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WO2025204344A1 - Liquide chimique, procédé de traitement d'objet à traiter et procédé de production de dispositif à semi-conducteur - Google Patents

Liquide chimique, procédé de traitement d'objet à traiter et procédé de production de dispositif à semi-conducteur

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Publication number
WO2025204344A1
WO2025204344A1 PCT/JP2025/005933 JP2025005933W WO2025204344A1 WO 2025204344 A1 WO2025204344 A1 WO 2025204344A1 JP 2025005933 W JP2025005933 W JP 2025005933W WO 2025204344 A1 WO2025204344 A1 WO 2025204344A1
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Prior art keywords
group
chemical solution
mass
germanium
acid
Prior art date
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Pending
Application number
PCT/JP2025/005933
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English (en)
Japanese (ja)
Inventor
広輔 宮崎
智威 高橋
和敬 高橋
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Fujifilm Corp
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Fujifilm Corp
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Publication of WO2025204344A1 publication Critical patent/WO2025204344A1/fr
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks

Definitions

  • Patent Document 1 discloses a composition for selectively etching a silicon-germanium alloy layer in the presence of a silicon layer, which contains 5 to 15 mass% of an oxidizing agent, 5 to 20 mass% of a fluoride ion source, a specific compound having a hydroxyl group or a carboxylic acid group, and water.
  • an object of the present invention is to provide a chemical solution that can selectively remove SiGe-containing materials with a high Ge concentration from a processing object having two types of SiGe-containing materials with different Ge concentrations.
  • Another object of the present invention is to provide a method for treating an object using the above-mentioned chemical solution and a method for manufacturing a semiconductor device.
  • a chemical solution used for a treatment object having two silicon-germanium-containing materials with different germanium concentrations, for removing at least a portion of the silicon-germanium-containing material with a higher germanium concentration comprising a fluoride ion source, an oxidizing agent, a specific unsaturated compound having a group represented by formula (1) described below, and a solvent.
  • the chemical solution according to [1] wherein the specific unsaturated compound has at least one selected from the group consisting of an ester bond, an ether bond, an amide group, an amino group, and a hydroxy group.
  • the present invention it is possible to provide a chemical solution that can selectively remove SiGe-containing materials with a high Ge concentration from a processing object having two types of SiGe-containing materials with different compositions. Furthermore, the present invention can provide a method for treating an object using the above-mentioned chemical solution and a method for manufacturing a semiconductor device.
  • the term "silicon (Si)-containing material” refers to a material containing Si element, which is different from the above-mentioned SiGe-containing material, and does not substantially contain Ge element. "Substantially not containing Ge element” means that the content of Ge element is less than 5 atomic % (preferably 0 atomic %) with respect to all atoms of the material.
  • the Si-containing material is preferably a material substantially composed of Si element only. "Substantially composed of Si element only” means that the content of Si element is 90 atomic % or more with respect to all atoms of the material. In a material substantially composed of Si element only, other elements (e.g., C element, N element, O element, B element, P element, etc., excluding Ge element) may be contained as long as the content of Si element is within the above range.
  • the bonding direction of a divalent group is not limited unless otherwise specified.
  • a divalent group e.g., -COO-
  • the compound may be either "X-O-CO-Z" or "X-CO-O-Z.”
  • substituents, etc. when there are multiple substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) represented by specific symbols, or when multiple substituents, etc. are specified at the same time, unless otherwise specified, this means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc.
  • ppm means “parts per million (10 -6 ),””ppb” means “parts per billion (10 -9 ),” and “ppt” means “parts per trillion (10 -12 ).” In this specification, 1 ⁇ (angstrom) corresponds to 0.1 nm.
  • each component of the drug solution described in this specification may be ionized in the drug solution or may form a salt.
  • the group represented by formula (1) in the specific unsaturated compound contained in the chemical solution of the present invention selectively adsorbs to SiGe-containing materials with a low Ge concentration, suppressing solubilization.
  • the chemical solution of the present invention when used on a workpiece having two SiGe-containing materials with different Ge concentrations, it is believed that at least a portion of the SiGe-containing material with a high Ge concentration can be selectively removed.
  • the ability to more selectively remove SiGe-containing materials with a high Ge concentration from a processing object having two types of SiGe-containing materials with different compositions will also be simply referred to as "the effect of the present invention is superior.”
  • the chemical solution of the present invention may also be preferable for the chemical solution of the present invention to have excellent SiGe selective solubility.
  • selective SiGe solubility refers to the ability to selectively remove SiGe-containing materials relative to Si-containing materials when used on a workpiece having two SiGe-containing materials with different Ge concentrations and a Si-containing material.
  • the chemical solution of the present invention is likely to exhibit excellent SiGe selective solubility due to the specific unsaturated compound being adsorbed to the Si-containing materials.
  • the fluoride ion source may be used alone or in combination of two or more.
  • the content of the fluoride ion source is preferably 10.0 mass% or less, more preferably less than 5.0 mass%, further preferably 3.0 mass% or less, particularly preferably 1.5 mass% or less, relative to the total mass of the chemical solution, in terms of more excellent effects of the present invention.
  • the content of the fluoride ion source is preferably 0.001 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.2 mass% or more, relative to the total mass of the chemical solution.
  • the fluoride ion source may be a solution containing a fluoride ion source. When a solution containing a fluoride ion source is used as the fluoride ion source, the content of the fluoride ion source is the content of the fluoride ion source contained in the solution.
  • the chemical solution of the present invention contains an oxidizing agent.
  • the standard oxidation-reduction potential of the oxidizing agent is preferably 1.0 V or higher, more preferably 1.3 V or higher, and even more preferably 1.5 V or higher, in terms of achieving better effects of the present invention.
  • There is no particular upper limit to the standard oxidation-reduction potential of the oxidizing agent but it is preferably 4.0 V or lower, and more preferably 2.5 V or lower.
  • the above standard oxidation-reduction potentials are based on the standard hydrogen electrode.
  • oxidizing agent examples include hydrogen peroxide, and peroxides such as peracetic acid, performic acid, perpropionic acid, and salts thereof; perhalogen acid compounds such as periodic acid, perchloric acid, and salts thereof; oxide halides such as iodic acid, chloric acid, hypochlorous acid, and salts thereof; nitric acid compounds such as nitric acid, cerium nitrate, and iron nitrate; persulfuric acid, persulfates, peroxodisulfuric acid, peroxodisulfates, and other persulfates; persulfides; percarbonates; perboric acid and salts thereof; permanganates; isocyanuric acid compounds such as isocyanuric acid, trichloroisocyanuric acid, and salts thereof; cerium compounds; and ferricyanides such as potassium ferricyanide.
  • peroxides such as peracetic acid, performic acid, perpropionic acid, and salts
  • the periodic acid includes metaperiodic acid (HIO 4 ) and orthoperiodic acid (H 5 IO 6 ).
  • the oxidizing agent is preferably periodic acid (standard oxidation-reduction potential 1.6 V), hydrogen peroxide (standard oxidation-reduction potential 1.8 V), peracetic acid (standard oxidation-reduction potential 1.4 V), performic acid, or perpropionic acid, and more preferably periodic acid or hydrogen peroxide.
  • the chemical solution may contain a component resulting from a reaction between an oxidizing agent and a solvent described below.
  • the chemical solution contains hydrogen peroxide
  • an acidic compound e.g., sulfuric acid
  • acetic acid part of the hydrogen peroxide may react with the acetic acid to produce peracetic acid, and the peracetic acid may function as an oxidizing agent.
  • the oxidizing agent may be used alone or in combination of two or more kinds.
  • the content of the oxidizing agent is preferably 0.01 to 20 mass%, more preferably 0.01 to 15 mass%, even more preferably 0.1 to 10 mass%, and particularly preferably 0.5 to 7 mass%, relative to the total mass of the chemical solution, in terms of more excellent effects of the present invention.
  • the chemical solution preferably contains an oxidizing agent in an amount of 0.1 to 5 mass %, more preferably 0.5 to 3 mass %, and even more preferably 0.5 to 1.5 mass %, in that the selective dissolution of SiGe is more excellent.
  • the chemical solution of the present invention contains a solvent.
  • the solvent includes water and organic solvents.
  • the organic solvent is preferably a water-soluble organic solvent.
  • the water-soluble organic solvent refers to an organic solvent having a solubility in water (100 g) at 25° C. of 20 g/100 g or more.
  • the solvent preferably contains a water-soluble organic solvent, and more preferably contains water and a water-soluble organic solvent.
  • carboxylic acid solvents examples include formic acid, acetic acid, and propionic acid.
  • ether-based solvents include dialkyl ethers such as diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, and cyclohexyl methyl ether; glycol ethers such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol propyl ether, diethylene glyco
  • a sulfoxide solvent is dimethyl sulfoxide (DMSO).
  • ester solvents include linear esters such as ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropanoate, propylene glycol monomethyl ether acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol diacetate, and propylene glycol diacetate, as well as cyclic esters such as propylene carbonate, ethylene carbonate, and diethyl carbonate.
  • linear esters such as ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropanoate
  • propylene glycol monomethyl ether acetate ethylene glycol monoacetate, diethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, propylene glycol monoe
  • solvents include ketone solvents such as acetone, dimethyl ketone (propanone), cyclobutanone, cyclopentanone, cyclohexanone, methyl ethyl ketone (2-butanone), 5-hexanedione, methyl isobutyl ketone, 1,4-cyclohexanedione, 1,3-cyclohexanedione, and cyclohexanone; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide; sulfone solvents such as sulfolane, 3-methyl
  • the water-soluble organic solvent preferably contains at least one selected from the group consisting of formic acid, acetic acid, propionic acid, and ethylene glycol monobutyl ether (EGBE), more preferably contains at least one selected from the group consisting of acetic acid, propionic acid, and EGBE, and even more preferably contains acetic acid.
  • EGBE ethylene glycol monobutyl ether
  • the chemical solution of the present invention contains a specific unsaturated compound having a group represented by formula (1).
  • each R independently represents a hydrogen atom, a carboxylic acid group, or a hydrocarbon group which may have a substituent.
  • the hydrocarbon group represented by R includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred.
  • the hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 4 to 12 carbon atoms.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear.
  • the aliphatic hydrocarbon group includes an alkyl group, an alkenyl group, and an alkynyl group, with an alkyl group or an alkenyl group being preferred.
  • the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthryl group, with a phenyl group being preferred.
  • R is preferably a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent, and more preferably a hydrogen atom or an alkyl group having 4 to 12 carbon atoms which may have a substituent.
  • Examples of the substituent that the hydrocarbon group may have include a hydroxy group, a carboxylic acid group, an amide group, an amino group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and an alkylene glycol structure-containing group, and a hydroxy group, a carboxylic acid group, or an alkylene glycol structure-containing group is preferred. * indicates the bond position.
  • the alkylene glycol structure-containing group is a group having an alkylene glycol structure, and specific examples thereof include groups represented by R X1 —(OL X1 ) s —L X2 —.
  • R X1 represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  • the hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred, and an alkyl group or an alkenyl group being more preferred.
  • the hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 12 carbon atoms.
  • R X1 is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom.
  • Each of L and X1 independently represents an alkylene group which may have a hydroxy group.
  • the alkylene group is preferably linear or branched, more preferably linear.
  • the alkylene group preferably has 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
  • s represents an integer of 1 or greater, and preferably an integer of 2 or greater.
  • the alkylene glycol structure-containing group is also preferably a polyalkylene glycol structure-containing group.
  • the upper limit of s is preferably 60 or less, more preferably 30 or less, and even more preferably 10 or less.
  • L X2 represents a single bond or a divalent linking group. Examples of the divalent linking group include —O—, —CO—, an alkylene group, an alkenylene group, and a group formed by combining these groups.
  • the specific unsaturated compound preferably has multiple groups represented by formula (1), as this provides better effects of the present invention.
  • the specific unsaturated compound preferably has two or more groups represented by formula (1), more preferably two to eight groups, and even more preferably three to six groups.
  • the specific unsaturated compound preferably has at least one bond selected from the group consisting of an ester bond (-CO-O-), an ether bond (-O-), an amide group (-CO-NR N 2 ), an amino group (-NR N 2 ), and a hydroxy group (-OH), more preferably has at least one bond selected from the group consisting of an ester bond and an ether bond, and even more preferably has an ether bond.
  • R 1 N each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  • the specific unsaturated compound preferably has an alkylene glycol structure, more preferably a polyalkylene glycol structure, as a structure containing an ether bond.
  • the alkylene group in the alkylene glycol structure and polyalkylene glycol structure is preferably linear or branched, more preferably linear.
  • the alkylene group preferably has 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
  • the specific unsaturated compound preferably has a polyethylene glycol structure in which the alkylene group is an ethylene group.
  • Examples of the specific unsaturated compound include compounds represented by formulas (2) to (4), of which compounds represented by formula (3) or (4) are preferred, and compounds represented by formula (4) are more preferred.
  • R 2 C CH-L 1 -(OL 2 ) n -R 2 Formula (4)
  • ⁇ R 2 C CH-L 1 -(OL 2 ) n -L 3 ⁇ m -X
  • R is the same as R in formula (1).
  • R 1 represents an alkyl group which may have a hydroxy group or a cyclic ether group, an alkenyl group which may have a hydroxy group or a cyclic ether group, or a carboxylic acid group.
  • the alkyl group and alkenyl group may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms.
  • the number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and still more preferably 3 to 10.
  • the number of carbon-carbon double bonds in the alkenyl group is 1 or more, and may be 2 or more.
  • the cyclic ether group include an epoxy group and an oxetanyl group.
  • the alkyl group or alkenyl group has a hydroxy group or a cyclic ether group
  • the number of the hydroxy group or the cyclic ether group is preferably 1 to 3, and more preferably 1.
  • R1 is preferably an alkyl group having 2 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms.
  • L 1 represents a single bond or a divalent linking group.
  • the divalent linking group include an alkylene group, an alkenylene group, —O—, —CO—, and groups formed by combining these groups.
  • the alkylene group and alkenylene group are preferably linear or branched, more preferably linear.
  • the alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms.
  • the alkenylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 3 to 10 carbon atoms.
  • L1 is preferably -alkylene group-, -alkylene group-CO-, -alkenylene group-, or -alkenylene group-CO-.
  • each L2 independently represents an alkylene group which may have a hydroxy group.
  • the alkylene group is preferably linear or branched, more preferably linear.
  • the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
  • a plurality of L2s may be the same or different, but are preferably the same.
  • n represents an integer of 1 or more. n is preferably 2 or more, and more preferably 3 or more. The upper limit of n is preferably 60 or less, more preferably 30 or less, and even more preferably 10 or less.
  • R2 represents a hydrogen atom, a hydroxy group, or a hydrocarbon group which may have a substituent.
  • the hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred.
  • the hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 12 carbon atoms.
  • the aliphatic hydrocarbon group includes an alkyl group, an alkenyl group, and an alkynyl group, with an alkyl group or an alkenyl group being preferred.
  • Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthryl group, with a phenyl group being preferred.
  • Examples of the substituent that the hydrocarbon group may have include a hydroxy group, a carboxylic acid group, an amide group, and an amino group.
  • R2 is preferably a hydrogen atom, a hydroxy group, or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, a hydroxy group, or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a hydrogen atom or a hydroxy group.
  • each L3 independently represents a single bond or a divalent linking group.
  • the divalent linking group include the divalent linking groups exemplified as the group represented by L 1 in formula (3).
  • L3 is preferably a single bond, —O—, or an alkylene group, more preferably a single bond, —O—, or an alkylene group having 1 to 4 carbon atoms.
  • X represents an m-valent linking group.
  • the m-valent linking group includes an m-valent hydrocarbon group which may have a substituent.
  • the hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred.
  • the number of carbon atoms in the hydrocarbon group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 3 to 8. When m is 4 and the number of carbon atoms in the hydrocarbon group is 1, the m-valent hydrocarbon group represents a carbon atom.
  • the substituent that the hydrocarbon group may have includes a hydroxy group, a carboxylic acid group, an amide group, an amino group, an alkoxy group, and a polyalkylene glycol structure-containing group, and a hydroxy group or a polyalkylene glycol structure-containing group is preferred.
  • the polyalkylene glycol structure-containing group is as described above.
  • the carbon number excluding the carbon number of the polyalkylene glycol structure-containing group satisfies the above-mentioned preferred range.
  • the number of the substituents is preferably 1 to 4, and more preferably 1 to 3.
  • the compound represented by formula (4) is preferably a compound represented by formula (5).
  • Formula (5) H-(C(W)H) t -H each W independently represents a hydroxy group, a polyalkylene glycol structure-containing group, or a group represented by R 2 C ⁇ CH-L 1 -(O-L 2 ) n -L 3 -, provided that three or more of the t Ws represent a group represented by R 2 C ⁇ CH-L 1 -(O-L 2 ) n -L 3 -.
  • t represents an integer of 3 or more, preferably an integer of 3 to 10, more preferably an integer of 4 to 8, and even more preferably an integer of 4 to 6.
  • the number of groups represented by R 2 C ⁇ CH-L 1 -(OL 2 ) n -L 3 - is 3 or more, preferably 3 to 8, more preferably 3 to 6, and even more preferably 3 or 4.
  • unsaturated compounds include unsaturated fatty acids such as linolenic acid, oleic acid, and sorbic acid; polyalkylene glycol alkenylene ethers such as polyoxyethylene oleyl ether; polyalkylene glycol unsaturated fatty acid esters such as polyethylene glycol oleate and polyethylene glycol linoleate; and sorbitol unsaturated fatty acid esters such as polyoxyalkylene sorbitol tetraoleate, sorbitol tetraoleate, sorbitol trioleate, sorbitol dioleate, and sorbitol monooleate.
  • unsaturated fatty acids such as linolenic acid, oleic acid, and sorbic acid
  • polyalkylene glycol alkenylene ethers such as polyoxyethylene oleyl ether
  • polyalkylene glycol unsaturated fatty acid esters such as polyethylene glycol oleate and poly
  • sorbitan unsaturated fatty acid esters examples include sorbitan monooleate, sorbitan trioleate, polyoxyalkylene sorbitan tetraoleate, and polyoxyalkylene sorbitan trioleate; oleamide; ethylene glycol monoallyl ether; allyl methyl ether; glycerol ⁇ , ⁇ '-diallyl ether (glycerol diallyl ether); pentaerythritol tetraallyl ether; ethylene glycol monovinyl ether; maleic acid; 3-phenyl-2-propen-1-ol; and 1,2-epoxy-5-hexene.
  • Emulgen 408 Emulgen 430
  • Rheodol 430V Rheodol 440V
  • Rheodol 460V Rheodol 460V
  • EMANON 4110 all manufactured by Kao Corporation
  • Sanicol M-700 Sanicol DMT-4715
  • Sanicol MMT-200 all manufactured by Sanyo Chemical Industries, Ltd.
  • the specific unsaturated compounds may be used alone or in combination of two or more.
  • the content of the specific unsaturated compound is preferably 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, and even more preferably 0.01 to 1% by mass, relative to the total mass of the chemical solution, in terms of better effects of the present invention.
  • the chemical solution of the present invention may further contain an anticorrosive agent, which is a component different from the components described above.
  • the anticorrosive agent is preferably a heterocyclic compound.
  • the heterocyclic compound may be either an aromatic heterocyclic compound or an aliphatic heterocyclic compound, with aromatic heterocyclic compounds being preferred.
  • the heterocyclic compound may be either a monocyclic or polycyclic compound, and is preferably a monocyclic compound.
  • the heterocyclic compound preferably has 4 to 20 ring atoms, more preferably 5 to 10 ring atoms, even more preferably 5 to 8 ring atoms, and particularly preferably 5 ring atoms.
  • the heterocyclic compound may have a substituent.
  • substituents examples include a hydroxy group, a carboxylic acid group, an amino group, an alkyl group, an aryl group, an alkoxy group, an acyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, a mercapto group, an imidazolyl group, and a halogen atom. If possible, the substituent may further have a hydroxy group, a carboxylic acid group, an amino group, a mercapto group, and a halogen atom as a substituent.
  • the number of heteroatoms contained as ring member atoms in the heterocyclic compound is 1 or more, preferably 2 or more, more preferably 2 to 4, and even more preferably 2 or 3, in terms of better effects of the present invention.
  • the heterocyclic compound preferably contains a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, and more preferably contains a nitrogen atom, i.e., the heterocyclic compound is preferably a nitrogen-containing heterocyclic compound.
  • the nitrogen-containing heterocyclic compound is preferably an azole or a derivative thereof.
  • Azoles are five-membered aromatic heterocyclic compounds containing a nitrogen atom.
  • the number of nitrogen atoms contained in the azole is preferably 1 to 4, and more preferably 1 to 3.
  • azoles include pyrrole, in which one of the atoms constituting the azole ring is a nitrogen atom; imidazole and pyrazole, in which two of the atoms constituting the azole ring are nitrogen atoms; thiazole, in which one of the atoms constituting the azole ring is a nitrogen atom and the other is a sulfur atom; triazole, in which three of the atoms constituting the azole ring are nitrogen atoms; and tetrazole, in which four of the atoms constituting the azole ring are nitrogen atoms.
  • the azole derivatives include azoles having a substituent.
  • the substituent include the substituents that the heterocyclic compounds described above may have.
  • the alkyl group and aryl group may further have the above-mentioned substituents as a substituent.
  • two of the substituents may be bonded to each other to form a ring which may have a substituent.
  • the ring may be either an aromatic ring or an aliphatic ring, and is preferably an aromatic ring.
  • rings formed by bonding the above substituents to each other include a benzene ring, an azole ring, a thiophene ring, a furan ring, and a pyridine ring.
  • the substituent that the ring may have include the substituents that the azole may have.
  • imidazole and its derivatives examples include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole, 4-hydroxyimidazole, 2,2'-biimidazole, 4-imidazolecarboxylic acid, histamine, and benzimidazole, with imidazole being preferred.
  • pyrazole and derivatives thereof examples include pyrazole, 2,4-dimethylpyrazole, 3,5-dimethylpyrazole, benzopyrazole, and 2-mercaptobenzopyrazole, with pyrazole being preferred.
  • Examples of thiazole and its derivatives include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole, with thiazole being preferred.
  • Examples of triazole and derivatives thereof include 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-1H-triazole, 1,2,3-triazole, 1-methyl-1,2,3-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxybenzotriazole, 5-methylbenzotriazole, and 2,2'- ⁇ [(5-methyl-1H-benzotriazol-1-yl)methyl]imino ⁇ diethanol, of which 1,2,4-triazole, 3-methyl-1,2,4-triazole, or 3-amino-1,2,4-1H-triazole is preferred, and
  • tetrazole and its derivatives examples include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyltetrazole, 5-aminotetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, and 1-(2-dimethylaminoethyl)-5-mercaptotetrazole, with 5-aminotetrazole being preferred.
  • imidazole, pyrazole, triazole, or derivatives thereof are preferred, triazole or derivatives thereof are more preferred, and 1,2,4-triazole is even more preferred.
  • the anticorrosive agent may be used alone or in combination of two or more kinds.
  • the content of the anticorrosive agent is preferably 0.01 to 10 mass %, more preferably 0.05 to 5 mass %, and even more preferably 0.5 to 2 mass %, based on the total mass of the chemical solution.
  • the chemical solution may contain other additives in addition to those mentioned above.
  • additives include amine compounds, silane compounds, surfactants, antifoaming agents, basic compounds, and acidic compounds, all of which are different from the above-mentioned fluoride ion source, oxidizing agent, solvent, specific unsaturated compound, and corrosion inhibitor.
  • the chemical solution may contain an amine compound.
  • the amine compound is preferably a compound in which one or more hydrogen atoms of ammonia are substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • the amine compound is also preferably an alkanolamine compound having at least one hydroxy group as the above-mentioned substituent.
  • the alkyl group which may have a substituent may be either linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 3.
  • Examples of the substituent which the alkyl group may have include a halogen atom, a cyano group, an amino group, and a hydroxy group, with an amino group or a hydroxy group being preferred.
  • Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 2,3-hydroxypropyl group, a 2-aminoethyl group, and a 3-aminopropyl group.
  • Examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group, a furyl group, a p-hydroxyphenyl group, and a p-chlor
  • amine compounds examples include methylamine, dimethylamine, trimethylamine, ethylamine, ethanolamine, diethylamine, diethanolamine, propylamine, diisopropanolamine, N-(3-aminopropyl)diethanolamine, and bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane, with diisopropanolamine or N-(3-aminopropyl)diethanolamine being preferred.
  • the content of the amine compound is preferably 0.01 to 1 mass% of the total mass of the chemical solution, and more preferably 0.02 to 0.1 mass%.
  • the chemical solution may contain a silane compound.
  • the silane compound is preferably a low molecular weight compound, and the molecular weight of the silane compound (when the silane compound has a molecular weight distribution, the weight average molecular weight) is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. The lower limit is often 50 or more, and preferably 80 or more.
  • the silane compound is not particularly limited as long as it is a compound having a silicon atom, but a compound having a hydrolyzable silyl group (a silyl group in which a hydrolyzable group is bonded to a silicon atom) is preferred.
  • the silane compound is preferably a compound represented by formula (S). (R S ) d Si(H) e (X) 4-de (S)
  • R N1 and R N2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom.
  • the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred.
  • X represents a hydrolyzable group.
  • the groups represented by the plurality of Xs may be the same or different, and are preferably the same.
  • Hydrolyzable groups include alkoxy groups and halogen atoms.
  • the alkyl group in the alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • the halogen atom includes a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.
  • X is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms.
  • silane compounds include the compounds described in paragraphs [0070] to [0081] of WO 2017/217320 and the compounds described in paragraphs [0056] to [0066] of JP 2009-242604 A, the contents of which are incorporated herein by reference.
  • the silane compounds may be used alone or in combination of two or more.
  • the content of the silane compound is preferably 0.01 to 10 mass %, more preferably 0.05 to 5 mass %, and even more preferably 0.01 to 3.5 mass %, based on the total mass of the chemical solution.
  • anionic surfactants examples include sulfonic acid surfactants having a sulfonic acid group, sulfate ester surfactants having a sulfate ester group, phosphonic acid surfactants having a phosphonic acid group, and phosphate ester surfactants having a phosphate ester group.
  • anionic surfactant for example, the compounds exemplified in paragraphs [0116] to [0123] of WO 2022/044893 can also be used, the contents of which are incorporated herein by reference.
  • the chemical solution may contain an antifoaming agent.
  • Surfactants may cause foaming depending on how they are used. Therefore, it is preferable that the chemical solution containing a surfactant contains an antifoaming agent that suppresses the generation of foaming, shortens the lifespan of the foam that is generated, and suppresses the retention of foam.
  • the antifoaming agent is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include silicone-based antifoaming agents, fatty acid ester-based antifoaming agents, and long-chain aliphatic alcohol-based antifoaming agents. Among these, silicone-based antifoaming agents are preferred because of their superior effect of suppressing foam residue.
  • the antifoaming agent does not include the compounds contained in the surfactants.
  • the chemical solution may contain a basic compound, which is a compound different from the above-mentioned components.
  • a basic compound is a compound that exhibits alkaline properties (pH greater than 7.0) in an aqueous solution.
  • the basic compound includes organic basic compounds and inorganic basic compounds.
  • organic basic compounds examples include quaternary ammonium salts, amine oxide compounds, nitro compounds, nitroso compounds, oxime compounds, ketoxime compounds, aldoxime compounds, lactam compounds, and isocyanide compounds. Note that organic basic compounds are compounds different from the above-mentioned heterocyclic compounds.
  • inorganic basic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, and ammonia or salts thereof.
  • the pH of the chemical solution is preferably 0.5 to 9, more preferably 1 to 7.
  • the pH of the chemical solution can be measured using a known pH meter according to the method of JIS Z8802-1984. The measurement temperature is 25°C.
  • the content (measured as ion concentration) of metals (e.g., metal elements Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) contained as impurities in the chemical solution is preferably 5 mass ppm or less, more preferably 1 mass ppm or less.
  • the metal content is more preferably a value lower than 1 mass ppm, that is, a value on the order of ppb or less, particularly preferably 100 mass ppb or less, and most preferably less than 10 mass ppb.
  • the lower limit is preferably 0.
  • a representative device of the former is the KS-19F, and a representative device of the latter is the Chem20.
  • Devices such as the KS-42 series and LiQuilaz II S series can be used to measure larger particles.
  • insoluble particles include particles of inorganic solids such as silica (including colloidal silica and fumed silica), alumina, zirconia, ceria, titania, germania, manganese oxide, and silicon carbide; and particles of organic solids such as polystyrene, polyacrylic resin, and polyvinyl chloride.
  • Methods for removing insoluble particles from the chemical solution include, for example, purification treatment such as filtering. It is also preferable that the chemical solution does not contain abrasive grains.
  • the chemical solution may contain coarse particles, but it is preferable that the content of coarse particles is low.
  • coarse particles refers to particles whose diameter (particle size) is 1 ⁇ m or more when the particle shape is considered as a sphere.
  • the coarse particles contained in the chemical solution include particles such as dust, dirt, organic solids, and inorganic solids contained as impurities in the raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids brought in as contaminants during the preparation of the chemical solution, which ultimately remain as particles without dissolving in the chemical solution.
  • the content of coarse particles in the chemical solution is preferably 100 or less, more preferably 50 or less, particles having a particle size of 1 ⁇ m or more per mL of the chemical solution.
  • the lower limit is preferably 0 or more, more preferably 0.01 or more, per mL of the chemical solution.
  • the content of coarse particles present in a chemical solution can be measured in the liquid phase using a commercially available measuring device that uses a laser as a light source and is a liquid-borne particle measuring method based on light scattering.
  • the drug solution of the present invention can be produced by a known method, which will be described in detail below.
  • the method for preparing the drug solution of the present invention may be, for example, a method in which the above-mentioned components are mixed together.
  • the order and/or timing of mixing the above components are not particularly limited, and examples thereof include a method in which a fluoride ion source, an oxidizing agent, a specific unsaturated compound, and, if necessary, optional components are sequentially added to a container containing a solvent, followed by stirring to mix.
  • a pH adjuster may be added to adjust the pH of the mixed solution to prepare the solution.
  • the stirring device and stirring method used to prepare the chemical solution may be any known device such as a stirrer or disperser.
  • stirrers include industrial mixers, portable stirrers, mechanical stirrers, and magnetic stirrers.
  • dispersers include industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.
  • the drug solution of the present invention may be prepared as a kit in which the raw materials thereof are divided into a plurality of parts.
  • the raw materials may be mixed in a predetermined ratio at or before use to prepare the drug solution of the present invention.
  • the drug solution may also be prepared as a concentrated solution.
  • the diluted solution obtained by diluting with a diluent liquid before use is used.
  • the kit may be a kit including the drug solution in the form of a concentrated solution and the diluent liquid.
  • purification It is preferable to subject one or more of the raw materials for preparing the chemical solution to a purification treatment in advance. If necessary, the chemical solution may also be subjected to a purification treatment.
  • the degree of purification is preferably such that the purity of the raw material is 99% by mass or more, and more preferably such that the purity of the undiluted solution is 99.9% by mass or more, with the upper limit being preferably 99.9999% by mass or less.
  • Examples of purification methods include passing the raw material through an ion exchange resin or a reverse osmosis membrane (RO membrane), reprecipitation, distillation of the raw material, and filtering.
  • the filter used for filtering can be any filter conventionally used for filtering purposes, without any particular limitations.
  • materials constituting the filter include filters made of fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyallylsulfone (PAS), and polyolefin resins (including high-density or ultra-high molecular weight) such as polyethylene and polypropylene (PP).
  • materials selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesins (including PTFE and PFA), and polyamide resins (including nylon) are preferred, with fluororesin filters being more preferred. Filtering raw materials using filters made of these materials can effectively remove highly polar contaminants that are likely to cause defects.
  • the purification process may involve a combination of the above purification methods.
  • the purification process may also be carried out multiple times.
  • the container for storing the above-mentioned drug solution, concentrated solution, or kit is not particularly limited, and any known container can be used as long as corrosiveness of the liquid does not pose a problem.
  • Specific examples of the container include the "Clean Bottle” series manufactured by Aicello Chemical Co., Ltd. and the “Pure Bottle” manufactured by Kodama Resin Industry Co., Ltd.
  • containers examples include, but are not limited to, the containers described in JP 2015-123351 A.
  • the containers exemplified in paragraphs [0121] to [0124] of WO 2022/004217 can also be used, the contents of which are incorporated herein by reference.
  • These containers are preferably cleaned from the inside before being filled with the chemical solution.
  • the liquid used for cleaning preferably has a reduced amount of metal impurities.
  • the chemical solution may be bottled in containers such as gallon bottles or coated bottles for transport and storage.
  • the workpiece may further contain Si-containing materials.
  • Si-containing materials By using the chemical solution of the present invention on a workpiece having a Si-containing material and two SiGe-containing materials with different Ge concentrations, it is possible to selectively remove at least a portion of the SiGe-containing material relative to the Si-containing material. In many cases, the at least a portion of the SiGe-containing material refers to a portion or all of the SiGe-containing material with a high Ge concentration.
  • the form of the Si-containing substance on the substrate may be any of a film, a wiring, a plate, a column, and a particle.
  • 1 shows an embodiment in which the workpiece 200 includes a plurality of first SiGe-containing materials 204 and second SiGe-containing materials 206, only one layer of either or both of the plurality of first SiGe-containing materials 204 and the plurality of second SiGe-containing materials 206 may be present.
  • 1 shows portions on the substrate 202 where neither the first SiGe inclusions 204 nor the second SiGe inclusions 206 are present, but such portions may be covered with either the first SiGe inclusions 204 or the second SiGe inclusions 206.
  • the first SiGe inclusions 204 are disposed directly on the substrate 202, but they may be disposed via another layer.
  • the second SiGe inclusions 206 may be supported by another material (not shown).
  • the method for manufacturing the workpiece is not particularly limited.
  • the workpiece may be manufactured by forming an insulating film on a substrate, disposing SiGe-containing material and/or Si-containing material on the insulating film using methods such as sputtering, chemical vapor deposition (CVD), or molecular beam epitaxy (MBE), and then performing a planarization process such as CMP.
  • CVD chemical vapor deposition
  • MBE molecular beam epitaxy
  • the chemical solution of the present invention can selectively remove SiGe-containing materials with a high Ge concentration from a workpiece containing two types of SiGe-containing materials with different compositions.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un liquide chimique qui est capable d'éliminer sélectivement un matériau contenant du silicium-germanium ayant une concentration élevée en germanium d'un objet à traiter comprenant deux types de matériaux contenant du silicium-germanium qui ont des compositions différentes. Un liquide chimique selon la présente invention est utilisé pour un objet à traiter comprenant deux matériaux contenant du silicium-germanium qui ont des concentrations de germanium différentes, et élimine au moins une partie d'un matériau contenant du silicium-germanium qui a une concentration élevée en germanium. Ce liquide chimique contient une source d'ions fluorure, un agent oxydant, un composé insaturé spécifique qui a un groupe représenté par la formule (1) R2C=CH-* et un solvant.
PCT/JP2025/005933 2024-03-26 2025-02-20 Liquide chimique, procédé de traitement d'objet à traiter et procédé de production de dispositif à semi-conducteur Pending WO2025204344A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2024-050281 2024-03-26
JP2024050281 2024-03-26
JP2024-139012 2024-08-20
JP2024139012 2024-08-20

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WO2025204344A1 true WO2025204344A1 (fr) 2025-10-02

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002511652A (ja) * 1998-04-10 2002-04-16 マサチューセッツ インスティテュート オブ テクノロジー シリコンゲルマニウムエッチング停止層システム
US20190393304A1 (en) * 2018-06-20 2019-12-26 International Business Machines Corporation DIELECTRIC ISOLATION AND SiGe CHANNEL FORMATION FOR INTEGRATION IN CMOS NANOSHEET CHANNEL DEVICES
WO2023161058A1 (fr) * 2022-02-23 2023-08-31 Basf Se Composition, son utilisation et procédé de gravure sélective d'un matériau silicium-germanium
JP2023541278A (ja) * 2020-09-11 2023-09-29 フジフイルム エレクトロニック マテリアルズ ユー．エス．エー．， インコーポレイテッド エッチング組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002511652A (ja) * 1998-04-10 2002-04-16 マサチューセッツ インスティテュート オブ テクノロジー シリコンゲルマニウムエッチング停止層システム
US20190393304A1 (en) * 2018-06-20 2019-12-26 International Business Machines Corporation DIELECTRIC ISOLATION AND SiGe CHANNEL FORMATION FOR INTEGRATION IN CMOS NANOSHEET CHANNEL DEVICES
JP2023541278A (ja) * 2020-09-11 2023-09-29 フジフイルム エレクトロニック マテリアルズ ユー．エス．エー．， インコーポレイテッド エッチング組成物
WO2023161058A1 (fr) * 2022-02-23 2023-08-31 Basf Se Composition, son utilisation et procédé de gravure sélective d'un matériau silicium-germanium

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