Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/22—Tin compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/22—Tin compounds
  • C07F7/2224—Compounds having one or more tin-oxygen linkages
• • 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention relates to a resist composition and a method for producing the same.
• Non-Patent Document 1 discloses a resist composition containing a compound containing a tin-oxocage and OH ⁇ , an acetate anion, a malonate anion, or a tosylate anion.
• Non-Patent Document 1 the resist composition described in Non-Patent Document 1 had insufficient sensitivity, and sufficient exposure was required to form a resist film (resist pattern).
• a resist composition containing an organotin compound and a specific organoboron compound provides high sensitivity and enables pattern formation with a low exposure dose, thus arriving at the present invention.
• the present invention comprises the following: [1] A resist composition comprising an organotin compound and an organoboron compound represented by the following formula: (In the formula, R 1 , R 2 and R 3 each independently represent an organic group bonded to boron through a carbon atom, an oxygen-containing organic group bonded to boron through an oxygen atom, or OH. The oxygen-containing organic group may contain a boron atom. Two groups selected from R 1 , R 2 and R 3 may be linked to form a ring structure.) [2] The resist composition according to [1] above, wherein the organotin compound has a Sn—O bond and a Sn—C bond.
• a method for forming a resist pattern comprising: a step (i) of applying the resist composition according to any one of the above items [1] to [6]; a step (ii) of drying the coated film of the resist composition; a step (iii) of exposing the coated film of the resist composition to light; and a step (iv) of developing the film of the resist composition.
• a method for producing a resist composition comprising the step of mixing an organotin compound and an organoboron compound represented by the following formula in an organic solvent:
• R 1 , R 2 and R 3 each independently represent an organic group bonded to boron through a carbon atom, an oxygen-containing organic group bonded to boron through an oxygen atom, or OH.
• the oxygen-containing organic group may contain a boron atom.
• Two groups selected from R 1 , R 2 and R 3 may be linked to form a ring structure.
• the use of the resist composition disclosed herein provides high sensitivity and enables pattern formation with low exposure doses.
• the resist composition of the present disclosure contains an organotin compound and a specified organoboron compound described below.
• the organotin compound may be either mononuclear tin or a tin cluster (polynuclear tin), but is preferably a tin cluster. Also, the organotin compound preferably has a Sn—O bond and a Sn—C bond.
• R 4 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, an alkenylalkyl group having 3 to 20 carbon atoms which may have a substituent, an alkynylalkyl group having 3 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a combination thereof, and when x is 2, each of them is independent.
• R5 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a combination thereof, and when y is 2 or 3, they are independent of each other.
• R 6 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a combination thereof, and when z is 2 or 3, they are independent of each other.
• the tin cluster is a tin compound in which a plurality of tin atoms are directly linked or indirectly linked by a ligand, and may be a cage-type compound.
• the tin cluster of the present disclosure may optionally include one or more ligands selected from aqua ligands, hydroxo ligands, oxo ligands, peroxo ligands, thiolato ligands, sulfide ligands, fluoro ligands, chloro ligands, iodo ligands, hydride ligands, cyanato ligands, azide ligands, carboxylato ligands, oxalato ligands, etc.
• the tin cluster of the present disclosure preferably includes one or two ligands selected from oxo ligands and peroxo ligands, and more preferably, a plurality of tin atoms are indirectly linked by oxo ligands and/or peroxo ligands.
• a plurality of tin atoms are indirectly linked by oxo ligands and/or peroxo ligands.
• structures such as Sn-O-Sn and Sn-O(-Sn)-Sn are included.
• structures such as Sn-O-O-Sn are included.
• the tin cluster is preferably a tin oxocluster, a tin peroxocluster, or a tin hydroxocluster, more preferably a tin oxocluster or a tin hydroxocluster, and even more preferably a tin oxocluster.
• an organic group is bonded to some or all of the tin atoms.
• the organic group bonded to the tin atom is cut when exposed to light, and it is presumed that the presence of the boron compound contained in the organoboron compound makes it easier for adjacent tin clusters to condense with each other starting from the cut site, resulting in a resist with extremely high sensitivity.
• the organic group bonded to the tin atom is preferably one or more organic groups selected from an alkyl group, an alkenyl group, and an aryl group.
• the alkyl group and the alkenyl group may be linear, branched, or cyclic.
• the organic group bonded to the tin atom is preferably an organic group having 1 to 30 carbon atoms, and the organic group may have one or more substituents.
• the organic group bonded to the tin atom is preferably an alkyl group, an alkenyl group, or an aryl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 2 to 6 carbon atoms.
• Tin clusters preferably contain 2 or more tin atoms in one molecule, preferably 30 or less, more preferably 20 or less, and even more preferably 18 or less.
• the tin cluster of the present disclosure is preferably composed of a cationic tin cluster and a counter anion, and the cationic tin cluster is preferably a divalent cation.
• the counter anion is preferably a hydroxide ion or an acetate ion.
• tin clusters according to the present disclosure include tin clusters of the following formula (1) or (2), with the cluster of the following formula (1) being preferred.
• R7 represents the organic group bonded to the tin atom, and X- represents a counter anion.
• Each R7 is independently preferably an alkyl group, an alkenyl group, or an aryl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 2 to 6 carbon atoms.
• R8 represents the organic group bonded to the tin atom
• R9 represents an organic group bonded to a carbon atom.
• Each R8 is preferably an alkyl group, an alkenyl group or an aryl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 2 to 6 carbon atoms.
• Each R9 is preferably an alkyl group, an alkenyl group or an aryl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
• the organoboron compound is a compound represented by the following formula (3) (hereinafter referred to as the "organoboron compound of the present disclosure").
• R 1 , R 2 and R 3 each independently represent an organic group bonded to boron through a carbon atom, an oxygen-containing organic group bonded to boron through an oxygen atom, or OH.
• the oxygen-containing organic group may contain a boron atom.
• Two groups selected from R 1 , R 2 and R 3 may be linked to form a ring structure.
• At least one of R 1 , R 2 , and R 3 is an organic group bonded to boron through a carbon atom, and at least one of R 1 , R 2 , and R 3 is an oxygen-containing organic group bonded to boron through an oxygen atom.
• the organoboron compound of the present disclosure preferably contains at least one selected from the group consisting of borate esters, boronic acids, boronic acid esters, borinic acid, borinic acid esters, borinic acid anhydrides, boroxines, and substituted boranes, and more preferably contains at least one selected from the group consisting of boronic acids, boronic acid esters, and boroxines.
• the borate ester refers to a compound in which R 1 , R 2 and R 3 in the above formula (3) are each independently an oxygen-containing organic group bonded to boron via an oxygen atom.
• the borate ester is preferably at least one selected from boric acid C 1-10 alkyl ester and boric acid C 6-20 aryl ester.
• the boric acid C 1-10 alkyl ester is preferably at least one selected from trimethyl borate, triethyl borate, tripropyl borate and triisopropyl borate.
• the boric acid C 6-20 aryl ester is preferably triphenyl borate.
• the boronic acid refers to a compound in which, in the above formula (3), R1 is an organic group bonded to boron at a carbon atom, and R2 and R3 are OH.
• the boronic acid is preferably at least one selected from alkylboronic acid, alkenylboronic acid, alkynylboronic acid, cycloalkylboronic acid, cycloalkenylboronic acid, arylboronic acid, and heteroarylboronic acid, and more preferably at least one selected from alkylboronic acid, cycloalkylboronic acid, cycloalkenylboronic acid, and arylboronic acid.
• the alkylboronic acid is preferably a C 1-10 alkylboronic acid, more preferably a C 1-7 alkylboronic acid, and even more preferably at least one selected from ethylboronic acid, isopropylboronic acid, butylboronic acid, isobutylboronic acid, and hexylboronic acid.
• the cycloalkylboronic acid is preferably a C 3-8 cycloalkylboronic acid, more preferably a C 4-7 cycloalkylboronic acid, and even more preferably at least one selected from cyclopentylboronic acid and cyclohexylboronic acid.
• the cycloalkenyl boronic acid is preferably a C 3-8 cycloalkenyl boronic acid, more preferably a C 4-7 cycloalkenyl boronic acid, and even more preferably 1-cyclopentenyl boronic acid.
• the aryl boronic acid is preferably at least one selected from aryl monoboronic acid and aryl diboronic acid.
• the aryl monoboronic acid is preferably a C 6-12 aryl monoboronic acid, more preferably a C 6-10 aryl monoboronic acid, and is preferably at least one selected from phenyl boronic acid, 4-methylphenyl boronic acid, 4-fluorophenyl boronic acid, 3,5-difluorophenyl boronic acid, 4-chlorophenyl boronic acid, 2-bromophenyl boronic acid, 4-cyanophenyl boronic acid, 4-methoxyphenyl boronic acid, 2,3-dimethoxyphenyl boronic acid, 3,4-dimethoxyphenyl boronic acid, 4-vinylphenyl boronic acid, 4-acetylphenyl boronic acid, 3,5-bis(trifluoromethyl)phenyl boronic acid, 4-(dimethyl
• the boronic acid ester refers to a compound in which, in the above formula (3), R 1 is an organic group bonded to boron through a carbon atom, and R 2 and R 3 are each independently an oxygen-containing organic group bonded to boron through an oxygen atom.
• the boronic acid ester is preferably at least one selected from the above-mentioned boronic acid esters, i.e., alkyl boronic acid esters, alkenyl boronic acid esters, alkynyl boronic acid esters, cycloalkyl boronic acid esters, cycloalkenyl boronic acid esters, aryl boronic acid esters, and heteroaryl boronic acid esters.
• the boronic acid ester is at least one selected from alkenyl boronic acid esters, alkynyl boronic acid esters, cycloalkyl boronic acid esters, cycloalkenyl boronic acid esters, and aryl boronic acid esters.
• the alkenyl boronic acid ester is preferably a C 1-6 alkenyl boronic acid ester, more preferably a C 2-3 alkenyl boronic acid ester, and even more preferably at least one selected from 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, diisopropyl allylboronate, 2-vinyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and dibutyl vinylboronate.
• the alkynyl boronic acid ester is preferably a C 1-6 alkynyl boronic acid ester, more preferably a C 1-4 alkynyl boronic acid ester, even more preferably an ethynyl boronic acid ester, and particularly preferably 2-ethynyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.
• the cycloalkyl boronic acid ester is preferably a C 3-8 cycloalkyl boronic acid ester, more preferably a C 3-6 cycloalkyl ester, and even more preferably at least one selected from 2-cyclopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 2-cyclohexyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.
• the cycloalkenyl boronic acid ester is preferably a C 3-8 cycloalkenyl boronic acid ester, more preferably a C 4-7 cycloalkenyl boronic acid ester, even more preferably a cyclohexenyl boronic acid ester, and particularly preferably 2-(1-cyclohexenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.
• the arylboronic acid ester is preferably a C 6-12 arylboronic acid ester, and is preferably 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-(4-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-(4-fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-(3,5-difluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-(4-chlorophenyl)-4,4,5, 5-tetramethyl-1,3,2-dioxaborolane, 2-(2-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-(4-cyanophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-(
• Borinic acid refers to a compound in which, in the above formula (3), R 1 and R 2 are each independently an organic group bonded to boron via a carbon atom, and R 3 is OH. It is preferable that R 1 and R 2 are each independently a C 1-4 alkyl group, a C 4-7 cycloalkyl group, or a C 6-12 aryl group.
• the borinic acid is more preferably at least one selected from dimethylborinic acid, diethylborinic acid, dipropylborinic acid, diisopropylborinic acid, dibutylborinic acid, ethylbutylborinic acid, dicyclohexylborinic acid, diphenylborinic acid, di(4-fluorophenyl)borinic acid, di(4-methylphenyl)borinic acid, di(4-methoxyphenyl)borinic acid, and di(4-(trifluoromethyl)phenyl)borinic acid.
• a borinic acid ester refers to a compound in which, in the above formula (3), R 1 and R 2 are each independently an organic group bonded to boron through a carbon atom, and R 3 is an oxygen-containing organic group bonded to boron through an oxygen atom.
• R 1 and R 2 are each preferably independently a C 1-4 alkyl group or a C 6-12 aryl group, and more preferably a phenyl group.
• R 3 is preferably an oxygen atom bonded to an amino C 1-6 alkyl group, more preferably an oxygen atom bonded to an amino C 1-4 alkyl group, and even more preferably an oxygen atom bonded to an aminoethyl group.
• the borinic acid ester is preferably a 2-aminoalkyl diarylborinate, more preferably a 2-aminoalkyl diphenylborinate, and even more preferably a 2-aminoethyl diphenylborinate.
• Borinic anhydride refers to a compound in which four hydrogen atoms contained in B2H4O are replaced by organic groups, and the four substituted organic groups are organic groups bonded to boron via carbon atoms.
• the borinic anhydride is preferably at least one selected from dialkylborinic anhydride and diarylborinic anhydride, and more preferably diphenylborinic anhydride.
• Boroxine refers to a compound in which three hydrogen atoms in B 3 H 3 O 3 are replaced by organic groups, and the three substituted organic groups are organic groups bonded to boron through carbon atoms or oxygen-containing organic groups bonded to boron through oxygen atoms.
• the boroxine is preferably at least one selected from trialkoxyboroxine, triarylboroxine, and trialkylboroxine, and is preferably at least one selected from 2,4,6-triphenylboroxine and 2,4,6-trimethoxyboroxine.
• the substituted borane refers to a compound in which three hydrogen atoms bonded to the boron atom of monoborane (BH 3 ) are replaced by R 1 , R 2 , and R 3 , and R 1 to R 3 are each independently an organic group bonded to boron via a carbon atom.
• the substituted borane is preferably a tri-substituted borane in which the three hydrogen atoms of monoborane are replaced by an aryl group which may have a substituent, and is particularly preferably at least one selected from triphenylborane and tris(pentafluorophenyl)borane.
• the resist composition of the present disclosure may contain an organic solvent.
• the organic solvent include alcohols such as ethanol, isopropanol, and 1-butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, and propionate.
• alcohols such as ethanol, isopropanol, and 1-butanol
• polyhydric alcohols such as ethylene glyco
• organic solvent examples include esters such as ethylene glycol monomethyl ether acetate; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, toluene, xylene, and trimethylbenzene; lactones such as ⁇ -butyrolactone; cyclic ethers such as dioxane; amines such as N,N-dimethylacetamide; and halogens such as chloroform, methylene chloride, and benzotrifluoride.
• the organic solvent may be used alone or in combination of two or more kinds. When two or more kinds are combined, the types and ratios thereof are arbitrary.
• the resist composition of the present disclosure may contain any optional components in addition to the organotin compound, the organoboron compound of the present disclosure, and the organic solvent.
• the ratio of boron atoms to tin contained in the resist composition of the present disclosure is preferably 1 to 1 x 10 moles of tin per mole of boron atoms, more preferably 1 to 1,000 moles, and even more preferably 1 to 20 moles. When within the above range, the film quality of the resist film tends to be improved.
• the ratio of the organotin compound to the organoboron compound of the present disclosure contained in the resist composition of the present disclosure is preferably 0.001 to 5 ⁇ 10 4 moles, more preferably 0.01 to 100 moles, and even more preferably 0.1 to 10 moles, of the organotin compound per mole of the organoboron compound of the present disclosure. When the ratio is within the above range, the film quality of the resist film tends to be improved.
• the resist composition of the present disclosure preferably contains 1 ppm or more of boron atoms, more preferably 10 ppm or more, and even more preferably 100 ppm or more. Within the above range, the quality of the resist film tends to improve.
• ppm refers to a value calculated in mass terms (for example, 10,000 ppm corresponds to 1 mass%).
• the resist composition of the present disclosure preferably contains tin at 1 ppm or more, more preferably 10 ppm or more, and even more preferably 100 ppm or more.
• the tin content in the resist composition of the present disclosure is preferably 60 mass% or less, more preferably 50 mass% or less, and even more preferably 40 mass% or less. When the tin content is within the above range, the film quality of the resist film tends to improve.
• the boron atom content and tin content can usually be analyzed by, for example, ICP, ICP-AES, or ICP-MS.
• the content of the organic solvent in the resist composition of the present disclosure is not particularly limited and may be set appropriately depending on, for example, the coating film thickness, etc., but the amount of the solvent is preferably 0.005 mL or more, more preferably 0.01 mL or more, and even more preferably 0.02 mL or more per 1 mg of the total solid content of the resist composition of the present disclosure. Also, the amount of the solvent is preferably 0.30 mL or less, more preferably 0.20 mL or less, and even more preferably 0.10 mL or less per 1 mg of the total solid content of the resist composition of the present disclosure. When the amount is within the above range, the film quality of the resist film tends to be improved.
• the total amount of solid content of the resist composition refers to the amount obtained by subtracting the content of the solvent from the total amount of the resist composition. The total amount of solid content can be measured by known analytical means such as liquid chromatography or gas chromatography.
• the resist composition of the present disclosure is preferably produced by a process including a step of mixing an organotin compound and an organoboron compound represented by the above formula (3) (the organoboron compound of the present disclosure) in an organic solvent (hereinafter also referred to as a “mixing step”).
• the type and amount of organic solvent used can be selected appropriately as described above.
• the method for producing the resist composition of the present disclosure preferably includes a purification step.
• An example of the purification step is a step of distilling off the solvent after the mixing step and washing with water or an organic solvent.
• the method for producing the resist composition of the present disclosure preferably includes a solvent addition step.
• a solvent for example, it is preferable to add a solvent to the resist composition of the present disclosure after the purification step to dissolve or disperse the composition.
• the organotin compound of the present disclosure used in the production of the resist composition of the present disclosure may be produced by a known method.
• a method of producing the compound represented by R A -Sn( ⁇ O)-OH (wherein R A represents an organic group) by reacting in the presence of an acid catalyst is preferred.
• R A an alkyl group, an alkenyl group or an aryl group having 1 to 20 carbon atoms is more preferred, an alkyl group having 1 to 20 carbon atoms is even more preferred, an alkyl group having 1 to 10 carbon atoms is particularly preferred, and an alkyl group having 2 to 6 carbon atoms is most preferred.
• the acid catalyst may be an organic acid or an inorganic acid, and examples of the acid catalyst that can be used include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and the like; paratoluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and the like.
• inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and the like
• paratoluenesulfonic acid methanesulfonic acid, trifluoromethanesulfonic acid, and the like.
• organoboron compounds used in the production of the resist composition of the present disclosure may be produced by known methods, or commercially available products may be used.
• the pattern forming method of the present disclosure includes a step (i) of applying a resist composition of the present disclosure, a step (ii) of drying the coating film of the resist composition, a step (iii) of exposing the coating film of the resist composition to light, and a step (iv) of developing the film of the resist composition.
• the method of forming a resist pattern according to the present disclosure includes a step (step (i)) of applying a resist composition according to the present disclosure.
• a coating film of the resist composition according to the present disclosure is formed.
• the method for applying the resist composition of the present disclosure is not particularly limited, and a resist film can be formed using any application method such as an inkjet method, a spray method, a spin coating method, a dip coating method, or a roll coating method. From the viewpoint of forming a uniform thin film, a spin coating method is preferred.
• the resist composition of the present disclosure is applied to, for example, a substrate, but there are no particular limitations on the substrate and the dimensions and size may be arbitrary.
• the material include silicon, SiC, nitride semiconductors, GaAs, and AlGaAs.
• the substrate on which the resist film is formed may have a thin film that is processed into a desired pattern by dry etching or the like.
• the thin film include a polysilicon thin film, a laminated film of a polysilicon thin film and a metal thin film, a metal thin film, and an insulating thin film such as a Si oxide film, a Si nitride film, or a Si oxynitride film.
• An organic film may be further formed on the thin film.
• the resist composition of the present disclosure may be used to form an upper resist film in a multilayer resist structure.
• step (i) The amount of the resist composition of the present disclosure applied in step (i) can be adjusted as appropriate, for example, so that the resist film has a thickness as described below.
• the method of forming a resist pattern according to the present disclosure includes a step (step (ii)) of drying the coating film of the resist composition.
• a coating film of the resist composition having a reduced solvent content is formed.
• Step (ii) is usually carried out after step (i).
• the method of drying the coating film of the resist composition of the present disclosure is not particularly limited.
• the heating temperature is preferably 50° C. or higher, more preferably 70° C. or higher, even more preferably 90° C. or higher, preferably 300° C. or lower, more preferably 250° C.
• step (ii) may be performed under two or more different conditions.
• the heating time is preferably 10 seconds or more, more preferably 20 seconds or more, even more preferably 30 seconds or more, preferably 300 seconds or lower, more preferably 200 seconds or lower, and even more preferably 150 seconds or lower.
• Step (ii) may be carried out under reduced pressure, normal pressure, or elevated pressure, or may be carried out in an inert atmosphere.
• the coating film after drying is preferably dried so that the amount of remaining solvent is as small as possible.
• the coating film after drying is preferably dried so that the solvent content is 1000 ppm or less.
• the method of forming a resist pattern according to the present disclosure includes a step of exposing a coating film of the resist composition to light (step (iii)). By exposing the coating film of the resist composition to light, a coating film is formed in which the exposed and unexposed parts are cured. Step (iii) is usually carried out after step (ii).
• the method for exposing a coating film of the resist composition of the present disclosure is not particularly limited, but is preferably carried out by irradiating with energy rays through a desired mask pattern.
• the energy ray may be, for example, ionizing radiation, non-ionizing radiation, etc.
• Ionizing radiation is radiation that has sufficient energy to ionize atoms or molecules.
• Ionizing radiation may be, for example, extreme ultraviolet (EUV), electron beam, ion beam, X-ray, alpha ray, beta ray, gamma ray, heavy particle beam, proton beam, etc.
• Non-ionizing radiation is radiation that does not have sufficient energy to ionize atoms or molecules.
• Non-ionizing radiation may be, for example, g-ray, i-ray, KrF excimer laser, ArF excimer laser, F2 excimer laser, etc.
• the method of forming a resist pattern according to the present disclosure includes a step (step (iv)) of developing a film of the resist composition according to the present disclosure.
• a resist pattern can be formed by the development treatment.
• Step (iv) is usually carried out after step (iii).
• the development of the film (resist film) of the resist composition of the present disclosure can be carried out using any of water, alkaline water, organic solvents, and mixtures thereof.
• solvents that can be used as developers include the organic solvents listed above.
• suitable organic solvents include aliphatic hydrocarbons such as hexane, heptane, octane, and decane; aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, cumene, and cymene; alcohols such as 4-methyl-2-pentanol, 1-butanol, isopropanol, 1-propanol, and methanol; esters such as ethyl lactate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethers such as tetrahydrofuran, dioxane, and anisole; and amines such as tetramethylammonium hydroxide.
• aliphatic hydrocarbons such as hexane,
• the developer may optionally contain viscosity modifiers, solubilizing aids, surfactants, etc., as desired.
• the developing time is preferably 10 seconds or more, more preferably 20 seconds or more, and even more preferably 30 seconds or more, and is preferably 300 seconds or less, more preferably 200 seconds or less, and even more preferably 100 seconds or less.
• the developing method is not particularly limited, and examples thereof include a dipping method, a paddle method, a spray method, and the like.
• the pattern forming method of the present disclosure may include any step other than the above steps (i), (ii), (iii), and (iv).
• An example of the optional step is a step (v) of baking the resist film after exposure to high-energy radiation, and the above step (v) is usually performed after the step (iii).
• the resist composition of the present disclosure can be used in the manufacture of semiconductor devices, masks for semiconductor manufacturing equipment, and the like.
• the method for producing a semiconductor device includes a step (ib) of applying the resist composition of the present disclosure onto a substrate, a step (ii-b) of drying the coating of the resist composition to form a resist film, a step (iii-b) of exposing the coating of the resist composition to light, and a step (iv-b) of developing the coating of the resist composition.
• steps (ib-b), (ii-b), (iii-b), and (iv-b) are the same as those of steps (i), (ii), (iii), and (iv), respectively.
• the method for producing a semiconductor device may include any steps other than the above steps.
• 1,4-dioxane was added to the resulting solid, which was recrystallized and purified, and then filtered to obtain 14 g of the target tin oxocluster paratoluenesulfonate ([(n-C 4 H 9 Sn) 12 ( ⁇ 3 -O) 14 ( ⁇ 2 -OH) 6 ] (4-CH 3 C 6 H 4 SO 3 ) 2 ).
• a resist solution was prepared by dissolving Compound A (54 mg) and 4-(trifluoromethyl)phenylboronic acid (6 mg) in 2-butanone to a solid concentration of 20 mg/mL.
• the resist solution was dropped onto a Si substrate cut into a 15 mm x 15 mm square through a membrane filter made of polytetrafluoroethylene (PTFE) with a pore size of 0.2 ⁇ m, spin-coated at 1500 rpm for 45 seconds, and then heated at 90° C. for 60 seconds to obtain a resist film.
• PTFE polytetrafluoroethylene
• the resist film thus obtained was irradiated with UV light for 15 seconds using a high pressure mercury lamp (illuminance at a wavelength of 365 nm: 52 mW/cm 2 ). At this time, half of the substrate was covered with aluminum foil to block the light so as to leave exposed and unexposed areas.
• the exposed substrate was developed by immersing it in ethylbenzene for 30 seconds, and then dried by blowing compressed air on it. After drying, the resist film remained in the exposed areas, while the resist film had been removed in the unexposed areas, confirming a negative contrast.
• Compound A was dissolved in toluene to a solid concentration of 20 mg/mL, and resist coating, exposure, and development were performed in the same manner as in Example 1. After development, the resist film remained on the substrate in both the exposed and unexposed areas, and no contrast was observed.
• Comparative Example 2 Except for using 2-heptanone as the developer instead of ethylbenzene, resist coating, exposure, and development were performed in the same manner as in Comparative Example 1. After development, no resist film remained on the substrate in either the exposed or unexposed areas, and no contrast was observed.

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• 2023
  • 2023-12-01 US US19/129,795 patent/US20260050210A1/en active Pending
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