WO2021176903A1 - Liquide de traitement - Google Patents

Liquide de traitement Download PDF

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Publication number
WO2021176903A1
WO2021176903A1 PCT/JP2021/003020 JP2021003020W WO2021176903A1 WO 2021176903 A1 WO2021176903 A1 WO 2021176903A1 JP 2021003020 W JP2021003020 W JP 2021003020W WO 2021176903 A1 WO2021176903 A1 WO 2021176903A1
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Prior art keywords
treatment liquid
acid
group
mass
sige
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PCT/JP2021/003020
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English (en)
Japanese (ja)
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篤史 水谷
泰雄 杉島
宣明 杉村
智威 高橋
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富士フイルム株式会社
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Publication of WO2021176903A1 publication Critical patent/WO2021176903A1/fr

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    • 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
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • 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

  • the present invention relates to a treatment liquid.
  • Patent Document 1 discloses an etching solution containing nitric acid, a fluorine-containing compound, and a nitrogen-containing organic compound A or a phosphorus-containing compound B having a plurality of repeating units having a nitrogen atom.
  • the present inventors examined a treatment liquid (etching liquid) based on the description of Patent Document 1, and found that the treatment liquid contains Si when treating a SiGe-containing substance and an object to be treated having a Si-containing substance. It has been found that there is room for further improvement in the etching selectivity of the SiGe-containing material with respect to the product. In addition, the present inventors have found that there is room for further improvement in the storage stability of the treatment liquid.
  • the present invention is excellent in etching selectivity of the SiGe-containing material with respect to the Si-containing material and excellent storage stability when treating the SiGe-containing material and the object to be treated having the Si-containing material.
  • the subject is to provide the liquid.
  • a treatment liquid used for SiGe-containing substances and objects to be treated having Si-containing substances which removes at least a part of the SiGe-containing layer, and is a fluoride ion source, nitric acid, a sulfonic acid compound, and a sulfate ester.
  • the fluoride ion source contains at least one selected from the group consisting of hydrofluoric acid and its salt, hexafluorophosphoric acid and its salt, hexafluorosilicic acid and its salt, and tetrafluoroboric acid and its salt. , [1] to [7]. [9] The treatment liquid according to any one of [1] to [8], wherein the content of the fluoride ion source is less than 1% by mass with respect to the total mass of the treatment liquid. [10] The treatment liquid according to any one of [1] to [9], wherein the content of the fluoride ion source is 0.01 to 0.5% by mass with respect to the total mass of the treatment liquid.
  • the present invention it is possible to provide a treatment liquid having excellent etching selectivity of the SiGe-containing material with respect to the Si-containing material and excellent storage stability.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the “content” of the component means the total content of the two or more kinds of components.
  • ppm means “parts-per-million ( 10-6 )
  • ppb means “parts-per-billion ( 10-9 )
  • ppt Means “parts-per-trillion ( 10-12 )”.
  • room temperature is "25 ° C”.
  • the pH of the treatment liquid is a value measured by F-51 (trade name) manufactured by HORIBA, Ltd. at room temperature (25 ° C.).
  • the molecular weight when there is a molecular weight distribution is the weight average molecular weight.
  • the weight average molecular weight of the resin (polymer) is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene.
  • the components of the treatment liquid referred to in the present specification may be ionized (ionized) in the treatment liquid.
  • salt refers to a salt of a compound containing a cationic nitrogen atom (N + ), for example, a halide salt of the compound such as fluoride, chloride, bromide and iodide; Hydroxides; nitrates; as well as sulfates.
  • Such salts may form salts with two or more anions.
  • the salt of the compound containing a sulfonic acid group, a phosphoric acid group and / or a carboxylic acid group include alkali metal salts of the compound such as lithium salt, sodium salt and potassium salt; and alkaline earth such as calcium salt. Metal salts; and ammonium salts.
  • Such salts may form salts with two or more cations. Further, in the polymer, only a part of the groups capable of forming a salt may form a salt, or the whole may form a salt.
  • the treatment liquid of the present invention is at least one organic acid selected from the group consisting of a fluoride ion source, nitric acid, a sulfonic acid compound, a sulfuric acid ester compound, a phosphoric acid ester compound, and a phosphonic acid compound (hereinafter, "" Also referred to as "specific organic acid”) and.
  • the effect of the present invention is excellent when the etching selectivity of the SiGe-containing material with respect to the Si-containing material is excellent and / or the storage stability is excellent with respect to the treatment liquid.
  • the treatment liquid of the present invention contains a fluoride ion source.
  • Fluoride ion source in the processing solution, a fluoride ion (F - and / or HF 2 - as in, ions containing fluorine atom) is a component that emits. Fluoride ions are believed to be able to assist in the removal of oxides of silicon and / or germanium formed under the action of nitric acid described below.
  • fluoride ion source examples include hydrofluoric acid (hydrofluoric acid, HF) and its salt, hexafluorophosphoric acid (HPF 6 ) and its salt (NH 4 PF 6, etc.), and hexafluorosilicic acid (fluorosilicic acid).
  • H 2 SiF 6 ) and its salts Na 2 SiF 6 , (NH 4 ) 2 SiF 6, etc.
  • ammonium fluoride NH 4 F
  • HHF 4 tetrafluoroboric acid HBF 4
  • tetrabutylammonium tetrafluoroborate etc.
  • hydrofluoric acid salt examples include aluminum fluoride, sodium fluoride, potassium fluoride, AlF 2 , LiF 4 , CaF 3 , NaHF 6 , NH 4 HF 2 , KHF 2 , and NR 1 R 2 R 3
  • examples thereof include a quaternary ammonium fluoride salt represented by R 4 F.
  • R 1 , R 2 , R 3 and R 4 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The total number of carbon atoms contained in R 1 , R 2 , R 3 , and R 4 is preferably 1 to 12.
  • Examples of the quaternary ammonium fluoride compound include tetramethylammonium fluoride, tetraethylammonium fluoride, methyltriethylammonium fluoride, and tetrabutylammonium fluoride.
  • the fluoride ion source is preferably hydrofluoric acid, hexafluorophosphoric acid, or hexafluorosilicic acid, and hydrofluoric acid is more preferable in that the effect of the present invention is more excellent.
  • the content of the fluoride ion source is not particularly limited, but 0.001% by mass or more is preferable, and 0.003% by mass or more is more, based on the total mass of the treatment liquid, in that the solubility in SiGe is moderately excellent. It is preferable, and 0.01% by mass or more is more preferable.
  • the upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably less than 1% by mass, and 0.5% by mass, based on the total mass of the treatment liquid, in that the solubility in SiGe is moderately excellent. The following is more preferable. Only one type of fluoride ion source may be used, or two or more types may be used. When two or more types of fluoride ion sources are used, the total amount thereof is preferably within the above range.
  • Nitric acid is considered to have a function of promoting etching of SiGe by acting on SiGe to form oxides (silicon oxide, germanium oxide, and / or silicon-germanium composite oxide, etc.). ing. Nitric acid may form a salt with a cation. Examples of the salt of nitric acid include ferric nitrate and potassium nitrate. Nitric acid preferably does not form a salt with a cation.
  • the content of nitric acid is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, based on the total mass of the treatment liquid, in terms of excellent solubility in SiGe. , 50% by mass or more is particularly preferable.
  • the treatment liquid of the present invention contains at least one specific organic acid selected from the group consisting of a sulfonic acid compound, a sulfate ester compound, a phosphoric acid ester compound, and a phosphonic acid compound.
  • R NA represents a group consisting of an alkyl group, an aryl group, or a combination thereof. These groups may have one or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom and a hydroxy group.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 6 or more carbon atoms, and more preferably 6 to 22 carbon atoms.
  • the aryl group preferably has 6 to 12 carbon atoms.
  • One or more of the ethylene groups in the alkyl group may be replaced with a vinylene group.
  • L NA represents a single bond or a divalent linking group.
  • the linking group of the bivalent, -O -, - CO -, - NR 11 -, - S -, - SO 2 -, - PO (OR 12) -, an alkylene group, an arylene group, or a combination of these A group consisting of is preferable.
  • R 11 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
  • the R 12 represents an alkyl group, an aryl group, or an aralkyl group.
  • the alkylene group and the arylene group may each independently have a substituent, and may have, for example, one or more specific anionic groups described later as the substituent.
  • the L NA is preferably a mono or polyoxyalkylene group (mono or polyoxyethylene group, etc.), a phenylene group, a biphenylene group, or a naphthylene group. These groups may have one or more substituents such as a specific anionic group described later.
  • the above M represents a hydrogen atom or a counter cation. Examples of the counter cation include alkali metal ions (lithium ion, sodium ion, potassium ion, etc.) and ammonium ion.
  • the R NA 2 represents a hydrogen atom, a counter cation, or a group represented by "R NA- L NA-".
  • R NA and L NA in the group represented by "R NA- L NA-” are as described above.
  • the above-mentioned compound represented by “R NA- L NA- Q NA " has a hydrophobic portion (lipophilic group) represented by "R NA- L NA " and a hydrophilic group represented by "Q NA”. Since it has, it has a function as a surfactant.
  • a polymer having a repeating unit containing the above-mentioned specific anionic group can also be mentioned.
  • the repeating unit containing a specific anionic group include styrene sulfonic acid, a repeating unit in the form of condensation of phenol sulfonic acid and formaldehyde, and a repeating unit in the form of condensation of aryl sulfonic acid and formaldehyde.
  • the repeating unit in which these repeating units form a salt can be mentioned.
  • the aryl group in the aryl sulfonic acid include an aryl group having 6 to 14 carbon atoms.
  • the repeating unit having the highest content among the repeating units containing a specific anionic group contained in the polymer is the repeating unit containing a sulfonic acid group.
  • the polymer is a sulfate ester compound, a phosphoric acid ester compound, or a phosphonic acid compound.
  • the polymer also contains a repeating unit other than the repeating unit containing the specific anionic group, the content (molar ratio) of the repeating unit containing the specific anionic group is the highest among all the repeating units. Is preferable.
  • the content of the repeating unit containing a specific anionic group in the polymer is preferably 51 to 100 mol%, more preferably 75 to 100 mol%, based on all the repeating units of the polymer.
  • the weight average molecular weight of the polymer is preferably 400 to 50,000.
  • the sulfonic acid compound contained as the specific organic acid in the treatment liquid is not particularly limited as long as it is a compound having an organic group and one or more sulfonic acid groups in the molecule.
  • a sulfonic acid-based surfactant is preferable.
  • the sulfonic acid-based surfactant include formalin condensates of aryl sulfonic acids such as alkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, alkyldiphenyl ether disulfonic acid, polyoxyalkylene alkyl ether sulfonic acid, styrene sulfonic acid, and phenol sulfonic acid. And their salts (lithium salt, sodium salt, potassium salt or ammonium salt).
  • the sulfonic acid-based surfactant among the compounds represented by the above-mentioned "R NA- L NA- Q NA ", the compound in which Q NA represents a sulfonic acid group and the above-mentioned sulfonic acid group are contained. Also included are polymers with repeating units that do.
  • Ar 1 (-SO 3 M) a (-R) b (-L-Ar 2- SO 3 M) c
  • Ar 1 represents an aromatic hydrocarbon group which may have a substituent.
  • a represents an integer of 1 to 3.
  • M represents a hydrogen atom or a counter cation.
  • R represents an aliphatic hydrocarbon group which may have a substituent.
  • c represents 0 or 1.
  • L represents a single bond, —O—, —S—, or an alkylene group having 1 to 3 carbon atoms.
  • Ar 2 represents an aromatic hydrocarbon group which may have a substituent.
  • k represents an integer of 1 or more.
  • Ar 3 and Ar 4 each independently represent an aromatic hydrocarbon group which may have a substituent.
  • k represents an integer of 2 or more
  • Ar 3 of 2 or more may be the same or different.
  • L 2 represents a single bond or an alkylene group having 1 to 3 carbon atoms.
  • M represents a hydrogen atom or a counter cation. When two or more Ms are present, the two or more Ms may be the same or different.
  • the sulfonic acid-based surfactant represented by the formula (1) will be described.
  • the aromatic hydrocarbon group represented by Ar 1 an aromatic hydrocarbon group having 6 to 14 carbon atoms is preferable, and a phenyl group or a naphthalene group is more preferable.
  • Ar 1 may further have a substituent other than the group represented by the formula (1). Examples of other substituents include a hydroxy group, a halogen atom (fluorine atom, chlorine atom, etc.), a cyano group, and an amino group.
  • a represents an integer of 1 to 3, and 1 or 2 is preferable, and 1 is more preferable.
  • the counter cation represented by M include alkali metal ions (lithium ion, sodium ion, potassium ion, etc.) and ammonium ion.
  • M a hydrogen atom, a sodium ion or an ammonium ion is preferable, and a hydrogen atom or an ammonium ion is more preferable.
  • the compound has 2 or more Ms (ie, a represents 2 or 3 and / or b represents 1), the 2 or more Ms are preferably the same.
  • b represents an integer of 1 to 5, and preferably represents an integer of 1 to 3.
  • the aliphatic hydrocarbon group represented by R may be linear or branched. Further, the aliphatic hydrocarbon group may have a cyclic structure. As the aliphatic hydrocarbon group, a linear or branched alkyl group is preferable.
  • the number of carbon atoms of the aliphatic hydrocarbon group is preferably 2 to 20, and more preferably 3 to 16.
  • the carbon number of R is preferably 8 to 20, more preferably 10 to 16.
  • the number of carbon atoms of the aliphatic hydrocarbon group is preferably 2 to 8, and more preferably 3 to 6.
  • the substituent that the aliphatic hydrocarbon group may have include a mono- or polyoxyalkylene group. That is, the aliphatic hydrocarbon group represented by R may be an aliphatic hydrocarbon group having a mono or polyoxyalkylene group.
  • the divalent alkylene group constituting the mono or polyoxyalkylene group is not particularly limited, but an ethylene group or a 1,2-propanediyl group is preferable, and an ethylene group is more preferable.
  • the number of repetitions of the mono or polyoxyalkylene group is preferably 1 to 6, and more preferably 1 to 3.
  • the aliphatic hydrocarbon group represented by R may further have a substituent other than the mono or polyoxyalkylene group. Examples of other substituents include halogen atoms (fluorine atom, chlorine atom, etc.), cyano group, amino group, and hydroxy group.
  • c 0 or 1.
  • Ar 1 and Ar 2 represent a phenyl group.
  • L represents a single bond, —O—, —S—, or an alkylene group having 1 to 3 carbon atoms. L preferably represents a single bond or —O—, and more preferably —O ⁇ .
  • Ar 2 an aromatic hydrocarbon group having 6 to 14 carbon atoms is preferable, a phenyl group or a naphthalene group is more preferable, and a phenyl group is further preferable.
  • the aromatic hydrocarbon group represented by Ar 2 may have a substituent.
  • substituents examples include an aliphatic hydrocarbon group, a hydroxy group, a halogen atom (fluorine atom, chlorine atom and the like), a cyano group, and an amino group.
  • the aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group represented by R, including its preferred embodiment.
  • the number of carbon atoms per sulfonic acid group of the sulfonic acid-based surfactant represented by the formula (1) is not particularly limited, but 1 to 20 is preferable, and 3 to 13 is more preferable.
  • sulfonic acid-based surfactant represented by the formula (1) include dodecylbenzenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, naphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, and the like.
  • examples thereof include dodecyldiphenyl ether disulfonic acid, polyoxyethylene lauryl ether sulfonic acid, polyoxyethylene oleyl ether sulfonic acid, and polyoxyethylene octyl dodecyl ether sulfonic acid.
  • the sulfonic acid-based surfactant represented by the formula (2) is a formalin condensate of aryl sulfonic acid such as phenol sulfonic acid.
  • k represents an integer of 1 or more. k preferably represents an integer of 1 to 20, and more preferably represents an integer of 3 to 13.
  • an aromatic hydrocarbon group having 6 to 14 carbon atoms is preferable, and a phenyl group or a naphthalene group is more preferable. Further, it is more preferable that at least one of the aromatic hydrocarbon groups represented by Ar 3 and Ar 4 is a naphthalene group.
  • k represents an integer of 2 or more
  • the aromatic hydrocarbon groups represented by Ar 3 of 2 or more may be the same or different.
  • the sulfonic acid-based surfactant represented by the formula (2) has two or more kinds of aromatic hydrocarbon groups different as Ar 3 , the order of their arrangement is not particularly limited, and two or more kinds of aromatics are not particularly limited.
  • the hydrocarbon groups may be randomly arranged, may be arranged alternately, or may be continuously arranged with the same kind of aromatic hydrocarbon groups.
  • Substituents that the aromatic hydrocarbon group represented by Ar 3 and Ar 4 may have include, for example, a hydroxy group, a lower alkyl group, a halogen atom (fluorine atom, chlorine atom, etc.), a cyano group, and a group. Amino groups are mentioned, and hydroxy groups or lower alkyl groups are preferable.
  • the lower alkyl group may be either linear or branched.
  • the lower alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • L 2 is preferably a single bond or a methylene group, and more preferably a single bond.
  • the counter cation represented by M has the same meaning as M in the above formula (1), including its preferred embodiment.
  • the weight average molecular weight of the sulfonic acid-based surfactant represented by the formula (2) is not particularly limited, but is preferably 400 to 50,000, more preferably 500 to 3400.
  • Specific examples of the sulfonic acid-based surfactant represented by the formula (2) include a phenol sulfonic acid formalin condensate, a naphthalene sulfonic acid formalin condensate, and a hydroxynaphthalene sulfonic acid formalin condensate.
  • Examples of the sulfonic acid-based surfactant other than the compounds represented by the above formulas (1) and (2) include alkyl sulfonic acids.
  • the alkyl group of the alkyl sulfonic acid preferably has 6 to 20 carbon atoms, more preferably 8 to 14 carbon atoms.
  • As the alkyl sulfonic acid dodecyl sulfonic acid, octyl sulfonic acid, decyl sulfonic acid, or salts thereof are preferable.
  • sulfonic acid-based surfactants examples include Takemoto Oil & Fat Co., Ltd.'s "Takesurf” series ("Takesurf A32-Q”, “Takesurf A45-Q”, “Takesurf A43-NQ” and “Takesurf A47-”. Q ”, etc.) and“ Pionin ”series (“Pionin A-44-B”, etc.), “Demor SS-L” and “Perex SS-H” manufactured by Kao Corporation, and “Laberin” manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. FC-45 ”(both are trade names).
  • the sulfate ester compound is not particularly limited as long as it is a compound having an organic group and one or more sulfate groups in the molecule, but a sulfate ester-based surfactant is preferable.
  • the sulfate ester-based surfactant examples include an alkyl sulfate ester, a polyoxyalkylene alkyl ether sulfate ester, a polyoxyalkylene aryl ether sulfate ester, and salts thereof.
  • the salt of the sulfate ester-based surfactant examples include a sodium salt, a potassium salt, an ammonium salt, and an organic amine salt, and a sodium salt or an ammonium salt is preferable.
  • the sulfate ester-based surfactant among the compounds represented by the above-mentioned "R NA- L NA- Q NA ", a compound in which Q NA represents a sulfuric acid group can also be mentioned.
  • the monovalent alkyl group contained in the alkyl sulfate ester and the polyoxyalkylene alkyl ether sulfuric acid ester is not particularly limited and may be linear or branched.
  • the alkyl group preferably has 2 to 24 carbon atoms, more preferably 6 to 18 carbon atoms. Further, one or more of the ethylene groups in the alkyl group may be replaced with a vinylene group.
  • the alkyl group may have a substituent. Examples of the substituent include a hydroxy group, a halogen atom (fluorine atom, chlorine atom, etc.), a cyano group, and an amino group.
  • the monovalent aryl group contained in the polyoxyalkylene aryl ether sulfate ester is not particularly limited, but a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • the aryl group may have a substituent. Examples of the substituent include an alkyl group, a hydroxy group, a halogen atom (fluorine atom, chlorine atom, etc.), a cyano group, and an amino group.
  • the alkyl group is synonymous with the alkyl group contained in the alkyl sulfate ester, including its preferred embodiment.
  • the divalent alkylene group contained in the polyoxyalkylene alkyl ether sulfate ester and the polyoxyalkylene aryl ether sulfate ester is not particularly limited, but an ethylene group or a 1,2-propanediyl group is preferable, and an ethylene group is more preferable. Further, the number of repetitions of the oxyalkylene group contained in these sulfate esters is preferably 1 to 12, more preferably 1 to 6.
  • sulfate ester-based surfactant examples include lauryl sulfate, myristyl sulfate, polyoxyethylene arylphenyl ether sulfate, polyoxyethylene lauryl ether sulfate, and salts thereof.
  • examples of commercially available sulfate ester-based surfactants include "New Calgen FS-75PG” manufactured by Takemoto Oil & Fat Co., Ltd. and "NIKKOL SBL-3N-27" manufactured by Nikko Chemicals Co., Ltd. (both are trade names). Can be mentioned.
  • the phosphoric acid ester compound is not particularly limited as long as it is a compound having an organic group and one or more phosphoric acid groups in the molecule, but a phosphoric acid ester-based surfactant is preferable.
  • Examples of the phosphoric acid ester-based surfactant include alkyl phosphoric acid esters, polyoxyalkylene alkyl ether phosphoric acid esters, and salts thereof.
  • the alkyl phosphoric acid ester and the polyoxyalkylene ether phosphoric acid may be any of phosphoric acid monoesters, diesters and triesters, and monoesters, diesters or mixtures thereof are preferable.
  • Examples of the salt of the phosphoric acid ester-based surfactant include a sodium salt, a potassium salt, an ammonium salt, and an organic amine salt. Further, as the phosphoric acid ester-based surfactant , among the compounds represented by the above-mentioned "R NA- L NA- Q NA ", a compound in which Q NA represents a phosphoric acid group can also be mentioned.
  • the monovalent alkyl group contained in the alkyl phosphate ester and the polyoxyalkylene alkyl ether phosphoric acid ester is synonymous with the monovalent alkyl group contained in the above-mentioned alkyl sulfate ester, including its preferred embodiment.
  • the divalent alkylene group contained in the polyoxyalkylene alkyl ether phosphoric acid ester is not particularly limited, but an alkylene group having 2 to 6 carbon atoms is preferable, an ethylene group or a 1,2-propanediyl group is more preferable, and ethylene is preferable. Groups are even more preferred.
  • the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether phosphoric acid ester is preferably 1 to 12, more preferably 1 to 6.
  • phosphoric acid ester-based surfactants include octyl phosphate, lauryl phosphate, tridecyl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, and bis (2-ethylhexyl) phosphate. , Distearyl phosphate ester, dodecyl phosphate ester, and polyoxyethylene lauryl ether phosphate ester in which the number of repetitions of the oxyethylene group is 1 to 6.
  • phosphoric acid ester-based surfactants include "NIKKOL Hosten HLP-1” manufactured by Nikko Chemicals Co., Ltd., and "CRODAFOS-03A-LQ” and “CRODAFOS-10A-LQ” manufactured by Crowder Japan Co., Ltd. Also the product name).
  • the phosphonic acid compound is not particularly limited as long as it is a compound having an organic group and one or more phosphonic acid groups in the molecule, but a phosphonic acid-based surfactant is preferable.
  • Examples of the phosphonic acid-based surfactant include alkylphosphonic acid, polyoxyalkylene alkyl ether phosphonic acid, and salts thereof.
  • Examples of the salt of the phosphonic acid-based surfactant include a sodium salt, a potassium salt, an ammonium salt, and an organic amine salt, and a sodium salt or an ammonium salt is preferable.
  • examples of the phosphonic acid-based surfactant include compounds in which Q NA represents a phosphonic acid group among the compounds represented by the above-mentioned "R NA- L NA- Q NA".
  • the monovalent alkyl group contained in the alkylphosphonic acid and the polyoxyalkylene alkyl ether phosphonic acid is synonymous with the monovalent alkyl group contained in the above-mentioned alkyl sulfate ester, including its preferred embodiment.
  • the divalent alkylene group contained in the polyoxyalkylene alkyl ether phosphonic acid is not particularly limited, but an alkylene group having 2 to 6 carbon atoms is preferable, an ethylene group or a 1,2-propanediyl group is more preferable, and an ethylene group. Is more preferable.
  • the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether phosphonic acid is preferably 1 to 12, more preferably 1 to 6.
  • phosphonic acid-based surfactant examples include decylphosphonic acid, dodecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, octadecylphosphonic acid, polyvinylphosphonic acid, and JP-A-2012-057108.
  • decylphosphonic acid dodecylphosphonic acid
  • tetradecylphosphonic acid hexadecylphosphonic acid
  • octadecylphosphonic acid polyvinylphosphonic acid
  • JP-A-2012-057108 The aminomethylphosphonic acid described is mentioned.
  • the treatment liquid preferably contains a sulfonic acid compound or a sulfuric acid ester compound as a specific organic acid in that the effect of the present invention is more excellent, and more preferably contains a sulfonic acid compound in that the storage stability is more excellent. preferable.
  • the content of the specific organic acid is not particularly limited, but 0.0001 to 10% by mass is preferable, and 0.0005 to 2% by mass is more, based on the total mass of the treatment liquid, in that the effect of the present invention is more excellent. It is preferably 0.001 to 0.5% by mass, and more preferably 0.001 to 0.5% by mass. Only one type of specific organic acid may be used, or two or more types may be used. When two or more kinds of specific organic acids are used, the total amount thereof is preferably within the above range.
  • the treatment liquid may contain water, and preferably contains water.
  • the water is not particularly limited, and examples thereof include distilled water, ion-exchanged water, and pure water.
  • the content of water in the treatment liquid is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, based on the total mass of the treatment liquid.
  • the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.
  • the treatment liquid may contain an alkanolamine, and is preferably further contained an alkanolamine in that it is superior in etching selectivity of the SiGe-containing material with respect to silicon nitride (SiN).
  • An alkanolamine is a compound having an alkane skeleton, one or more hydroxy groups, and one or more amino groups in the molecule.
  • the alkane skeleton such as an alkyl group contained in the alkanolamine is not particularly limited and may be linear or branched, and may be composed of only carbon atoms constituting the alkane skeleton or an alkane skeleton.
  • a cyclic structure may be formed by a carbon atom constituting the carbon atom and a nitrogen atom constituting the amino group.
  • the amino group contained in the alkanolamine may be any of a primary amino group (-NH 2 ), a secondary amino group (> NH) and a tertiary amino group (> N-), and is secondary.
  • Amino groups or tertiary amino groups are preferred.
  • the number of amino groups contained in the alkanolamine is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 3.
  • the number of hydroxy groups contained in the alkanolamine is not particularly limited, but is preferably 1 to 8 and more preferably 2 to 5.
  • the carbon number of the alkanolamine is preferably 1 to 20, more preferably 4 to 16.
  • the molecular weight of the alkanolamine is preferably 15 or more and less than 400, more preferably 15 to 300.
  • R 1 represents an alkyl group having 1 to 8 carbon atoms which may have a hydroxy group or an amino group.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a hydroxy group.
  • R 3 represents an alkyl group having 1 to 8 carbon atoms which may have a hydroxy group. Two groups selected from R 1 , R 2 and R 3 may form a ring. Further, at least one of R 1 , R 2 and R 3 represents an alkyl group having a hydroxy group and having 1 to 8 carbon atoms.
  • the number of carbon atoms of the alkyl group represented by R 1 to R 3 is preferably 1 to 6, and more preferably 2 to 6.
  • the total number of carbon atoms of the alkyl groups represented by R 1 to R 3 is preferably 4 to 16, and more preferably 6 to 10.
  • the number of hydroxy groups that each of R 1 to R 3 may have is not particularly limited, but 1 to 5 are preferable.
  • the total number of hydroxy groups contained in R 1 to R 3 is preferably 2 to 5.
  • the number of amino groups that R 1 may have is not particularly limited, but is preferably 1 or 2, and more preferably 1.
  • Examples of the ring formed by the two groups selected from R 1 , R 2 and R 3 include a piperidine ring, a pyridine ring, a piperazine ring, a morpholine ring, and a pyrrolidine ring.
  • alkanolamine examples include diethanolamine, diisopropanolamine, triisopropanolamine, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethoxy) ethanol, triethanolamine, 1- [bis (2-hydroxy).
  • Amino] -2-propanol, diisopropanolamine, or N-octylglucamine is preferable, and N- (3-aminopropyl) diethanolamine and N-butyldiethanolamine are more excellent in solubility in SiGe and the effect of the present invention.
  • 1- [bis (2-hydroxyethyl) amino] -2-propanol and diisopropanolamine are more preferable.
  • alkanolamine Only one type of alkanolamine may be used, or two or more types may be used.
  • the content of the alkanolamine is not particularly limited, but 0.001 to 10% by mass is preferable, and 0.01 to 5% by mass is more preferable, based on the total mass of the treatment liquid, in that the effect of the present invention is more excellent. , 0.05 to 1% by mass is more preferable.
  • the ratio of the content of the specific organic acid to the content of the alkanolamine is 0.001 to the mass ratio in that the solubility in SiGe is more excellent. 10.0 is preferable, 0.01 to 2.0 is more preferable, and 0.03 to 1.0 is further preferable.
  • the treatment liquid may contain a metal component.
  • the metal component include metal particles and metal ions.
  • the content of a metal component indicates the total content of metal particles and metal ions.
  • the treatment liquid may contain either one of metal particles and metal ions, or may contain both.
  • the metal atom contained in the metal component examples include Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na. , Ni, Pb, Sn, Sr, Ti, and a metal atom selected from the group consisting of Zn.
  • the metal component may contain one kind of metal atom or two or more kinds.
  • the metal particles may be simple substances or alloys, and may exist in a form in which the metal is associated with an organic substance.
  • the metal component may be a metal component unavoidably contained in each component (raw material) contained in the treatment liquid, or may be a metal component unavoidably contained during the production, storage, and / or transfer of the treatment liquid. However, it may be added intentionally.
  • the content of the metal component is often 0.01 mass ppt to 10 mass ppm, and 0.1 mass ppt to 1 mass ppm with respect to the total mass of the treatment liquid. preferable.
  • the sodium content in the treatment liquid is preferably 100 mass ppb or less, more preferably 10 mass ppb or less, and further preferably 3 mass ppb or less. This is because when the sodium content in the treatment liquid is within the above range, the content of impurity particles contained in the treatment liquid can be suppressed to a low level.
  • the sodium content in the treatment liquid means the total content of sodium particles and sodium ions.
  • the lower limit of the sodium content in the treatment liquid is not particularly limited and may be below the detection limit, but in many cases it is 0.01 mass ppt or more.
  • the type and content of the metal component in the treatment liquid can be measured by the SP-ICP-MS method (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).
  • the SP-ICP-MS method uses the same apparatus as the ICP-MS method (inductively coupled plasma mass spectrometry), and differs only in data analysis. Data analysis of the SP-ICP-MS method can be performed by commercially available software.
  • the content of the metal component to be measured is measured regardless of its existence form. Therefore, the total mass of the metal particles and the metal ions to be measured is quantified as the content of the metal component.
  • the content of metal particles can be measured. Therefore, the content of metal ions in the sample can be calculated by subtracting the content of the metal particles from the content of the metal component in the sample.
  • Agilent 8800 triple quadrupole ICP-MS inductively coupled plasma mass spectrometry, for semiconductor analysis, option # 200
  • Agilent Technologies is used as an example. It can be measured by the method described.
  • NexION350S manufactured by PerkinElmer and Agilent 8900 manufactured by Agilent Technologies can also be used.
  • the treatment liquid may contain components other than the above.
  • other components that the treatment liquid may contain include an oxidizing agent other than nitric acid, a surfactant other than the specific organic acid, and an organic solvent.
  • oxidizing agents other than nitrates include peroxides, persulfides (monopersulfides and dipersulfides, etc.), percarbonates, oxide halides (iodic acid, periodic acid, etc.), perboric acid, and the like.
  • surfactant other than the specific organic acid examples include anionic surfactants other than the specific organic acid, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
  • organic solvent examples include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, sulfone-based solvents, sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents.
  • the method for producing the above-mentioned treatment liquid is not particularly limited, and a known production method can be used. For example, a method of mixing a fluoride ion source, nitric acid and a specific organic acid in a predetermined amount can be mentioned. When mixing the above components, if necessary, optional components such as water and alkanolamine may be mixed together. Further, when producing the treatment liquid, the treatment liquid may be filtered and purified using a filter, if necessary.
  • the treatment liquid may be contained in a container and stored until use. Such a container and the treatment liquid contained in the container are collectively referred to as a treatment liquid container.
  • the treatment liquid is taken out from the stored treatment liquid container and used. Further, the treatment liquid may be transported as a treatment liquid container, and the treatment liquid may be provided between the manufacturer and the user, or between the storage place and the place of use.
  • the container has a degassing mechanism for adjusting the pressure (internal pressure) in the container.
  • the degassing mechanism is, for example, a gas generated when the temperature of the treatment liquid inside the container rises during storage of the treatment liquid container and / or gas is generated from the treatment liquid due to decomposition of some components of the treatment liquid. Is a mechanism that releases the gas from the inside of the container to the outside and keeps it within a certain range without excessively increasing the internal pressure.
  • Examples of the degassing mechanism include a check valve and a degassing cap provided with the degassing mechanism. Further, from the viewpoint of convenience of handling the treatment liquid, the treatment liquid is provided between the manufacturer and the user or between the storage place and the place of use by the method using such a treatment liquid container. Is preferable.
  • the container has a high degree of cleanliness inside the container and less elution of impurities for semiconductor applications.
  • Examples of usable containers include the "clean bottle” series manufactured by Aicello Chemical Corporation and the "pure bottle” manufactured by Kodama Resin Industry.
  • the inner wall of the container (particularly the container body) is preferably formed of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin and polyethylene-polypropylene resin, or a resin different from this. Further, it is also preferable that the inner wall of the container (particularly the container body) is formed of a metal that has been subjected to rust prevention and metal elution prevention treatment, such as stainless steel, Hastelloy, Inconel and Monel.
  • a fluororesin (perfluororesin) is preferable.
  • a container whose inner wall is a fluororesin By using a container whose inner wall is a fluororesin, it is possible to suppress the occurrence of a problem of elution of ethylene or propylene oligomer as compared with a container whose inner wall is a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin.
  • Examples of the container whose inner wall is a fluororesin include a FluoroPure PFA composite drum manufactured by Entegris.
  • the containers described on page 4 of the special table No. 3-502677, page 3 of the pamphlet of International Publication No. 2004/016526, and pages 9 and 16 of the pamphlet of International Publication No. 99/046309 are also included. Can be used.
  • quartz and an electropolished metal material are also preferably used for the inner wall of the container (particularly the container body).
  • the metal material used for producing the electropolished metal material contains at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is 25 with respect to the total mass of the metal material. It is preferably a metal material having a mass% of more than%, and examples thereof include stainless steel and nickel-chromium alloys.
  • the total content of chromium and nickel in the metal material is preferably 30% by mass or more with respect to the total mass of the metal material.
  • the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is preferably 90% by mass or less with respect to the total mass of the metal material.
  • the stainless steel is not particularly limited, and known stainless steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable.
  • austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), and SUS316. (Ni content 10% by mass, Cr content 16% by mass) and SUS316L (Ni content 12% by mass, Cr content 16% by mass) can be mentioned.
  • the nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Of these, nickel-chromium alloys having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass are preferable. Examples of the nickel-chromium alloy include Hastelloy (trade name, the same shall apply hereinafter), Monel (trade name, the same shall apply hereinafter), and Inconel (trade name, the same shall apply hereinafter).
  • Hastelloy C-276 Ni content 63% by mass, Cr content 16% by mass
  • Hastelloy-C Ni content 60% by mass, Cr content 17% by mass
  • Hastelloy C- 22 Ni content 61% by mass, Cr content 22% by mass
  • the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, or cobalt in addition to the above alloy, if necessary.
  • the method for electropolishing a metal material is not particularly limited, and a known method can be used.
  • a known method can be used.
  • the methods described in paragraphs [0011]-[0014] of JP2015-227501 and paragraphs [0036]-[0042] of JP2008-264929 can be used.
  • the metal material is preferably buffed.
  • the method of buffing is not particularly limited, and a known method can be used.
  • the size of the abrasive grains used for finishing the buffing is not particularly limited, but # 400 or less is preferable because the unevenness on the surface of the metal material tends to be smaller.
  • the buffing is preferably performed before the electrolytic polishing. Further, the metal material is obtained by performing one or two or more combinations of treatments such as buffing, acid cleaning, and magnetic fluid polishing in a plurality of stages performed by changing the count such as the size of abrasive grains. May be good.
  • the inside of these containers is cleaned before filling with the treatment liquid.
  • the liquid used for cleaning preferably has a reduced amount of metal impurities in the liquid.
  • the treatment liquid may be bottling, transported or stored in a container such as a gallon bottle or a coated bottle after production.
  • the inside of the container may be replaced with an inert gas (chisso, argon, etc.) having a purity of 99.99995% by volume or more for the purpose of preventing changes in the components in the treatment liquid during storage.
  • an inert gas chisso, argon, etc.
  • a gas having a low water content is preferable.
  • the temperature may be normal temperature, but the temperature may be controlled in the range of ⁇ 20 ° C. to 20 ° C. in order to prevent deterioration.
  • the treatment liquid may be a kit in which the raw material is divided into a plurality of parts. Further, the treatment liquid may be prepared as a concentrated liquid. When the treatment liquid is a concentrated liquid, the concentration ratio thereof is appropriately determined depending on the composition of the composition, but is preferably 5 to 2000 times. That is, the concentrated solution is diluted 5 to 2000 times before use.
  • the treatment liquid of the present invention is used in a treatment method for treating a SiGe-containing substance and an object to be treated having a Si-containing substance (hereinafter, also simply referred to as "the present treatment method").
  • the present treatment method By this treatment method, at least a part of the Si-containing material contained in the object to be treated is removed (etched).
  • the SiGe-containing material is a material containing a combination of silicon (Si) and germanium (Ge), and is preferably usable as a semiconductor material.
  • the SiGe-containing material may intentionally or unavoidably contain components other than silicon and germanium.
  • the total content of silicon and germanium in the SiGe-containing material is preferably 95 to 100% by mass, more preferably 99 to 100% by mass, still more preferably 99.9 to 100% by mass, based on the total mass of the SiGe-containing material. ..
  • the elemental ratio of silicon (Si) to germanium (Ge) in the SiGe-containing material (ratio of atom% occupied by Si atoms to atom% occupied by Ge atoms in the SiGe-containing material, Si: Ge) is determined. 99: 1 to 30:70 is preferable, 95: 5 to 50:50 is more preferable, and 85:15 to 65:35 is even more preferable.
  • the Si-containing material is a material containing silicon (Si).
  • the Si-containing material may intentionally or unavoidably contain a component other than silicon.
  • the silicon content in the Si-containing material is preferably 95 to 100% by mass, more preferably 99 to 100% by mass, still more preferably 99.9 to 100% by mass, based on the total mass of the Si-containing material.
  • the form of the SiGe-containing substance and the Si-containing substance contained in the object to be treated is not particularly limited, and may be, for example, any of a film-like form, a wiring-like form, and a particle-like form.
  • the thickness thereof is not particularly limited and may be appropriately selected depending on the intended use, for example, 1 to 50 nm.
  • the SiGe-containing material and the Si-containing material may be arranged only on one main surface of the substrate, or may be arranged on both main surfaces. Further, the SiGe-containing material and the Si-containing material may be arranged on the entire main surface of the substrate, or may be arranged on a part of the main surface of the substrate.
  • FIG. 1 is a cross-sectional view showing an example of the form of the object to be treated.
  • the object to be processed 10 shown in FIG. 1 has a substrate 12 and SiGe-containing layers 14 and a coating layer 16 alternately laminated on the substrate 12. Further, in the object to be processed 10 shown in FIG. 1, at least one of the substrate 12 and the coating layer 16 is composed of a Si-containing substance.
  • the form of the object to be treated is not limited to the mode shown in FIG.
  • the object 10 shown in FIG. 1 has two layers of a SiGe-containing layer 14 and two layers of a coating layer 16, but the SiGe-containing layer 14 and the coating layer 16 may have only one layer, respectively. Alternatively, there may be three or more layers.
  • the SiGe-containing layer 14 and / or the coating layer 16 may not exist.
  • the SiGe-containing layer 14 is directly arranged on the substrate 12, but it may be arranged via another layer.
  • the coating layer 16 may be a layer made of a material other than the SiGe-containing material. When a plurality of coating layers 16 are present, the materials constituting the plurality of coating layers 16 may be different from each other. Above all, the object 10 to be treated preferably has at least one coating layer 16 which is a Si-containing layer.
  • the material constituting the substrate 12 is not particularly limited, and examples thereof include group III-V compounds such as silicon, silicon germanium, and GaAs, and any combination thereof. Of these, Si-containing substances are preferable.
  • the type of substrate is not particularly limited, and is a semiconductor wafer, a glass substrate for a photomask, a glass substrate for a liquid crystal display, a glass substrate for plasma display, a substrate for FED (Field Emission Display), a substrate for an optical disk, a substrate for a magnetic disk, and Examples thereof include various substrates such as a substrate for a magneto-optical disk.
  • the size, thickness, shape, and layer structure of the substrate are not particularly limited and can be appropriately selected as desired.
  • the object to be treated may contain a metal hard mask.
  • the object 10 shown in FIG. 1 may further contain a metal hard mask.
  • the metal hard mask contains, for example, any one or more of Cu, Co, W, AlO x , AlN, AlO x N y , WO x , Ti, TiN, ZrO x , HfO x , and TaO x.
  • the metal hard mask one or more of Cu, Co, W, AlO x , AlN, AlO x N y , WO x , Ti, TiN, ZrO x , HfO x , and TaO x can be used as the metal hard mask. It is preferably contained in an amount of 30 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 95 to 100% by mass with respect to the total mass.
  • the object to be treated may have various layers and / or structures as desired.
  • the substrate may have members such as metal wiring, gate electrodes, source electrodes, drain electrodes, insulating layers, ferromagnetic layers, and / or non-magnetic layers.
  • the substrate may have an exposed integrated circuit structure, such as an interconnect mechanism for metal wiring and dielectric materials. Examples of the material used for the interconnection mechanism include aluminum, copper-aluminum alloy, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten.
  • the substrate may have layers of silicon oxide, silicon nitride, silicon carbide, and / or carbon-doped silicon oxide.
  • the manufacturing method of the object to be processed is not particularly limited.
  • an insulating film is formed on the substrate, and SiGe is formed on the insulating film by a sputtering method, a chemical vapor deposition (CVD) method, a molecular beam epitaxy (MBE) method, or the like.
  • CVD chemical vapor deposition
  • MBE molecular beam epitaxy
  • a flattening treatment such as CMP may be carried out to produce the object to be treated shown in FIG.
  • Examples of the method for treating the object to be treated include a method for dissolving SiGe by bringing the SiGe-containing substance and the object to be treated having the Si-containing substance into contact with the above-mentioned treatment liquid.
  • the method of bringing the object to be treated into contact with the treatment liquid is not particularly limited. Examples include a method of flowing the treatment liquid on top and any combination thereof. Above all, a method of immersing the object to be treated in the treatment liquid is preferable.
  • a mechanical stirring method may be used.
  • the mechanical stirring method include a method of circulating the treatment liquid on the object to be treated, a method of flowing or spraying the treatment liquid on the object to be treated, and stirring the treatment liquid by ultrasonic waves or megasonic. The method can be mentioned.
  • the contact time between the object to be treated and the treatment liquid can be adjusted as appropriate.
  • the treatment time (contact time between the treatment liquid and the object to be treated) is not particularly limited, but is preferably 0.25 to 20 minutes, more preferably 0.5 to 15 minutes.
  • the temperature of the treatment liquid during the treatment is not particularly limited, but is preferably 20 to 75 ° C, more preferably 20 to 60 ° C.
  • This treatment using the above treatment liquid is excellent in etching selectivity of SiGe with respect to Si. That is, this treatment can satisfactorily dissolve SiGe while suppressing the dissolution of Si in the object to be treated.
  • the ratio of the dissolution rate of SiGe to the dissolution rate of Si in this treatment is preferably 25 or more, more preferably 50 or more, and even more preferably 100 or more.
  • the upper limit is not particularly limited, but is preferably 1000 or less.
  • the dissolution rate of SiGe in this treatment is preferably 25 ⁇ / min or more, more preferably 40 to 300 ⁇ / min, further preferably 50 to 200 ⁇ / min, and particularly preferably 75 to 125 ⁇ / min.
  • the dissolution rate of Si in this treatment is preferably less than 10 ⁇ / min, more preferably 0.01 to 5 ⁇ / min, and even more preferably 0.01 to 3 ⁇ / min.
  • the other material may or may be dissolved together with SiGe by this treatment. It does not have to be.
  • the other material may be dissolved intentionally or inevitably.
  • the other material is not intentionally dissolved, it is preferable that the amount of the other material inevitably dissolved is small. In the present specification, the fact that the amount of the material that is inevitably dissolved is small is also referred to as excellent member resistance to the material.
  • the treatment liquid preferably has excellent member resistance to SiN.
  • the dissolution rate of SiN in this treatment is preferably less than 10 ⁇ / min, more preferably 0.01 to 5 ⁇ / min, even more preferably 0.01 to 3 ⁇ / min, and particularly preferably 0.01 to 2 ⁇ / min.
  • the ratio of the dissolution rate of SiGe to the dissolution rate of SiN in this treatment is preferably 25 or more, more preferably 50 or more, still more preferably 100 or more.
  • the upper limit is not particularly limited, but is preferably 1000 or less.
  • FIG. 2 is a cross-sectional view showing an example of an object to be treated that has been treated with the treatment liquid.
  • the object to be processed 10 shown in FIG. 2 shows an aspect after the object to be processed 10 shown in FIG. 1 is processed by this processing method.
  • the coating layer 16 is a material that is not intentionally dissolved, and a part of the SiGe-containing layer 14 is dissolved from the side surface by this treatment method to form a recess.
  • the coating is applied.
  • the layer 16 is preferably supported by another material (not shown).
  • this treatment method may include a rinsing step of rinsing the object to be treated with a rinsing liquid.
  • a rinsing step may be further performed after the object to be treated is brought into contact with the treatment liquid.
  • rinsing solution examples include water, hydrofluoric acid (preferably 0.001 to 1% by mass hydrofluoric acid), hydrochloric acid (preferably 0.001 to 1% by mass hydrochloric acid), and aqueous hydrogen solution (preferably 0.5 to 1% by mass). 31 mass% aqueous solution of hydrogen peroxide, more preferably 3 to 15 mass% aqueous solution of hydrogen peroxide), mixed solution of hydrofluoric acid and aqueous solution of hydrogen peroxide (FPM), mixed solution of sulfuric acid and aqueous solution of hydrogen peroxide (SPM).
  • Aqueous solution of ammonia water and aqueous solution of hydrogen peroxide APM
  • Aqueous solution of hydrogen peroxide APM
  • mixture of aqueous solution of hydrochloric acid and aqueous solution of hydrogen peroxide HPM
  • water of carbon dioxide preferably 10 to 60 mass ppm water of carbon dioxide
  • ozone water preferably Is 10 to 60 mass ppm ozone water
  • hydrogen water preferably 10 to 20 mass ppm hydrogen water
  • citrate aqueous solution preferably 0.01 to 10 mass% citrate aqueous solution
  • sulfuric acid preferably 1 to 10 mass.
  • the volume ratio of "37% by mass hydrochloric acid: 60% by mass nitric acid” is (Osui) corresponding to the combination of "2.6: 1.4" to "3.4: 0.6"), ultrapure water, nitric acid.
  • perchloric acid preferably 0.001 to 1% by mass perchloric acid
  • oxalic acid aqueous solution preferably 0.01 to 10% by mass oxalic acid aqueous solution
  • acetic acid Preferably 0.01 to 10 mass% acetic acid aqueous solution or acetic acid stock solution
  • perioic acid aqueous solution preferably 0.5 to 10 mass% perioic acid aqueous solution.
  • Perioic acid is, for example, ortho-periodine. Acids and metaperiodic acids are preferred).
  • composition ratios ammonia water is 28% by mass ammonia water, hydrofluoric acid is 49% by mass, sulfuric acid is 98% by mass sulfuric acid, hydrochloric acid is 37% by mass hydrochloric acid, and hydrogen peroxide solution is 30% by mass. %
  • the composition ratio in the case of aqueous hydrogen peroxide is intended.
  • the volume ratio is based on the volume at room temperature.
  • Hydrofluoric acid, nitric acid, perchloric acid, and hydrochloric acid are intended as aqueous solutions in which HF, HNO 3 , HClO 4 , and HCl are dissolved in water, respectively.
  • Ozone water, carbon dioxide water, and hydrogen water are intended as aqueous solutions in which O 3 , CO 2 , and H 2 are dissolved in water, respectively.
  • These rinsing liquids may be mixed and used as long as the purpose of the rinsing step is not impaired. Further, the rinse liquid may contain an organic solvent.
  • Specific methods of the rinsing step include a method of bringing the rinsing liquid into contact with the object to be treated.
  • the contacting method is carried out by immersing the substrate in the rinse liquid contained in the tank, spraying the rinse liquid on the substrate, flowing the rinse liquid on the substrate, or any combination thereof.
  • the treatment time is not particularly limited, but is, for example, 5 seconds to 5 minutes.
  • the temperature of the rinsing liquid during the treatment is not particularly limited, but is preferably 16 to 60 ° C, more preferably 18 to 40 ° C. When SPM is used as the rinsing liquid, the temperature is preferably 90 to 250 ° C.
  • the present treatment method may include a drying step of carrying out a drying treatment, if necessary, after the rinsing step.
  • the method of drying treatment is not particularly limited, but spin drying, flow of dry gas on the substrate, heating means of the substrate such as heating with a hot plate or an infrared lamp, IPA (isopropyl alcohol) steam drying, marangoni drying, rotagoni drying, or , A combination thereof.
  • the drying time varies depending on the specific method used, but is usually about 30 seconds to several minutes.
  • This treatment method may be used for cleaning an object to be treated. More specifically, the treatment liquid may be used for a cleaning application in which the semiconductor substrate after dry etching is used as an object to be processed and the dry etching residue on the Si substrate is removed. At this time, the dry etching residue may or may not be a SiGe-containing substance. Further, the object to be treated may or may not have a SiGe-containing substance in a form other than the dry etching residue. Examples of the cleaning treatment method of applying the treatment liquid to the object to be treated in such a cleaning application include a method of bringing the object to be treated into contact with the treatment liquid, and specifically, a method of dissolving the above-mentioned SiGe.
  • the same may be applied to the method of bringing the object to be treated into contact with the above-mentioned treatment liquid described in the above section. Further, after the cleaning treatment, the rinsing step and / or the drying treatment described in the above-mentioned method for dissolving SiGe may be carried out. Further, the cleaning treatment may be carried out at the same time as the above-mentioned method for dissolving SiGe.
  • the treatment method using the treatment liquid may be carried out in combination before or after other steps performed in the method for manufacturing a semiconductor device.
  • the present treatment method may be incorporated into other steps during the implementation of the present treatment method, or the present treatment method may be incorporated into the other steps.
  • Other steps include, for example, a step of forming each structure such as a metal wiring, a gate structure, a source structure, a drain structure, an insulating layer, a ferromagnetic layer and / or a non-magnetic layer (layer formation, etching, chemical mechanical polishing, and chemical mechanical polishing, and , Transformation, etc.), resist forming step, exposure step and removal step, heat treatment step, cleaning step, and inspection step.
  • This processing method is performed at any stage of the back end process (BEOL: Back end of the line), the middle process (MOL: Middle of the line), and the front end process (FEOL: Front end of the line). May be good.
  • the processing liquid is applied to, for example, NAND, DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), ReRAM (Resistive Random Access Memory), FRAM (registered trademark) (Ferroelectric Random Access Memory), MRAM. (Magnetoresistive Random Access Memory), PRAM (Phase change Random Access Memory), or a logic circuit or processor.
  • each component shown below was mixed so as to have the content shown in the table below to prepare a treatment liquid to be applied to each test.
  • semiconductor-grade high-purity raw materials were used, and further purification treatment was carried out as necessary.
  • the polymer compound (polymer) used as a raw material contains only typical repeating units for constituting the polymer of the name.
  • the aryl sulfonic acid formalin condensate used in the examples contains only repeating units in the form of condensation of aryl sulfonic acid and formaldehyde.
  • AA-1 N- (3-aminopropyl) diethanolamine
  • AA-2 3-morpholino-1,2-propanediol
  • AA-3 N-butyldiethanolamine
  • AA-4 N-ethylglucamine
  • AA-5 N-methylglucamine
  • AA-6 1- [bis (2-hydroxyethyl) amino] -2-propanol
  • AA-7 diisopropanolamine
  • AA-8 N-octylglucamine
  • the measurement was performed again with the treatment liquid to be measured appropriately concentrated, and the measurement was obtained.
  • the Na content was calculated by converting the measured value into the concentration of the treatment liquid before concentration.
  • a substrate on which silicon germanium (Si: Ge 75: 25 (elemental ratio)) is laminated with a film thickness of 100 nm, a substrate on which polysilicon (Si) is laminated with a film thickness of 100 nm, and silicon nitride (SiN) as a film thickness.
  • Substrates laminated at 100 nm were prepared, and each of these substrates was cut into 2 ⁇ 2 cm squares to prepare a test piece.
  • the test body was immersed in the treatment liquid (25 ° C.) of the example or comparative example for 10 minutes.
  • the film thicknesses of the SiGe film, the Si film, and the SiN film were measured with an optical film thickness meter Ellipsometer M-2000 (manufactured by JA Woollam). From the measured film thickness before and after immersion, the dissolution rate ( ⁇ / min) of each film when each treatment liquid was used was calculated. From the calculated dissolution rate of the SiGe membrane, the solubility of each treatment liquid in the SiGe membrane was evaluated based on the following evaluation criteria.
  • Dissolution rate is 90 to 110 ⁇ / min
  • B Dissolution rate is 75 ⁇ / min or more and less than 90 ⁇ / min or 110 ⁇ / min or more and less than 125 ⁇ / min
  • C Dissolution rate is 50 ⁇ / min or more and less than 75 ⁇ / min or 125 ⁇ / min or more Less than 200 ⁇ / min
  • D Dissolution rate is 25 ⁇ / min or more and less than 50 ⁇ / min or 200 ⁇ / min or more
  • E Dissolution rate is less than 25 ⁇ / min
  • the ratio of the dissolution rate of the SiGe film to the dissolution rate of the Si film (SiGe / Si dissolution rate ratio) and the dissolution rate of the SiN film of the SiGe film.
  • the dissolution rate ratio (SiGe / SiN dissolution rate ratio) was calculated. From each of the calculated dissolution rate ratios, the etching selectivity of the SiGe film with respect to the Si film and the etching selectivity of the SiGe film with respect to the SiN film were evaluated based on the following evaluation criteria.
  • SiGe / Si dissolution rate ratio is 100 or more
  • SiGe / SiN dissolution rate ratio is 100 or more
  • the content of impurity particles in the treatment liquid was measured by the following method. First, a silicon wafer having a diameter of 300 mm was prepared. Using a wafer surface inspection device (SP-5; manufactured by KLA Tencor), the number of particles having a diameter of more than 19 nm existing on the wafer was measured (this is the initial value). Next, the wafer was set in a spin discharge device, and each treatment liquid was discharged to the surface of the wafer at a flow rate of 1.5 L / min while rotating the wafer. The wafer was then spin dried.
  • SP-5 wafer surface inspection device
  • the number of particles having a diameter of more than 19 nm existing on the wafer after the treatment liquid was applied was measured (this is used as a measured value).
  • the difference between the initial value and the measured value (measured value-initial value) was calculated to obtain the number of impurity particles derived from each treatment liquid. From the number of impurity particles obtained, the content of impurity particles in each treatment liquid was evaluated based on the following evaluation criteria.
  • Table 1 shows the composition of the treatment liquid used in each performance test and the results of each performance evaluation.
  • the "Amount (%)” column indicates the content (mass%) of each component with respect to the total mass of the treatment liquid.
  • the “ratio 1” column indicates the ratio of the content (mass%) of the specific organic acid to the content (mass%) of the alkanolamine (content of the specific organic acid / content of alkanolamine).
  • the “Na” column indicates the content of Na (mass ppb) with respect to the total mass of each treatment liquid.
  • the “treatment temperature (° C.)” column indicates the temperature of the treatment liquid in the immersion treatment of the SiGe film, the Si film and the SiN film.

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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)
  • Materials For Photolithography (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un liquide de traitement qui a une excellente stabilité au stockage et une excellente sélectivité de gravure d'une substance contenant du SiGe par rapport à une substance contenant du Si, lorsqu'un objet à traiter ayant la substance contenant du SiGe et la substance contenant du Si est traité. Un liquide de traitement selon la présente invention est utilisé pour traiter un objet à traiter ayant une substance contenant du SiGe et une substance contenant du Si pour éliminer au moins une partie d'une couche contenant du SiGe, le liquide de traitement contenant au moins un acide organique sélectionné dans le groupe constitué par une source d'ions fluorure, un acide nitrique, un composé d'acide sulfonique, un composé ester d'acide sulfurique, un composé ester d'acide phosphorique et un composé d'acide phosphonique.
PCT/JP2021/003020 2020-03-04 2021-01-28 Liquide de traitement WO2021176903A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023248649A1 (fr) * 2022-06-20 2023-12-28 富士フイルム株式会社 Liquide de traitement, procédé de traitement de substrat et procédé de fabrication de dispositif à semi-conducteur
WO2024004980A1 (fr) * 2022-07-01 2024-01-04 三菱瓦斯化学株式会社 Composition de nettoyage de substrat semi-conducteur, procédé de nettoyage de substrats semi-conducteurs et procédé de production de substrats semi-conducteurs

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013538007A (ja) * 2010-09-01 2013-10-07 ビーエーエスエフ ソシエタス・ヨーロピア 酸性水溶液及びエッチング液並びに単結晶及び多結晶シリコン基板の表面をしぼ加工する方法
JP2019050365A (ja) * 2017-08-25 2019-03-28 バーサム マテリアルズ ユーエス，リミティド ライアビリティ カンパニー 半導体デバイスの製造中にシリコン−ゲルマニウム／シリコン積層体からシリコン−ゲルマニウム合金を選択的に除去するためのエッチング液

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013538007A (ja) * 2010-09-01 2013-10-07 ビーエーエスエフ ソシエタス・ヨーロピア 酸性水溶液及びエッチング液並びに単結晶及び多結晶シリコン基板の表面をしぼ加工する方法
JP2019050365A (ja) * 2017-08-25 2019-03-28 バーサム マテリアルズ ユーエス，リミティド ライアビリティ カンパニー 半導体デバイスの製造中にシリコン−ゲルマニウム／シリコン積層体からシリコン−ゲルマニウム合金を選択的に除去するためのエッチング液

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023248649A1 (fr) * 2022-06-20 2023-12-28 富士フイルム株式会社 Liquide de traitement, procédé de traitement de substrat et procédé de fabrication de dispositif à semi-conducteur
WO2024004980A1 (fr) * 2022-07-01 2024-01-04 三菱瓦斯化学株式会社 Composition de nettoyage de substrat semi-conducteur, procédé de nettoyage de substrats semi-conducteurs et procédé de production de substrats semi-conducteurs

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