 1 describes a positive resist composition that contains (A) an ionic compound and (B) a resin that has a repeating unit (b1) that has a repeating unit having an interactive group that interacts with the ionic group in the ionic compound, and whose main chain is decomposed by irradiation with X-rays, electron beams, or extreme ultraviolet rays.
• Patent Document 2 describes a resist composition containing a main chain cleavage-type polymer that includes a predetermined monomer unit in which the ⁇ -position is halogenated and a predetermined monomer unit having an aromatic hydrocarbon group having a hydroxyl group.
• the present invention aims to provide an actinic ray- or radiation-sensitive resin composition that has extremely excellent resolution and LWR performance when forming ultrafine patterns (e.g., line and space patterns with line widths of 15 nm or less, hole patterns with hole diameters of 15 nm or less, etc.).
• ultrafine patterns e.g., line and space patterns with line widths of 15 nm or less, hole patterns with hole diameters of 15 nm or less, etc.
• An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin whose main chain is decomposed by irradiation with actinic rays or radiation and an ionic compound, Film A formed from the above composition and film B exposed to the above actinic ray or radiation so that the dissolution rate in butyl acetate of film A was 0.1 nm/sec were an actinic ray-sensitive or radiation-sensitive resin composition, wherein the cationic residual rate of the ionic compound in the film B is 50 mol % or less when the cationic residual rate of the ionic compound in the film A is taken as 100 mol %.
• the present invention provides an actinic ray- or radiation-sensitive resin composition that exhibits excellent resolution and LWR performance in the formation of ultrafine patterns (e.g., line and space patterns with line widths of 15 nm or less, hole patterns with hole diameters of 15 nm or less, etc.).
• ultrafine patterns e.g., line and space patterns with line widths of 15 nm or less, hole patterns with hole diameters of 15 nm or less, etc.
• the present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
• the notation of groups (atomic groups) that does not indicate whether they are substituted or unsubstituted includes both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention.
• alkyl group includes not only alkyl groups that do not have a substituent (unsubstituted alkyl groups), but also alkyl groups that have a substituent (substituted alkyl groups).
• organic group in the present specification refers to a group that contains at least one carbon atom.
• the substituent is preferably a monovalent substituent.
• actinic rays or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, electron beams (EB: Electron Beam), etc.
• light refers to actinic rays or radiation.
• the term "exposure” includes not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-rays, and the like, but also drawing with particle beams such as electron beams (EB: Electron Beam) and ion beams.
• EUV light Extreme Ultraviolet
• EB Electron Beam
• the word "to” is used to mean that the numerical values before and after it are included as the lower limit and upper limit.
• the bonding direction of the divalent group described in this specification is not limited unless otherwise specified.
• Y when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-.
• the above compound may be "X-CO-O-Z" or "X-O-CO-Z".
• the weight average molecular weight (Mw) and dispersity (also called molecular weight distribution) (Mw/Mn) of the resin are defined as polystyrene equivalent values measured using a Gel Permeation Chromatography (GPC) device (Tosoh HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: Tosoh TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: refractive index detector).
• GPC Gel Permeation Chromatography
• the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and is specifically a value calculated using the following software package 1 based on a database of Hammett's substituent constants and publicly known literature values. All pKa values described in this specification are values calculated using this software package.
• pKa can also be obtained by molecular orbital calculation.
• a specific example of this method is a method of calculating H + dissociation free energy in an aqueous solution based on a thermodynamic cycle.
• the H + dissociation free energy can be calculated, for example, by DFT (density functional theory), but various other methods have been reported in literature, and the calculation method is not limited to this.
• DFT density functional theory
• Gaussian16 is an example.
• the pKa in this specification refers to a value calculated using the software package 1 based on a database of Hammett's substituent constants and known literature values.
• a value obtained by Gaussian 16 based on DFT density functional theory
• the pKa in this specification refers to "pKa in an aqueous solution” as described above, but when the pKa in an aqueous solution cannot be calculated, "pKa in a dimethyl sulfoxide (DMSO) solution” will be adopted.
• DMSO dimethyl sulfoxide
• halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
• solids refers to components that form an actinic ray-sensitive or radiation-sensitive resin film, and does not include solvents.
• any component that forms an actinic ray-sensitive or radiation-sensitive resin film is considered to be a solid, even if it is in liquid form.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin whose main chain is decomposed by irradiation with actinic rays or radiation and an ionic compound, Film A formed from the above composition and film B exposed to the above actinic ray or radiation so that the dissolution rate in butyl acetate of film A was 0.1 nm/sec were an actinic ray-sensitive or radiation-sensitive resin composition in which a cationic residual ratio of an ionic compound in the film B is 50 mol % or less when a cationic residual ratio of an ionic compound in the film A is taken as 100 mol %; It is.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has the above-mentioned constitution, and is extremely excellent in resolution and LWR performance in the formation of ultrafine patterns (for example, a line and space pattern having a line width of 15 nm or less, or a hole pattern having a hole diameter of 15 nm or less).
• ultrafine patterns for example, a line and space pattern having a line width of 15 nm or less, or a hole pattern having a hole diameter of 15 nm or less.
• undecomposed substances such as ionic compounds contained in the actinic ray-sensitive or radiation-sensitive resin composition may remain in the exposed area.
• the undecomposed product of the ionic compound can interact with the resin and become an interactant with the resin.
• the present inventors have found that the undecomposed product of the ionic compound in the exposed area and the interactant between the undecomposed product and the resin can become undissolved residue in the exposed area, which may affect the resolution and LWR performance of the obtained pattern.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin whose main chain is decomposed when irradiated with actinic rays or radiation, and an ionic compound, and is a material that is patterned by decomposition of the main chain of the resin when exposed to light.
• Film A was formed from the composition of the present invention, and film B was prepared by exposing film A to butyl acetate so that the dissolution rate of film A in butyl acetate was 0.1 nm/sec.
• the inventors focused on the residual cation rate of ionic compounds in film B.
• the cationic residual ratio of the ionic compound in the film B satisfies 50 mol % or less when the cationic residual ratio of the ionic compound in the film A is 100 mol %.
• the cationic residual ratio of the ionic compound in the film B is 50 mol % or less, and the cationic residual ratio of 50 mol % or less in the exposed area leads to a reduction in the undecomposed ionic compound in the exposed area, and the undissolved residue in the exposed area can be reduced. Therefore, it is possible to reduce the amount of undecomposed ionic compound remaining in the exposed area and the interactor between the undecomposed ionic compound and the resin, and it is presumed that the resolution and LWR performance of the obtained pattern are extremely excellent.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is an actinic ray-sensitive or radiation-sensitive resin composition containing a resin whose main chain is decomposed by irradiation with actinic rays or radiation and an ionic compound.
• the resins and ionic compounds whose main chains are decomposed by irradiation with actinic rays or radiation will be described later.
• the composition of the present invention is used to form a film A.
• the method for forming the film A is not particularly limited, but examples thereof include the method for forming an actinic ray-sensitive or radiation-sensitive film described below.
• the dissolution rate of Membrane A in butyl acetate is determined as follows. An actinic ray-sensitive or radiation-sensitive resin composition was applied onto a silicon wafer having a diameter of 12 inches, and baked at 120° C. for 60 seconds to form an actinic ray-sensitive or radiation-sensitive film (film A) having a thickness of 40 nm. This silicon wafer was developed with a developer (butyl acetate) for 300 seconds, and the film thickness after development was measured.
• the dissolution rate (nm/sec) of film A was calculated by subtracting the film thickness after development from the film thickness (40 nm) of film A before treatment and dividing the value by the development time (300 seconds).
• the film thickness was measured at five points on a 12-inch wafer using an optical film thickness meter ("VM3200", manufactured by SCREEN Corporation), and the average value was used.
• Film B is obtained by exposing film A to light so that the dissolution rate in butyl acetate becomes 0.1 nm/sec.
• the above exposure is not particularly limited, but open frame exposure is preferred. Open frame exposure refers to exposing the entire surface of the wafer-shaped film A to light (so-called solid exposure) without using a mask or the like using an exposure device.
• the dissolution rate of Membrane B in butyl acetate is determined as follows.
• the dissolution rate of Film B in butyl acetate was obtained by dividing the change in film thickness of Film B by the time required for treatment.
• An actinic ray-sensitive or radiation-sensitive resin composition was applied onto a silicon wafer having a diameter of 12 inches, and baked at 120° C. for 60 seconds to form an actinic ray-sensitive or radiation-sensitive film (Film A) having a film thickness of 40 nm. This wafer is exposed by an exposure device to obtain film B.
• film thickness after development was measured, and the film thickness after development was subtracted from the film thickness of the film B before treatment (40 nm) and divided by the development time (30 seconds) to calculate the dissolution rate (nm/sec) of the film B.
• the film thickness was measured at five points on the surface of a 12-inch wafer using an optical film thickness meter ("VM3200", manufactured by SCREEN Co., Ltd.) and the average value was used.
• Film B was obtained by exposing film A to light at an exposure dose that gave a dissolution rate of film B of 0.1 nm/sec.
• the residual cation ratio is 50 mol % or less, more preferably 40 mol % or less, and further preferably 30 mol % or less.
• the residual cation ratio is preferably 5 mol % or more, and more preferably 10 mol % or more.
• the content of the ionic compound in the composition is reduced, which makes it easier to adjust the residual cation ratio to 50 mol % or less.
• the dissolution rate of the film A in butyl acetate is preferably 0.010 nm/sec or less, and more preferably 0.005 nm/sec or less.
• the dissolution rate of the film A in butyl acetate is greater than 0 nm/sec.
• the pKa of the conjugate acid of the anion moiety of the ionic compound contained in the composition is increased, which is believed to decrease the solubility in the unexposed area by increasing the interaction between the resin contained in the composition and the ionic compound. It is also possible to adjust the polarity of the resin contained in the composition. Specifically, it is possible to provide a group in the resin that interacts with the ionic compound. It is considered that the solubility of the unexposed area can be reduced from two perspectives: the interaction between the resin and the ionic compound, and the affinity of the resin itself to the developer. It is also possible to increase the molecular weight of the resin contained in the composition. It is considered that the solubility of the unexposed area can be reduced by increasing the size of the resin.
• Actinic ray-sensitive or radiation-sensitive resin composition Various components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention will be described below.
• the actinic ray-sensitive or radiation-sensitive resin composition contains a resin (hereinafter also referred to as a specific resin) whose main chain is decomposed upon irradiation with actinic rays or radiation.
• the resin is a so-called main chain cleavage type polymer, in which the main chain is decomposed (the main chain is cleaved) by irradiation with actinic rays or radiation.
• the resin is preferably a resin whose main chain is decomposed by irradiation with X-rays, electron beams (EB: Electron Beam) or extreme ultraviolet rays (EUV light: Extreme Ultraviolet), more preferably a resin whose main chain is decomposed by irradiation with electron beams or extreme ultraviolet rays, and even more preferably a resin whose main chain is decomposed by irradiation with extreme ultraviolet rays.
• EB Electron Beam
• EUV light Extreme Ultraviolet
• the specific resin is preferably a resin containing a repeating unit represented by general formula (1), and more preferably a resin containing a repeating unit represented by general formula (1) and a repeating unit represented by general formula (2).
• the repeating unit represented by formula (1) and the repeating unit represented by formula (2) will be described below.
• X represents a halogen atom.
• L 1 represents -O- or -NR 1 -.
• R 1 represents a hydrogen atom or an organic group.
• R 0 and A 1 each independently represent a hydrogen atom or an organic group.
• R 0 may be linked to A 1 or R 1 to form a ring.
• the halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the halogen atom represented by X is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom, in that the effects of the present invention are more excellent.
• the organic group represented by R 1 , R 0 and A 1 is not particularly limited, and examples thereof include the groups exemplified as the organic group W below.
• Examples of the organic group W include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, an aralkyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group (an alkylcarbonyl group or an arylcarbonyl group), an acyloxy group (an alkylcarbonyloxy group or an arylcarbonyloxy group), a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkylthio group, an arylthio group,
• each of the above groups may further have a substituent, if possible.
• an alkyl group which may have a substituent is also included as one form of the organic group W.
• the above-mentioned substituent is not particularly limited, and examples thereof include one or more of the groups shown as the above-mentioned organic group W, a halogen atom, a nitro group, a primary to tertiary amino group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a silyl group, a hydroxy group, a carboxy group, a sulfonic acid group, and a phosphoric acid group (hereinafter, these are referred to as "substituents T").
• the organic group W has, for example, 1 to 20 carbon atoms.
• the organic group W has, for example, 1 to 30 atoms other than
• the alkyl group exemplified as the organic group W preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
• the alkyl group may be either linear or branched. Examples of the alkyl group include linear or branched alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group.
• the substituent which the alkyl group may have is not particularly limited, and examples thereof include the groups exemplified as the substituent T described above.
• the compound has a group that interacts with an ionic compound (hereinafter, also referred to as an "interactive group") as a substituent, in that the interactivity with an ionic compound (e.g., a photodecomposable onium salt compound, etc., which may be contained in the actinic ray-sensitive or radiation-sensitive resin composition and which will be described later) is further improved, thereby making the effects of the present invention more excellent.
• an ionic compound e.g., a photodecomposable onium salt compound, etc., which may be contained in the actinic ray-sensitive or radiation-sensitive resin composition and which will be described later
• the group that interacts with the ionic compound is not particularly limited, but examples thereof include a hydroxyl group (such as an alcoholic hydroxyl group and a phenolic hydroxyl group), a carboxyl group, a sulfonic acid group, an amino group, an amide group, a sulfonamide group, and a thiol group.
• the phenolic hydroxyl group refers to a hydroxyl group substituted on a ring atom of an aromatic ring (aromatic hydrocarbon ring or aromatic heterocycle).
• the interactive group is preferably at least one selected from a hydroxyl group, an amino group, an amide group, and a thiol group.
• alkyl group portion in the alkoxy group (including the alkoxy group portion in a substituent containing an alkoxy group (e.g., an alkoxycarbonyloxy group)), the alkyl group portion in the aralkyl group, the alkyl group portion in the alkylcarbonyl group, the alkyl group portion in the alkylcarbonyloxy group, the alkyl group portion in the alkylthio group, the alkyl group portion in the alkylsulfinyl group, and the alkyl group portion in the alkylsulfonyl group, which are exemplified in the organic group W, the above-mentioned alkyl groups are preferable.
• the substituents which the alkoxy group, the aralkyl group, the alkylcarbonyloxy group which may have a substituent, the alkylthio group which may have a substituent, the alkylsulfinyl group which may have a substituent, and the alkylsulfonyl group which may have a substituent are the same as the substituents in the alkyl group which may have a substituent.
• Cycloalkyl groups exemplified in the organic group W include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.
• the number of carbon atoms in the cycloalkyl groups is preferably 5 to 20, and more preferably 5 to 15.
• the alkenyl group exemplified in the organic group W may be either linear or branched.
• the number of carbon atoms in the alkenyl group is preferably 2 to 20.
• examples of the substituent which the alkenyl group may have include the same as the substituent in the alkyl group which may have a substituent.
• the number of carbon atoms of the cycloalkenyl group exemplified in the organic group W is preferably 5 to 20.
• the alkynyl group exemplified in the organic group W may be either linear or branched.
• the number of carbon atoms in the alkynyl group is preferably 2 to 20.
• examples of the substituent which the alkynyl group may have include the same examples as the substituent in the alkyl group which may have a substituent.
• the number of carbon atoms of the cycloalkynyl group exemplified in the organic group W is preferably 5 to 20.
• the aryl group exemplified as the organic group W may be either a monocyclic or polycyclic (eg, 2 to 6 rings) group, unless otherwise specified.
• the aryl group preferably has 6 to 15 ring atoms, and more preferably has 6 to 10 ring atoms.
• the aryl group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group.
• examples of the substituent which the aryl group may have include the same substituents as those in the alkyl group which may have a substituent.
• the aryl group moiety in the substituent containing an aryl group includes the same examples as the aryl groups exemplified as the organic group W above.
• the heteroaryl group exemplified as the organic group W may be either a monocyclic or polycyclic (eg, 2 to 6 rings) group, unless otherwise specified.
• the number of heteroatoms contained as ring members in the heteroaryl group is, for example, 1 to 10.
• Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.
• the heteroaryl group preferably has 5 to 15 ring atoms.
• examples of the substituent which the heteroaryl group may have include the same substituents as those in the alkyl group which may have a substituent.
• the heterocycle exemplified in the organic group W is intended to mean a ring containing a heteroatom as a ring member atom, and unless otherwise specified, may be either an aromatic heterocycle or an aliphatic heterocycle, and may be either a monocycle or a polycycle (e.g., 2 to 6 rings, etc.).
• the number of heteroatoms contained in the heterocycle as ring member atoms is, for example, 1 to 10.
• Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.
• the heterocycle preferably has 5 to 15 ring atoms.
• examples of the substituent which the hetero ring may have include the same examples as the substituents in the alkyl group which may have a substituent.
• the lactone group exemplified as the organic group W is preferably a 5- to 7-membered lactone group, and more preferably a 5- to 7-membered lactone ring to which another ring structure is condensed in the form of a bicyclo structure or a spiro structure.
• examples of the substituent which the lactone group may have include the same substituents as those in the alkyl group which may have a substituent.
• R 0 and R 1 are preferably a hydrogen atom.
• a 1 is preferably an organic group having a halogen atom (preferably one or more selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom), and is preferably an organic group having an iodine atom.
• the organic group may further have a substituent other than a halogen atom.
• R 0 may be linked to A 1 or R 1 to form a ring.
• the ring formed by bonding R0 with A1 or R1 is not particularly limited and may be either a monocyclic ring or a polycyclic ring.
• the ring may contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, and/or a carbonyl carbon as a ring member atom.
• the ring is preferably a 5- or 6-membered alicyclic ring.
• repeating units represented by general formula (1) are given below, but are not limited to these.
• the content of the repeating unit represented by formula (1) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units.
• the upper limit is, for example, preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, and particularly preferably 60 mol% or less, based on the total repeating units.
• the specific resin may contain one type of repeating unit represented by general formula (1) alone or two or more types. When two or more types are contained, it is preferable that the total content is within the above-mentioned suitable content range.
• Y represents a hydrocarbon group.
• A2 represents an organic group.
• R0 represents a hydrogen atom or an organic group. R0 may be linked to A2 to form a ring.
• Examples of the hydrocarbon group represented by Y include a linear or branched alkyl group, a cycloalkyl group, and an aryl group.
• the linear or branched alkyl group represented by Y is preferably an alkyl group exemplified as the organic group W, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group or an ethyl group.
• the cycloalkyl group represented by Y is preferably a cycloalkyl group exemplified as the organic group W, and more preferably a cyclopentyl group or a cyclohexyl group.
• the aryl group represented by Y is preferably an aryl group exemplified as the organic group W, and more preferably a phenyl group or a naphthyl group.
• the organic group represented by R 0 is not particularly limited, and examples thereof include the organic group W described above.
• the organic group represented by A2 is not particularly limited, but preferably represents an optionally substituted hydrocarbon group in which, for example, -CH 2 - may be substituted with one or more groups selected from the group consisting of -O-, -CO-, and -NR T -.
• R T represents a hydrogen atom or an organic group.
• Examples of the hydrocarbon group which may have a substituent include an alkyl group which may have a substituent (which may be either linear or branched), a cycloalkyl group which may have a substituent, and an aryl group which may have a substituent (which may be either monocyclic or polycyclic).
• the alkyl group which may have a substituent is preferably an alkyl group exemplified as the organic group W, and more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent.
• Examples of the substituent which the alkyl group may have include the same examples as the substituents in the alkyl group which may have a substituent as described above as the organic group W.
• the above-mentioned cycloalkyl group which may have a substituent is preferably a cycloalkyl group exemplified as the organic group W, and more preferably a cycloalkyl group having 5 to 15 carbon atoms which may have a substituent.
• the aryl group which may have a substituent is preferably an aryl group exemplified as the organic group W, and more preferably a phenyl group which may have a substituent.
• Examples of the substituent which the aryl group may have include the same examples as the substituents in the alkyl group which may have a substituent as described above as the organic group W.
• the organic group represented by R 1 T is not particularly limited, and examples thereof include the organic group W described in the upper part.
• the optionally substituted hydrocarbon group represented by A2 above in which -CH 2 - may be substituted with one or more groups selected from the group consisting of -O-, -CO-, and -NR T - is not particularly limited, and examples thereof include optionally substituted hydrocarbon groups such as -OL 2 -R a , -NR b R c , and -CO-L 3 -R d .
• the above R a to R d each independently represent a hydrocarbon group which may have a substituent.
• R b and R c may be linked to each other to form a ring.
• the above L 2 represents a single bond or -CO-.
• the above L 3 represents -O- or -NR e -.
• R e represents a hydrogen atom or an organic group.
• the ring formed by Rb and Rc bonding to each other is not particularly limited and may be either a monocyclic ring or a polycyclic ring.
• the ring may contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, and/or a carbonyl carbon as a ring member.
• the ring is preferably a 5- or 6-membered alicyclic ring.
• the organic group represented by R e is not particularly limited, and examples thereof include the organic group W described in the upper part.
• A2 preferably has a halogen atom as a substituent. That is, A2 preferably represents an organic group having a halogen atom. Among them, the halogen atom is preferably an iodine atom in that the effect of the present invention is more excellent.
• the repeating unit represented by general formula (2) preferably contains at least one repeating unit selected from the group consisting of repeating units represented by general formulae (2)-1 to (2)-4, and more preferably contains a repeating unit represented by general formula (2)-1.
• the repeating units represented by formulae (2)-1 to (2-4) will be described below.
• Y in general formula (2)-1 to general formula (2)-4 has the same meaning as Y in general formula (2), and the preferred embodiments are also the same.
• Ar represents an aryl group which may have a substituent.
• the aryl group which may have a substituent is preferably an aryl group exemplified as the organic group W, and more preferably a phenyl group which may have a substituent.
• Examples of the substituent which the aryl group may have include the same examples as the substituents in the alkyl group which may have a substituent as described above as the organic group W.
• Ar preferably represents an aryl group having a substituent, and the substituent preferably includes a halogen atom. In other words, Ar preferably represents an aryl group having a substituent that includes a halogen atom.
• Ar preferably represents an aryl group having a substituent, and the substituent preferably includes an iodine atom.
• the aryl group has a halogen atom as a substituent
• the number of the halogen atoms is not particularly limited, but for example, 1 to 5 is preferable, and 1 to 3 is more preferable.
• R a , R b , R c , and R d each independently represent a hydrocarbon group which may have a substituent.
• Examples of the hydrocarbon groups represented by R a , R b , R c , and R d which may have a substituent include alkyl groups which may have a substituent (which may be either linear or branched), alkyl groups which may have a substituent, and aryl groups which may have a substituent (which may be either monocyclic or polycyclic).
• the alkyl group which may have a substituent is preferably an alkyl group exemplified as the organic group W, and more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent.
• Examples of the substituent which the alkyl group may have include the same examples as the substituents in the alkyl group which may have a substituent as described above as the organic group W.
• the cycloalkyl group which may have a substituent is preferably a cycloalkyl group exemplified as the organic group W, and more preferably an alkyl group having 5 to 15 carbon atoms which may have a substituent.
• Examples of the substituent which the cycloalkyl group may have include the same examples as the substituents in the alkyl group which may have a substituent as described above as the organic group W.
• the aryl group which may have a substituent is preferably an aryl group exemplified as the organic group W, and more preferably a phenyl group which may have a substituent.
• Examples of the substituent which the aryl group may have include the same examples as the substituents in the alkyl group which may have a substituent as described above as the organic group W.
• the above R a and R d preferably represent a hydrocarbon group having a substituent, and the substituent preferably contains a halogen atom.
• the above R a and R d preferably represent a hydrocarbon group having a substituent containing a halogen atom.
• the above R a and R d more preferably represent a hydrocarbon group having a substituent, and the substituent preferably contains an iodine atom.
• At least one of Rb and Rc preferably represents a hydrocarbon group having a substituent, and the substituent preferably includes a halogen atom.
• at least one of Rb and Rc preferably represents a hydrocarbon group having a substituent including a halogen atom.
• At least one of Rb and Rc more preferably represents a hydrocarbon group having a substituent, and the substituent preferably includes an iodine atom.
• Rb and Rc may be bonded to each other to form a ring.
• the ring formed by Rb and Rc bonding to each other is not particularly limited, and may be either a monocyclic ring or a polycyclic ring.
• the ring may contain heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms, and/or carbonyl carbon as ring members. Among these, the ring is preferably a 5- or 6-membered alicyclic ring.
• L3 represents -O- or -NR e -, where R e represents a hydrogen atom or an organic group.
• R e represents a hydrogen atom or an organic group.
• the organic group represented by R e is not particularly limited, and examples thereof include the organic group W described in the upper part.
• the repeating unit represented by general formula (2) is also preferably a repeating unit derived from a monomer selected from the group consisting of ⁇ -methylstyrenes, isopropenyl ethers, isopropenylamines, and methacrylic acid esters.
• repeating units represented by general formula (2) are given below, but are not limited to these.
• the content of the repeating unit represented by formula (2) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units.
• the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on the total repeating units.
• the specific resin may contain one type of repeating unit represented by general formula (2) alone or two or more types. When two or more types are contained, it is preferable that the total content is within the above-mentioned suitable content range.
• the specific resin is preferably a copolymer containing a repeating unit represented by the above general formula (1) and a repeating unit represented by the above general formula (2).
• the specific resin may be a random copolymer, a block copolymer, or an alternating copolymer, and is more preferably an alternating copolymer.
• the total content of the repeating units represented by the general formula (1) and the repeating units represented by the general formula (2) is preferably 90 mol% or more, and more preferably 95 mol% or more, based on the total repeating units.
• the upper limit is preferably 100 mol% or less.
• the specific resin may contain repeating units other than the repeating units described above, as long as the effects of the present invention are not impaired.
• the content of these repeating units is preferably 30 mol % or less, and more preferably 15 mol % or less, relative to the total repeating units.
• the specific resin also preferably has a group that interacts with an ionic compound (hereinafter also referred to as an "interactive group").
• the interactive group may be contained in the repeating unit represented by the above general formula (1), or may be contained in the repeating unit represented by the above general formula (2).
• the group that interacts with the ionic compound is not particularly limited, but examples thereof include a hydroxyl group (such as an alcoholic hydroxyl group and a phenolic hydroxyl group), a carboxyl group, a sulfonic acid group, an amino group, an amide group, a sulfonamide group, and a thiol group.
• the phenolic hydroxyl group refers to a hydroxyl group substituted on a ring atom of an aromatic ring (aromatic hydrocarbon ring or aromatic heterocycle).
• the interactive group is preferably at least one selected from a hydroxyl group, an amino group, an amide group, and a thiol group.
• the weight average molecular weight of the specific resin is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more.
• the weight average molecular weight of the specific resin is preferably 200,000 or less, more preferably 150,000 or less, even more preferably 100,000 or less, and particularly preferably 85,000 or less.
• the weight average molecular weight is determined by GPC method in terms of polystyrene.
• the dispersity (molecular weight distribution) of the specific resin is usually 1.0 to 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.9, and even more preferably 1.0 to 1.8. When the dispersity is within the above range, the resolution and resist shape are likely to be excellent.
• the specific resin can be synthesized according to conventional methods (e.g., radical polymerization).
• the content of the specific resin is preferably 50.0 mass% or more, more preferably 60.0 mass% or more, and even more preferably 70.0 mass% or more, based on the total solid content of the composition.
• the upper limit is 99.9 mass% or less, and preferably 99.5 mass% or less.
• the specific resin may be used alone or in combination. When two or more types are used, the total content is preferably within the above-mentioned suitable content range.
• the actinic ray-sensitive or radiation-sensitive resin composition contains an ionic compound.
• the ionic compound is more preferably a compound having an onium salt structure that generates an acid when irradiated with actinic rays or radiation (photodecomposition type onium salt compound).
• the actinic ray-sensitive or radiation-sensitive resin composition contains an ionic compound such as a photodegradable onium salt compound, the resin whose main chain is decomposed by irradiation with the actinic ray or radiation is likely to aggregate with the ionic compound through an interactive group that may be contained in the resin in the unexposed portion.
• the ionic compound dissociates from the interactive group or the photodegradable onium salt compound is cleaved, which may release the aggregated structure.
• the dissolution contrast between the unexposed and exposed portions of the actinic ray-sensitive or radiation-sensitive resin film is further increased by the above action, and the effect of the present invention is more likely to be excellent.
• the photodecomposable onium salt compound is preferably a compound which has at least one salt structure moiety composed of an anion moiety and a cation moiety and which decomposes upon exposure to generate an acid (preferably an organic acid).
• the above-mentioned salt structure portion of the photodecomposable onium salt compound is preferably composed of an organic cation portion and an organic anion portion having extremely low nucleophilicity, since this portion is easily decomposed by exposure to light and has excellent organic acid generation properties.
• the salt structure moiety may be a part or the whole of the photodecomposable onium salt compound.
• the case where the salt structure moiety is a part of the photodecomposable onium salt compound corresponds to, for example, a structure in which two or more salt structure moieties are linked together, such as the photodecomposable onium salt PG2 described later.
• the number of salt structure moieties in the photodecomposable onium salt is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
• organic acid generated from the photodecomposable onium salt compound by the action of exposure to light examples include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.
• the organic acid generated from the photodecomposable onium salt compound by the action of exposure may be a polyvalent acid having two or more acid groups.
• the organic acid generated by decomposition of the photodecomposable onium salt compound by exposure is a polyvalent acid having two or more acid groups.
• the cationic moiety constituting the salt structure moiety is preferably an organic cationic moiety, and among these, an organic cation represented by formula (ZaI) (cation (ZaI)) or an organic cation represented by formula (ZaII) (cation (ZaII)) as described below is preferred.
• Photodecomposable onium salt compound PG1 An example of a suitable embodiment of the photodecomposable onium salt compound is an onium salt compound represented by "M + X - ", which generates an organic acid upon exposure to light (hereinafter also referred to as "photodecomposable onium salt compound PG1").
• M + represents an organic cation
• X - represents an organic anion.
• the photodecomposable onium salt compound PG1 will be described below.
• the organic cation represented by M + in the photodecomposable onium salt compound PG1 is preferably an organic cation represented by formula (ZaI) (cation (ZaI)), an organic cation represented by formula (ZaII) (cation (ZaII)), or an ammonium cation.
• R 201 , R 202 and R 203 each independently represent an organic group.
• the number of carbon atoms in the organic group represented by R 201 , R 202 , and R 203 is usually 1 to 30, and preferably 1 to 20.
• Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
• Examples of the group formed by bonding two of R 201 to R 203 include an alkylene group (e.g., a butylene group and a pentylene group) and -CH 2 -CH 2 -O-CH 2 -CH 2 -.
• Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), an organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and an organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.
• the cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in the above formula (ZaI) is an aryl group.
• the arylsulfonium cation all of R 201 to R 203 may be aryl groups, or some of R 201 to R 203 may be aryl groups, with the remainder being alkyl groups or cycloalkyl groups.
• one of R 201 to R 203 may be an aryl group, and the remaining two of R 201 to R 203 may be bonded to form a ring structure, which may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group in the ring.
• Examples of the group formed by bonding two of R 201 to R 203 include alkylene groups in which one or more methylene groups may be substituted with oxygen atoms, sulfur atoms, ester groups, amide groups, and/or carbonyl groups (e.g., butylene group, pentylene group, or -CH 2 -CH 2 -O-CH 2 -CH 2 -).
• arylsulfonium cation examples include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
• the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may be an aryl group having a heterocyclic structure with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
• the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group which the arylsulfonium cation optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.
• Preferred substituents that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 may have are each independently an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (e.g., 6 to 14 carbon atoms), an alkoxy group (e.g., 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., 1 to 15 carbon atoms), a halogen atom (e.g., fluorine, iodine), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, a phenylthio group, and the like.
• an alkyl group e.g., 1 to 15 carbon atoms
• the above-mentioned substituent may further have a substituent if possible.
• the above-mentioned alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.
• Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represent an organic group not having an aromatic ring.
• the aromatic ring also includes an aromatic ring containing a heteroatom.
• the organic group not having an aromatic ring represented by R 201 to R 203 generally has 1 to 30 carbon atoms, and preferably has 1 to 20 carbon atoms.
• Each of R 201 to R 203 independently represents preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.
• Examples of the alkyl group and cycloalkyl group for R 201 to R 203 include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups).
• R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
• the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
• R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, or a hydroxyl group. , a nitro group, an alkylthio group, or an arylthio group.
• R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
• R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
• R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
• the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings.
• the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.
• the group formed by combining any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y includes alkylene groups such as butylene and pentylene, in which the methylene group may be substituted with a heteroatom such as an oxygen atom.
• the groups formed by combining R5c and R6c , and R5c and Rx are preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
• R 1c to R 5c , R 6c , R 7c , R x , R y , and any two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may each have a substituent.
• the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
• l represents an integer of 0 to 2.
• r represents an integer of 0 to 8.
• R 13 is a hydrogen atom, a halogen atom (for example, a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group having a cycloalkyl group (cycloalkyl A cycloalkyl group may be a group itself or a group containing a cycloalkyl group as a part of the group. These groups may have a substituent.
• R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), an alkyl group, A group having a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself, or may have a cycloalkyl group as a part thereof) These groups may have a substituent.
• a halogen atom e.g., a fluorine atom, an iodine atom, etc.
• an alkyl group A group having a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfon
• each independently represents the above group such as a hydroxyl group.
• Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R 15 may be bonded to each other to form a ring. When the ring structure is formed, the ring structure may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, it is preferable that two R 15 are alkylene groups and are bonded to each other to form a ring structure.
• the alkyl group, the cycloalkyl group, the naphthyl group, and the ring formed by bonding two R 15 together may have a substituent.
• the alkyl groups of R 13 , R 14 , and R 15 are preferably linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1 to 10.
• the alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like.
• R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
• the aryl group of R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group of R 204 and R 205 may be an aryl group having a heterocycle with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
• the alkyl group and cycloalkyl group of R 204 and R 205 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, or a norbornyl group).
• a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms e.g., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group
• a cycloalkyl group having 3 to 10 carbon atoms e.g
• the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
• substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (e.g., 6 to 15 carbon atoms), an alkoxy group (e.g., 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
• the ammonium cation is not particularly limited, but examples thereof include ammonium cations represented by N + (R 301 ) 4 .
• Each R 301 independently represents an alkyl group (for example, having a carbon number of 1 to 15).
• the alkyl group may have a substituent.
• the organic anion represented by X 2 - in the photodecomposable onium salt compound PG1 is preferably a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
• non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
• the organic anion is preferably, for example, an organic anion represented by the following formula (DA):
• a 31 - represents an anionic group
• R a1 represents a hydrogen atom or a monovalent organic group
• L a1 represents a single bond or a divalent linking group.
• a 31 - represents an anionic group.
• the anionic group represented by A 31 - is not particularly limited, but is preferably, for example, a group selected from the group consisting of groups represented by formulas (B-1) to (B-14), and among these, formula (B-1), formula (B-2), formula (B-3), formula (B-4), formula (B-5), formula (B-6), formula (B-10), formula (B-12), formula (B-13), or formula (B-14) is more preferable.
• R 1 X1 each independently represents a monovalent organic group.
• R X2 each independently represents a hydrogen atom or a substituent other than a fluorine atom or a perfluoroalkyl group. Two R X2 in formula (B-7) may be the same or different.
• R XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group.
• R XF1 At least one represents a fluorine atom or a perfluoroalkyl group.
• the two R XF1 in formula (B-8) may be the same or different.
• R X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
• n1 represents an integer of 0 to 4.
• R XF2 represents a fluorine atom or a perfluoroalkyl group.
• the bond to the bonding position represented by * in formula (B-14) is preferably a phenylene group which may have a substituent. Examples of the substituent which the phenylene group may have include a halogen atom.
• R 1 X1 each independently represents a monovalent organic group.
• R X1 is preferably an alkyl group (which may be linear or branched, and preferably has 1 to 15 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms), or an aryl group (which may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms).
• the above group represented by R X1 may have a substituent.
• the atom in R X1 in formula (B-5) that is directly bonded to N- is neither a carbon atom in --CO-- nor a sulfur atom in --SO 2 --.
• the cycloalkyl group in R X1 may be a monocyclic or polycyclic group.
• Examples of the cycloalkyl group in R X1 include a norbornyl group and an adamantyl group.
• the substituent that the cycloalkyl group in R X1 may have is not particularly limited, but is preferably an alkyl group (which may be linear or branched, and preferably has 1 to 5 carbon atoms). One or more of the carbon atoms that are ring members of the cycloalkyl group in R X1 may be replaced with a carbonyl carbon atom.
• the alkyl group in R 3 X1 preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms.
• the substituent that the alkyl group in R X1 may have is not particularly limited, but is preferably, for example, a cycloalkyl group, a fluorine atom, or a cyano group. Examples of the cycloalkyl group as the above-mentioned substituent include the cycloalkyl groups explained in the case where R X1 is a cycloalkyl group.
• the above-mentioned alkyl group in R X1 may be a perfluoroalkyl group.
• the alkyl group in R X1 may have one or more -CH 2 - substituted with a carbonyl group.
• the aryl group in R X1 is preferably a benzene ring group.
• the substituent that the aryl group in R may have is not particularly limited, but is preferably an alkyl group, a fluorine atom, or a cyano group. Examples of the alkyl group as the substituent include the alkyl groups described in the case where R is an alkyl group.
• R X2 each independently represents a hydrogen atom or a substituent other than a fluorine atom or a perfluoroalkyl group (for example, an alkyl group not containing a fluorine atom and a cycloalkyl group not containing a fluorine atom).
• Two R X2 in formula (B-7) may be the same or different.
• R XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, among the multiple R XF1 , at least one represents a fluorine atom or a perfluoroalkyl group.
• the two R XF1 in formula (B-8) may be the same or different.
• the number of carbon atoms of the perfluoroalkyl group represented by R XF1 is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.
• R X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
• the halogen atom represented by R X3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom is preferable.
• the monovalent organic group represented by R 1 X3 is the same as the monovalent organic group described as R 1 X1 .
• n1 represents an integer of 0 to 4.
• n1 is preferably an integer of 0 to 2, and more preferably 0 or 1. When n1 represents an integer of 2 to 4, multiple R 3 X3 may be the same or different.
• R XF2 represents a fluorine atom or a perfluoroalkyl group.
• the perfluoroalkyl group represented by R 2 XF2 preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
• the monovalent organic group for R a1 is not particularly limited, but generally has 1 to 30 carbon atoms, and preferably has 1 to 20 carbon atoms.
• R a1 is preferably an alkyl group, a cycloalkyl group, or an aryl group.
• the alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.
• the cycloalkyl group may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms.
• the aryl group may be monocyclic or polycyclic, and is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms.
• the cycloalkyl group may contain heteroatoms as ring members.
• the heteroatom is not particularly limited, but examples thereof include a nitrogen atom and an oxygen atom.
• the alkyl group, cycloalkyl group and aryl group may further have a substituent.
• a 31- and R a1 may be bonded to each other to form a ring.
• the divalent linking group represented by L a1 is not particularly limited, but represents an alkylene group, a cycloalkylene group, an aromatic group, -O-, -CO-, -COO-, or a group formed by combining two or more of these.
• the alkylene group may be linear or branched and preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.
• the cycloalkylene group may be monocyclic or polycyclic and preferably has 3 to 20 carbon atoms, and more preferably has 3 to 10 carbon atoms.
• the aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 15 carbon atoms.
• the aromatic ring constituting the aromatic group is not particularly limited, and examples thereof include aromatic rings having 6 to 20 carbon atoms, specifically, benzene ring, naphthalene ring, anthracene ring, thiophene ring, etc.
• aromatic rings constituting the aromatic group a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable.
• the alkylene group, cycloalkylene group and aromatic group may further have a substituent, and the substituent is preferably a halogen atom.
• L a1 preferably represents a single bond.
• the photodecomposable onium salt compound PG1 it is also preferable to use, for example, the photoacid generators disclosed in paragraphs [0135] to [0171] of WO 2018/193954, paragraphs [0077] to [0116] of WO 2020/066824, and paragraphs [0018] to [0075] and [0334] to [0335] of WO 2017/154345.
• the molecular weight of the photodegradable onium salt compound PG1 is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
• Photodecomposable onium salt compound PG2 Another example of a suitable embodiment of the photodecomposable onium salt compound includes the following compound (I) and compound (II) (hereinafter, "compound (I) and compound (II)” are also referred to as “photodecomposable onium salt compound PG2").
• the photodecomposable onium salt compound PG2 has two or more of the above-mentioned salt structural moieties and is a compound that generates a polyvalent organic acid upon exposure to light.
• the photodecomposable onium salt compound PG2 will now be described.
• Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which is irradiated with actinic rays or radiation to form the following first acidic group derived from the structural moiety X: and a second acidic moiety derived from the structural moiety Y shown below.
• Structural moiety X a structural moiety consisting of an anionic moiety A 1 ⁇ and a cationic moiety M 1 + , which forms a first acidic moiety represented by HA 1 upon irradiation with actinic rays or radiation.
• Structural moiety Y anionic moiety A A structural moiety consisting of M 2 ⁇ and a cationic moiety M 2 + , which forms a second acidic moiety represented by HA 2 upon irradiation with actinic rays or radiation.
• compound (I) satisfies the following condition I.
• Compound PI which is obtained by replacing the cationic moiety M 1 + in the structural moiety X and the cationic moiety M 2 + in the structural moiety Y in compound (I) with H + , has an acid dissociation constant a1 derived from the acidic moiety represented by HA 1 , which is obtained by replacing the cationic moiety M 1 + in the structural moiety X with H + , and an acid dissociation constant a2 derived from the acidic moiety represented by HA 2 , which is obtained by replacing the cationic moiety M 2 + in the structural moiety Y with H + , and the acid dissociation constant a2 is greater than the acid dissociation constant a1.
• the compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
• the structural moieties X may be the same or different from each other.
• the two or more A 1 ⁇ and the two or more M 1 + may be the same or different from each other.
• the A 1 - and A 2 - , and the M 1 + and M 2 + may be the same or different, but it is preferable that the A 1 - and A 2 - are different.
• the anionic moiety A 1 - and the anionic moiety A 2 - are structural moieties containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of the following formulae (AA-1) to (AA-3) and (BB-1) to (BB-6). In the following formulae (AA-1) to (AA-3) and (BB-1) to (BB-6), * represents a bonding position.
• R A represents a monovalent organic group. Examples of the monovalent organic group represented by R A include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.
• the cationic moiety M 1 + and the cationic moiety M 2 + are structural moieties containing a positively charged atom or atomic group, and examples thereof include organic cations having a monovalent charge.
• the organic cation is not particularly limited, but is preferably an organic cation represented by the above formula (ZaI) (cation (ZaI)) or an organic cation represented by the above formula (ZaII) (cation (ZaII)).
• Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, and is a compound that generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z when irradiated with actinic rays or radiation.
• Structural moiety Z a non-ionic moiety capable of neutralizing an acid
• the compound (II) can generate a compound PII (acid) having an acidic site represented by HA 1 in which the cationic site M 1 + in the structural site X is replaced with H + .
• the compound PII represents a compound having the acidic site represented by HA 1 and a structural site Z which is a nonionic site capable of neutralizing an acid.
• the definition of the structural moiety X, and the definitions of A 1 - and M 1 + in compound (II) are the same as the definition of the structural moiety X, and the definitions of A 1 - and M 1 + in compound (I) described above, and the preferred embodiments are also the same.
• the two or more structural moieties X may be the same or different from each other, and the two or more A 1 ⁇ and the two or more M 1 + may be the same or different from each other.
• the nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a functional group having an electron or a group capable of electrostatically interacting with a proton.
• functional groups having a group or electrons capable of electrostatically interacting with a proton include functional groups having a macrocyclic structure such as cyclic polyether, or functional groups having a nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation.
• the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:
• Examples of partial structures of functional groups having groups or electrons that can electrostatically interact with protons include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, with primary to tertiary amine structures being preferred.
• the molecular weight of the photodegradable onium salt compound PG2 is preferably 100 to 10,000, more preferably 100 to 2,500, and even more preferably 100 to 1,500.
• the pKa of the conjugate acid of the anion moiety of the ionic compound is not particularly limited, but is preferably 2.00 or more, more preferably 3.00 or more, and even more preferably 4.00 or more.
• the pKa of the conjugate acid of the anion moiety of the ionic compound is not particularly limited, but is preferably 10.00 or less, more preferably 9.00 or less, and even more preferably 8.00 or less.
• the pKa of the conjugate acid of the anion part of the ionic compound is within the above-mentioned range, since this can enhance the interaction with the interactive group that may be contained in the resin, the main chain of which is decomposed by actinic rays or radiation, contained in the composition of the present invention, and can reduce the solubility in unexposed areas.
• the ionic compound has two or more anion moieties, it is sufficient that the conjugate acid pKa value of one of the anion moieties falls within the above range.
• the pKa can be determined by the method described above.
• the ionic compound has two or more anion moieties, it is preferable that the pKa value of the conjugate acid of one of the anion moieties is within the above range.
• ionic compounds are shown below, but the present invention is not limited to these.
• the pKa values of the conjugate acids of the anions of the ionic compounds are also shown.
• the content of the ionic compound is not particularly limited, but is preferably 0.1 to 20 mass% based on the total solid content of the composition.
• the lower limit of the content is more preferably 0.5 mass% or more, even more preferably 0.7 mass% or more, and particularly preferably 1.0 mass% or more.
• the upper limit of the content is more preferably 10.0 mass% or less, and even more preferably 5.0 mass% or less.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a solvent.
• the solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate.
• the solvent may further contain components other than the components (M1) and (M2).
• component (M1) at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferred, with propylene glycol monomethyl ether acetate (PGMEA) being more preferred.
• PGMEA propylene glycol monomethyl ether acetate
• the propylene glycol monoalkyl ether propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE) are preferred.
• the lactate ester is preferably ethyl lactate, butyl lactate, or propyl lactate.
• the acetate ester is preferably methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate. Also preferred is butyl butyrate.
• alkoxypropionate methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferred.
• chain ketone 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone is preferred.
• the cyclic ketone is preferably methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone.
• the lactone is preferably ⁇ -butyrolactone.
• the alkylene carbonate propylene carbonate is preferred.
• component (M2) is propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, gamma-butyrolactone, or propylene carbonate.
• PGME propylene glycol monomethyl ether
• ethyl lactate ethyl 3-ethoxypropionate
• methyl amyl ketone cyclohexanone
• butyl acetate pentyl acetate
• gamma-butyrolactone gamma-butyrolactone
• the solvent preferably includes an ester-based solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and 2 or less heteroatoms.
• an ester-based solvent having 7 or more carbon atoms and 2 or less heteroatoms amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, or butyl butanoate is preferred, and isoamyl acetate is more preferred.
• the component (M2) those having a flash point (hereinafter also referred to as fp) of 37° C. or more are preferable.
• fp flash point
• a component (M2) propylene glycol monomethyl ether (fp: 47° C.), ethyl lactate (fp: 53° C.), ethyl 3-ethoxypropionate (fp: 49° C.), methyl amyl ketone (fp: 42° C.), cyclohexanone (fp: 44° C.), pentyl acetate (fp: 45° C.), methyl 2-hydroxyisobutyrate (fp: 45° C.), ⁇ -butyrolactone (fp: 101° C.), or propylene carbonate (fp: 132° C.) are preferable.
• propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone are more preferable, and propylene glycol monoethyl ether or ethyl lactate are even more preferable.
• flash point used herein means the value listed in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Co.
• the solvent preferably contains the component (M1). More preferably, the solvent consists essentially of the component (M1) alone, or is a mixed solvent of the component (M1) and other components. In the latter case, the solvent further preferably contains both the component (M1) and the component (M2).
• the mass ratio (M1/M2) of the component (M1) to the component (M2) is preferably in the range of "100/0" to "15/85", more preferably in the range of "100/0" to "40/60", and even more preferably in the range of "100/0" to "60/40".
• the solvent is preferably composed of only the component (M1) or contains both the component (M1) and the component (M2), and the mass ratio thereof is as follows.
• the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and even more preferably 60/40 or more.
• the mass ratio of component (M1) to component (M2) is, for example, 99/1 or less.
• the solvent further contains components other than components (M1) and (M2)
• the content of the components other than components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.
• the content of the solvent in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30 mass %, and more preferably 1 to 20 mass %, in order to provide better coatability.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a surfactant.
• a surfactant When the composition contains a surfactant, a pattern having excellent adhesion and fewer development defects can be formed.
• the surfactant is preferably a fluorine-based and/or silicon-based surfactant. Examples of fluorine-based and/or silicone-based surfactants include the surfactants disclosed in paragraphs [0218] and [0219] of WO 2018/193954.
• surfactants may be used alone or in combination of two or more.
• the content of the surfactant is preferably 0.0001 to 2 mass %, and more preferably 0.0005 to 1 mass %, based on the total solid content of the composition.
• the present invention also relates to an actinic ray-sensitive or radiation-sensitive film (preferably a resist film) formed using the actinic ray-sensitive or radiation-sensitive resin composition.
• the present invention also relates to a pattern forming method, comprising the steps of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition, exposing the actinic ray-sensitive or radiation-sensitive film, and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.
• the procedure for the pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, but it is preferable that the method comprises the following steps.
• Step 1 A step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition.
• Step 2 A step of exposing the actinic ray-sensitive or radiation-sensitive film.
• Step 3 A step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
• Step 1 is a step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition.
• Examples of a method for forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition include a method of coating the actinic ray-sensitive or radiation-sensitive resin composition on a substrate.
• 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 actinic ray-sensitive or radiation-sensitive resin composition can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide) such as those used in the manufacture of integrated circuit elements by a suitable application method such as a spinner or coater.
• the application method is preferably spin coating using a spinner.
• the rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm.
• the substrate may be dried to form an actinic ray-sensitive or radiation-sensitive film. If necessary, various undercoats (inorganic films, organic films, anti-reflection films) may be formed under the actinic ray-sensitive or radiation-sensitive film.
• the drying method may be, for example, a method of drying by heating. Heating can be performed by a means provided in a normal exposure machine and/or a developing machine, and may also be performed using a hot plate or the like.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.
• the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.
• the thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 10 to 120 nm, since it allows for the formation of fine patterns with higher precision.
• the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
• the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.
• a top coat may be formed on the actinic ray-sensitive or radiation-sensitive film by using a top coat composition. It is preferable that the top coat composition does not mix with the actinic ray-sensitive or radiation-sensitive film, and can be uniformly applied on the actinic ray-sensitive or radiation-sensitive film.
• the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method, for example, a top coat can be formed based on the description in paragraphs [0072] to [0082] of JP2014-059543A. For example, it is preferable to form a top coat containing a basic compound such as that described in JP 2013-061648 A on the actinic ray-sensitive or radiation-sensitive film.
• the basic compound that the top coat may contain include basic compounds that may be contained in the actinic ray-sensitive or radiation-sensitive resin composition.
• the top coat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
• Step 2 is a step of exposing the actinic ray- or radiation-sensitive film to light.
• the exposure method may be a method in which the formed actinic ray-sensitive or radiation-sensitive film is irradiated with actinic rays or radiation through a predetermined mask.
• actinic rays or radiation examples include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, and preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 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.
• the heating temperature is preferably from 80 to 150°C, more preferably from 80 to 140°C, and even more preferably from 80 to 130°C.
• the heating time is preferably from 10 to 1,000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposure machine and/or developing machine, and may be carried out using a hot plate or the like.
• Step 3 is a step of developing the exposed actinic ray- or radiation-sensitive film with a developer to form a pattern.
• the developer is preferably a developer containing an organic solvent (hereinafter, also referred to as an organic developer).
• Examples of the developing method include a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of piling up the developing solution on the substrate surface by surface tension and leaving it still for a certain period of time to develop (paddle method), a method of spraying the developing solution on the substrate surface (spray method), and a method of continuously discharging the developing solution while scanning a developing solution discharge nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method).
• a step of stopping the development while replacing the solvent with another solvent may be carried out.
• the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds.
• the temperature of the developer is preferably from 0 to 50°C, and more preferably from 15 to 35°C.
• the organic developer preferably contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
• the above-mentioned solvents may be mixed in combination, or may be mixed with a solvent other than the above or with water.
• the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
• the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.
• the above pattern forming method preferably includes, after step 3, a step of washing with a rinsing liquid.
• the rinse liquid used in the rinse step following the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. It is preferable to use a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.
• the method of the rinsing step is not particularly limited, and examples thereof include a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (spin coating method), a method of immersing a substrate in a tank filled with the rinsing liquid for a certain period of time (dip method), and a method of spraying the rinsing liquid onto the substrate surface (spray method).
• the pattern forming method of the present invention may also include a heating step (Post Bake) after the rinsing step. This step removes the developer and rinsing solution remaining between the patterns and inside the pattern due to baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern.
• the heating step after the rinsing step is usually performed at 40 to 250°C (preferably 90 to 200°C) for usually 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
• the formed pattern may be used as a mask to perform an etching process on the substrate. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlayer film and the substrate) to form a pattern on the substrate.
• the method for processing the substrate is not particularly limited, a method is preferred in which the substrate (or the underlayer film and the substrate) is dry-etched using the pattern formed in step 3 as a mask to form a pattern on the substrate.
• the dry etching is preferably oxygen plasma etching.
• the actinic ray- or radiation-sensitive resin composition and the various materials used in the pattern formation method of the present invention preferably do not contain impurities such as metals.
• the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
• examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.
• methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as the raw materials that make up the various materials, filtering the raw materials that make up the various materials, and performing distillation under conditions that minimize contamination as much as possible, such as lining the inside of the equipment 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.
• 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.
• the actinic ray-sensitive or radiation-sensitive resin composition may contain water as an impurity. When water is contained as an impurity, the smaller the content of water, the more preferable, but the water may be contained in an amount of 1 to 30,000 ppm by mass based on the entire actinic ray-sensitive or radiation-sensitive resin composition.
• the actinic ray-sensitive or radiation-sensitive resin composition may also contain residual monomers as impurities (for example, monomers derived from raw material monomers used in the synthesis of the specific resin). When the residual monomers are contained as impurities, the smaller the content of the residual monomers, the more preferable, but the residual monomers may be contained in an amount of 1 to 30,000 ppm by mass based on the total solid content of the composition.
• An organic processing liquid such as a rinse liquid may contain a conductive compound to prevent breakdown of chemical liquid piping and various parts (filters, O-rings, tubes, etc.) due to static electricity buildup and subsequent static electricity discharge.
• the conductive compound is not particularly limited, but an example thereof is methanol.
• the amount added is not particularly limited, but from the viewpoint of maintaining favorable development characteristics or rinsing characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less.
• the chemical liquid piping may be made of, for example, stainless steel (SUS), or various piping coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
• the filter and O-ring may be made of antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
• the present invention also relates to a method for producing an electronic device, which includes the above-mentioned pattern formation method, and an electronic device produced by this production method.
• the electronic device of the present invention is suitably mounted in electric and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment).
• the weight average molecular weight (Mw) and dispersity (Mw/Mn) of Resins E-1 to E-36 were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent amount).
• the composition ratio (mol % ratio) of the resins was measured by 13 C-NMR (Nuclear Magnetic Resonance).
• composition ratio (molar ratio) of the repeating units of the above resin E-2 determined by NMR (nuclear magnetic resonance) was 50/50 (repeating units derived from the deacetylated (OH) monomer M-1/repeating units derived from ⁇ -chloromethyl acrylate).
• the weight average molecular weight of the obtained resin E-2 measured by GPC was 34,000 in terms of polystyrene, and the polydispersity (Mw/Mn) was 1.91.
• the actinic ray-sensitive or radiation-sensitive resin composition was applied onto a silicon wafer having a diameter of 12 inches, and then baked at 120° C. for 60 seconds to form a coating film.
• the thickness of the actinic ray-sensitive or radiation-sensitive film (film A) was adjusted to 40 nm.
• the dissolution rate of Membrane A in butyl acetate is determined as follows. The above film A was developed with a developer (butyl acetate) for 300 seconds, and the film thickness after development was measured. The dissolution rate (nm/sec) of film A was calculated by subtracting the film thickness after development from the film thickness (40 nm) of film A before treatment and dividing the result by the development time (300 seconds). The film thickness was measured at five points on a 12-inch wafer using an optical film thickness meter ("VM3200", manufactured by SCREEN Corporation), and the average value was used.
• the dissolution rate of Film A (unexposed film) is shown in Table 3.
• Film A is subjected to open frame exposure using an EUV exposure device (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36) so that the dissolution rate in butyl acetate is 0.1 nm/sec, to obtain film B.
• the dissolution rate of Membrane B in butyl acetate is determined as follows. The dissolution rate of Membrane B in butyl acetate was determined by dividing the change in thickness of Membrane B by the time required for the treatment.
• the film thickness after development was measured, and the film thickness after development was subtracted from the film thickness of the film B before treatment (40 nm) and divided by the development time (30 seconds) to calculate the dissolution rate (nm/sec) of the film B.
• the film thickness was measured at five points on the surface of a 12-inch wafer using an optical film thickness meter ("VM3200", manufactured by SCREEN Co., Ltd.) and the average value was used.
• Film A was exposed to open frame light using an EUV exposure device (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36) at an exposure dose such that the dissolution rate of Film B was 0.1 nm/sec, to obtain Film B.
• EUV exposure device Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36
• Table 3 shows the cation residual rates in the examples and comparative examples.
• the composition shown in Table 3 was applied onto a silicon wafer having a diameter of 12 inches, and then baked at 120° C. for 60 seconds to form a coating film.
• the thickness of the actinic ray-sensitive or radiation-sensitive film was adjusted to 40 nm.
• the silicon wafer having the actinic ray-sensitive or radiation-sensitive film obtained by the above-mentioned procedure was subjected to pattern irradiation using an EUV exposure device (Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech).
• EUV exposure device Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech.
• a reticle a mask with a line:space ratio of 1:1 was used.
• the cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.)
• the optimum exposure dose when resolving a 1:1 line and space resist pattern with a line width of 20 nm was defined as the sensitivity (Eopt) (mJ/cm 2 ).
• ⁇ LWR> A 20 nm (1:1) line and space pattern resolved at an exposure dose showing the above sensitivity (Eopt) was observed from above using a critical dimension scanning electron microscope (SEM (S-9380II manufactured by Hitachi, Ltd.)). The line width of the pattern was observed at 100 random points, the standard deviation ( ⁇ ) was calculated, and the measurement variation of the line width was evaluated as 3 ⁇ (nm). A smaller value indicates better performance.
• Examples 1 to 34 when a pattern is formed using an actinic ray-sensitive or radiation-sensitive resin composition having a cation decomposition rate of 50 mol % or less, it is found that the resolution and LWR performance are extremely excellent in the formation of an ultrafine pattern.
• Comparative Examples 1 to 4 in which an actinic ray-sensitive or radiation-sensitive resin composition having a cation decomposition rate of more than 50 mol% is used, when a pattern is formed using the actinic ray-sensitive or radiation-sensitive resin composition, it is found that the resolution and LWR performance are inferior in the formation of an ultrafine pattern.
• the present invention provides an actinic ray- or radiation-sensitive resin composition that exhibits excellent resolution and LWR performance in the formation of ultrafine patterns (e.g., line and space patterns with line widths of 15 nm or less, and hole patterns with hole diameters of 15 nm or less).
• ultrafine patterns e.g., line and space patterns with line widths of 15 nm or less, and hole patterns with hole diameters of 15 nm or less.

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• 2023
  • 2023-12-26 WO PCT/JP2023/046817 patent/WO2024150677A1/ja not_active Ceased
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