WO2021176913A1 - 処理液、処理液収容体 - Google Patents

処理液、処理液収容体 Download PDF

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Publication number
WO2021176913A1
WO2021176913A1 PCT/JP2021/003521 JP2021003521W WO2021176913A1 WO 2021176913 A1 WO2021176913 A1 WO 2021176913A1 JP 2021003521 W JP2021003521 W JP 2021003521W WO 2021176913 A1 WO2021176913 A1 WO 2021176913A1
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Prior art keywords
ether
salt
treatment liquid
group
acid
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English (en)
French (fr)
Japanese (ja)
Inventor
宣明 杉村
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2022505043A priority Critical patent/JPWO2021176913A1/ja
Publication of WO2021176913A1 publication Critical patent/WO2021176913A1/ja
Priority to US17/899,862 priority patent/US20230017832A1/en
Anticipated expiration legal-status Critical
Priority to JP2023208933A priority patent/JP7614310B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/10—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a boron compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/60—Wet etching
    • H10P50/66—Wet etching of conductive or resistive materials
    • H10P50/663—Wet etching of conductive or resistive materials by chemical means only
    • H10P50/667—Wet etching of conductive or resistive materials by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/69—Etching of wafers, substrates or parts of devices using masks for semiconductor materials
    • H10P50/691—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/10—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H10P70/15—Cleaning before device manufacture, i.e. Begin-Of-Line process by wet cleaning only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/20—Cleaning during device manufacture

Definitions

  • the present invention relates to a treatment liquid and a treatment liquid container.
  • Patent Document 1 water, an oxidizing agent, a water-miscible organic solvent, a fluoride ion source, and optionally a surfactant, and silicon-germanium is selected with respect to silicon from a microelectronic device.
  • An etching solution suitable for removing the solvent (claim 1) is disclosed.
  • Fluoride ion source and Oxidizing agent and Contains additives are polyvinyl alcohol, polystyrene sulfonic acid and its salt, nitrogen atom-containing polymer other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acid and its salt, alkyl.
  • Diphenyl ether disulfonic acid and its salt Diphenyl ether disulfonic acid and its salt, phenolsulfonic acid formarin condensate and its salt, arylphenol sulfonic acid formarin condensate and its salt, polyoxyethylene alkyl ether sulfonic acid and its salt, polyoxyethylene alkyl ether carboxylic acid and its salt, Polyoxyethylene alkyl ether phosphate and its salts, polyoxyethylene alkylphenyl ether phosphate and its salts, lauryldimethylaminoacetic acid betaine, dimethyllaurylamine oxide, silicon compounds, alkylamines, aromatic amines, nitrogen-containing heterocyclic compounds, A treatment solution which is at least one selected from the group consisting of amino acids other than cysteine, a quaternary ammonium salt having 16 or less carbon atoms, and a boron-containing compound.
  • the additive contains a nitrogen atom-containing polymer other than the polyethyleneimine
  • the nitrogen atom-containing polymers other than polyethyleneimine are polyvinylpyrrolidone, polyallylamine, polyvinylamine, polyacrylamide, dimethylamine / epihalohydrin-based polymer, hexadimethrin salt, polydialylamine, polydimethyldialylammonium salt, poly (4-vinylpyridine), and the like.
  • the treatment solution according to [1] which is one or more selected from the group consisting of polyornithine, polylysine, polyarginine, polyhistidine, polyvinylimidazole, and polymethyldiallylamine.
  • the additive contains at least one of the alkylnaphthalene sulfonic acid and a salt thereof.
  • the additive contains at least one of the alkyldiphenyl ether disulfonic acid and a salt thereof.
  • the additive contains at least one of the polyoxyethylene alkyl ether sulfonic acid and a salt thereof.
  • the polyoxyethylene alkyl ether sulfonic acid is one or more selected from the group consisting of polyoxyethylene lauryl ether sulfonic acid, polyoxyethylene oleyl ether sulfonic acid, and polyoxyethylene octyldodecyl ether sulfonic acid.
  • the additive contains at least one of the polyoxyethylene alkyl ether carboxylic acid and a salt thereof.
  • the polyoxyethylene alkyl ether carboxylic acid is one or more selected from the group consisting of polyoxyethylene lauryl ether carboxylic acid, polyoxyethylene dodecyl ether carboxylic acid, and polyoxyethylene tridecyl ether carboxylic acid.
  • the additive contains at least one of the polyoxyethylene alkyl ether phosphoric acid and a salt thereof.
  • the treatment solution according to any one of [1] to [6], wherein the polyoxyethylene alkyl ether phosphoric acid is polyoxyethylene lauryl ether phosphoric acid.
  • the additive contains the silicon compound and The treatment solution according to any one of [1] to [7], wherein the silicon compound is at least one selected from the group consisting of alkoxysilane, silanol compound, oximesilane, disilazane, and siloxane.
  • the above alkoxysilanes are tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxy.
  • Silane hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, t-butylmethoxydimethylsilane, 3-aminopropyldimethylmethoxysilane , Ethoxy (trimethyl) silane, methoxy (trimethyl) silane, hexyl (dimethoxy) silane, methyldiethoxysilane, triethoxysilane, 3-aminopropyldimethylethoxysilane, and 3- (2-aminoethoxyamino) propyltrimethoxy.
  • the silanol compounds are trimethylsilanol, dimethylsilanediol, diphenylsilanediol, silanetriol, 3-aminopropylsilanetriol, methylsilanetriol, 2-methyl-2-propylsilanetriol, methylacetatesilanetriol, 2- (chloroethyl).
  • oxime silanes are di (ethylaldoxime) silane, mono (ethylaldoxime) silane, tris (ethylaldoxime) silane, tetra (ethylaldoxime) silane, methyltris (methylethylketooxime) silane, and methyltosyl (acetooxime) silane.
  • the treatment liquid according to any one of. [12] The treatment liquid according to any one of [8] to [11], wherein the disilazane is hexamethyldisilazane. [13] Any of [8] to [12], wherein the siloxane is at least one selected from the group consisting of hexamethyldisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
  • the treatment liquid described in Crab The treatment liquid described in Crab.
  • the additive contains the alkylamine and
  • the above alkylamines are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylethylenediamine, hexamethylenediamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, stearyl.
  • the treatment solution according to any one of [1] to [13], which is one or more selected from the group consisting of amines, cyclohexylamines, phenethylamines, and m-xylylenediamines.
  • the additive contains the aromatic amine and The treatment liquid according to any one of [1] to [14], wherein the aromatic amine is at least one selected from the group consisting of aniline and toluidine.
  • the additive contains the nitrogen-containing heterocyclic compound and The nitrogen-containing heterocyclic compound is selected from the group consisting of pyrrolidine, piperidine, piperidine, morpholin, pyrrole, pyrazole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, thiazole, 4-dimethylaminopyridine, and laurylpyridinium chloride.
  • the treatment solution according to any one of [1] to [15], which is one or more.
  • the additive contains an amino acid other than the cysteine and A group consisting of alanine, arginine, aspartic acid, aspartic acid, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.
  • the treatment solution according to any one of [1] to [16], which is one or more selected from.
  • the additive contains the quaternary ammonium salt having 16 or less carbon atoms.
  • the quaternary ammonium salt having 16 or less carbon atoms is a tetramethylammonium salt, a tetraethylammonium salt, a tetrapropylammonium salt, a tetrabutylammonium salt, a methyltripropylammonium salt, a methyltributylammonium salt, an ethyltrimethylammonium salt, or a dimethyldiethyl.
  • the additive contains the boron-containing compound and The treatment liquid according to any one of [1] to [18], wherein the boron-containing compound is boric acid.
  • the organic solvents are ethylene glycol, propylene glycol, butyl diglycol, 1,4-butanediol, tripropylene glycol methyl ether, propylene glycol propyl ether, diethylene glycol n-butyl ether, hexyloxypropylamine, poly (oxyethylene) diamine, and the like.
  • the treatment liquid according to any one of [1] to [25] which is used for an object to be treated containing SiGe and is a treatment liquid for removing at least a part of SiGe contained in the object to be processed.
  • the treatment liquid according to any one of [1] to [26], wherein the elemental ratio of Si to Ge in the above SiGe is in the range of Si: Ge 95: 5 to 50:50.
  • a metal hard mask containing 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 are used for the treatment liquid.
  • a treatment liquid container comprising a container and the treatment liquid according to any one of [1] to [28] contained in the container.
  • the container is a treatment liquid container having a degassing mechanism for adjusting the pressure in the container.
  • the present invention it is possible to provide a treatment liquid capable of improving the smoothness of the portion to be treated when SiGe is etched.
  • the present invention can also provide a treatment liquid container for the above treatment liquid.
  • 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.
  • ppm means “parts-per-million ( 10-6 )
  • ppb means “parts-per-billion ( 10-9 )
  • ppt means “ppt”. It 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 + ) or the like, for example, a halide of the compound such as fluoride, chloride, bromide, or iodide.
  • a halide of the compound such as fluoride, chloride, bromide, or iodide.
  • salts include salts; hydroxides; nitrates; and sulfates.
  • Such salts may form salts with two or more anions.
  • the salt is an additive, it is also preferable that the salt is other than fluoride.
  • Examples of the salt of the compound containing a sulfonic acid group, a phosphoric acid group, a carboxylic acid group and the like include alkali metal salts of the compound such as lithium salt, sodium salt and potassium salt; alkaline earth such as calcium salt. Metal salts; and ammonium salts and the like can be mentioned. 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 contains a fluoride ion source, an oxidizing agent, and an additive.
  • the above additives include polyvinyl alcohol, polystyrene sulfonic acid and its salt, nitrogen atom-containing polymer other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acid and its salt, alkyl.
  • Diphenyl ether disulfonic acid and its salt Diphenyl ether disulfonic acid and its salt, phenol sulfonic acid formarin condensate and its salt, arylphenol sulfonic acid formalin condensate and its salt, polyoxyethylene alkyl ether sulfonic acid, polyoxyethylene alkyl ether carboxylic acid, polyoxyethylene alkyl phosphate , Polyoxyethylene alkylphenyl ether phosphate, lauryldimethylaminoacetate betaine, dimethyllaurylamine oxide, silicon compounds, alkylamines, aromatic amines, nitrogen-containing heterocyclic compounds, amino acids other than cysteine, quaternary with 16 or less carbon atoms
  • One or more selected from the group consisting of ammonium salts and boron-containing compounds One or more selected from the group consisting of ammonium salts and boron-containing compounds.
  • One or more kinds of additives selected from the above group are also hereinafter referred to
  • the present inventor has selected a component exhibiting properties effective for improving the smoothness of the portion to be treated as a specific additive, and by incorporating such a specific additive in the treatment liquid, the problem of the present invention can be solved. I think it has been resolved.
  • the treatment liquid of the present invention is also excellent in solubility selectivity for SiGe.
  • the treatment liquid of the present invention has excellent solubility in SiGe and excellent corrosion resistance to Si (silicon).
  • the present invention states that the treatment liquid of the present invention can improve the smoothness of the portion to be treated when SiGe is etched, has excellent solubility in SiGe, and / or has excellent corrosion resistance to Si. It is also said that the effect is excellent.
  • the treatment liquid 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 oxidants described below.
  • fluoride ion source examples include hydrofluoric acid (HF), ammonium fluoride (NH 4 F), fluoroborate (KBF 4 , NH 4 BF 4, etc.), fluoroboric acid, tetrabutylammonium tetrafluoroborate, and six.
  • R 1 NR 2 R 3 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 compound represented by R 1 NR 2 R 3 R 4 F include tetramethylammonium fluoride, tetraethylammonium fluoride, methyltriethylammonium fluoride, and tetrabutylammonium fluoride.
  • the fluoride ion source is preferably hydrofluoric acid or ammonium fluoride.
  • the content of the fluoride ion source is not particularly limited, but 0.001 to 10% by mass is preferable, and 0.01 to 5% by mass is preferable with respect to the total mass of the treatment liquid in that the effect of the present invention is more excellent. More preferably, 0.1 to 3% by mass is further 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.
  • the treatment liquid contains an oxidizing agent. It is believed that it acts on SiGe to form oxides (silicon oxide, germanium oxide, and / or silicon-germanium composite oxide, etc.) and functions to etch SiGe.
  • the oxidizing agent include peroxides, persulfides (for example, monopersulfides and dipersulfides), percarbonates, their acids, and salts thereof.
  • the oxidizing agent is preferably a peroxide (a compound containing one or more peroxy groups (—O—O—)).
  • the peroxide may be peroxy acid (peracetic acid, perbenzoic acid, salts thereof, etc.).
  • oxidative halides include, for example, oxidative halides (iodic acid, periodic acid, and salts thereof, etc.), perboric acid, permanganate, permanganate, etc.
  • oxidative halides include salts, cerium compounds, and ferricianides (potassium ferricyanide, etc.).
  • More specific oxidizing agents include, for example, peracetic acid, hydrogen peroxide, periodic acid, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and urea. -Hydrogen peroxide additions can be mentioned. Of these, the oxidizing agent is preferably peracetic acid or hydrogen peroxide.
  • the content of the oxidizing agent is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 5% by mass, based on the total mass of the treatment liquid, in that the effect of the present invention is more excellent.
  • the above is more preferable.
  • the upper limit of the content is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and particularly preferably less than 10% by mass, based on the total mass of the treatment liquid. Only one kind of oxidizing agent may be used, or two or more kinds may be used. When two or more kinds of oxidizing agents are used, the total amount thereof is preferably within the above range.
  • the treatment liquid contains one or more of the specific additives.
  • Specific additives include polyvinyl alcohol, polystyrene sulfonic acid and its salt, nitrogen atom-containing polymer other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acid and its salt, alkyl.
  • Diphenyl ether disulfonic acid and its salt Diphenyl ether disulfonic acid and its salt, phenol sulfonic acid formarin condensate and its salt, arylphenol sulfonic acid formalin condensate and its salt, polyoxyethylene alkyl ether sulfonic acid, polyoxyethylene alkyl ether carboxylic acid, polyoxyethylene alkyl phosphate , Polyoxyethylene alkylphenyl ether phosphate, lauryldimethylaminoacetate betaine, dimethyllaurylamine oxide, silicon compounds, alkylamines, aromatic amines, nitrogen-containing heterocyclic compounds, amino acids other than cysteine, quaternary with 16 or less carbon atoms It is a component selected from the group consisting of ammonium salts and boron-containing compounds.
  • the above-mentioned fluoride ion source and oxidizing agent are not included in the specific additive.
  • the specific additives are polyvinyl alcohol, polystyrene sulfonic acid and its salt, nitrogen atom-containing polymer other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalene sulfonic acid and its salt.
  • Alkyldiphenyl ether disulfonic acid and its salt Alkyldiphenyl ether disulfonic acid and its salt, phenol sulfonic acid formarin condensate and its salt, arylphenol sulfonic acid formalin condensate and its salt, polyoxyethylene alkyl ether sulfonic acid and its salt, polyoxyethylene alkyl ether carboxylic acid and its salt Salt, polyoxyethylene alkyl ether phosphoric acid and its salt, polyoxyethylene alkylphenyl ether phosphoric acid and its salt, alkylamine, aromatic amine, nitrogen-containing heterocyclic compound, amino acids other than cysteine, 4 having 16 or less carbon atoms
  • One or more selected from the group consisting of a secondary ammonium salt and a boron-containing compound is preferable. More preferably, one or more selected from the group consisting of alkyldiphenyl ether disulfonic acid and phenol sulfonic acid formalin condensate.
  • the content of the specific additive is not particularly limited, but 0.001 to 10% by mass is preferable, and 0.01 to 5% 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 preferable, and 0.1 to 3% by mass is more preferable. Only one type of specific additive may be used, or two or more types may be used. When two or more kinds of specific additives are used, the total amount thereof is preferably within the above range. Hereinafter, each specific additive will be described.
  • Polyvinyl alcohol is a polymer containing repeating units represented by -CH 2-CH (OH)-. If that also contains other repeating units, of all kinds of repeating units, -CH 2 -CH (OH) - - Polyvinyl alcohol -CH 2 -CH (OH) content of the repeating unit represented by (mole ratio ) Is preferably the maximum.
  • the content of the repeating unit represented by -CH 2- CH (OH)-in polyvinyl alcohol 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 polyvinyl alcohol is preferably 400 to 50,000.
  • Polystyrene sulfonic acid and its salt Polystyrene sulfonic acid is a polymer containing repeating units based on styrene sulfonic acid.
  • the salt of polystyrene sulfonic acid is a salt (alkali metal salt such as sodium salt, alkaline earth metal salt, or ammonium) in part or all of the sulfonic acid group of the repeating unit based on styrene sulfonic acid in the above polystyrene sulfonic acid. It is a polymer in the form of (salt, etc.).
  • polystyrene sulfonic acid and its salt are a general term for styrene sulfonic acid-based repeating units (repeating units based on styrene sulfonic acid and repeating units in the form in which the sulfonic acid group of the repeating unit based on styrene sulfonic acid is a salt. ) Is a polymer containing.
  • the content (molar ratio) of the styrene sulfonic acid-based repeating unit may be the largest among all the types of repeating units. preferable.
  • the content of the styrene sulfonic acid-based repeating unit in the polystyrene sulfonic acid and the salt thereof 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 polystyrene sulfonic acid and its salt is preferably 400 to 50,000.
  • the nitrogen atom-containing polymer other than polyethyleneimine is preferably other than the specific additives described above.
  • the nitrogen atom-containing polymer other than polyethyleneimine is a polymer containing a repeating unit containing a nitrogen atom (N-containing repeating unit).
  • N-containing repeating unit does not include -CH 2- CH 2-N ⁇ .
  • the polymer contains N-containing repeating units, even if -CH 2- CH 2- N ⁇ is contained as part of all the repeating units, the polymer contains nitrogen atoms other than polyethyleneimine. Corresponds to polymer.
  • the content (molar ratio) of the N-containing repeating unit is preferably the largest among all the types of repeating units.
  • the content of the N-containing repeating unit in the nitrogen atom-containing polymer other than polyethyleneimine 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 nitrogen atom-containing polymer other than polyethyleneimine is preferably 400 to 50,000.
  • Examples of the monomer from which the N-containing repeating unit is derived include vinylpyrrolidone, allylamine, vinylamine, acrylamide, hexadimethrin salt (halide salt, hydroxide, nitrate, sulfate, etc.), diallylamine, and dimethyldialylammonium salt (diallylamine, dimethyldialylammonium salt, etc.).
  • 4-vinylpyridine, ornithine, lysine, arginine, histidine, vinylimidazole, and methyldialylamine may be used as the N-containing repeating unit.
  • a repeating unit composed of dimethylamine and epichlorohydrin preferably epichlorohydrin
  • Nitrogen atom-containing polymers other than polyethyleneimine include polyvinylpyrrolidone, polyallylamine, polyvinylamine, polyacrylamide, and dimethylamine / epihydrin-based polymers (preferably dimethylamine-epihalohydrin copolymer, more preferably dimethylamine-epichlorohydrin).
  • Polymer hexadimethrin salt (halide salt, hydroxide, nitrate, or sulfate, etc.), polydialylamine, polydimethyldiallylammonium salt (halide salt, hydroxide salt, nitrate, or sulfate, etc.) , Poly (4-vinylpyridine), polyornithine, polylysine, polyarginine, polyhistidine, polyvinylimidazole, and one or more selected from the group consisting of polymethyldialylamine is preferable.
  • Polyoxyethylene laurylamine The polyoxyethylene laurylamine is preferably other than the specific additives described above.
  • Polyoxyethylene laurylamine is, for example, a compound represented by "C 12 H 25- N [(C 2 H 4 O) PE H] 2". In “C 12 H 25- N [(C 2 H 4 O) PE H] 2 ", the two PEs independently represent an integer from 1 to 100.
  • the alkylnaphthalene sulfonic acid and its salt are preferably other than the specific additives described above.
  • the alkylnaphthalene sulfonic acid is preferably a compound represented by "(AL-) NL R NP- SO 3 H".
  • NL represents an integer of 1 to 7.
  • AL represents an alkyl group.
  • the alkyl group may be linear or branched, and may have a cyclic structure in whole or in part.
  • the alkyl group preferably has 1 to 25 carbon atoms. When there are a plurality of ALs, the plurality of ALs may be the same or different from each other.
  • R NP represents a naphthalene ring group which may have a substituent other than AL- and -SO 3 H.
  • the alkylnaphthalene sulfonic acid salt is in the form in which some or all of the sulfonic acid groups in the above alkylnaphthalene sulfonic acid are salts (alkali metal salt such as sodium salt, alkaline earth metal salt, ammonium salt, etc.). Compound is preferred.
  • the alkylnaphthalene sulfonic acid and its salt are preferably at least one selected from the group consisting of propylnaphthalene sulfonic acid, triisopropylnaphthalene sulfonic acid, and dibutylnaphthalene sulfonic acid. Salts of these compounds are also preferred.
  • alkyldiphenyl ether disulfonic acid and its salt The alkyldiphenyl ether disulfonic acid and its salt are preferably other than the specific additives described above.
  • the alkyldiphenyl ether disulfonic acid is preferably a compound represented by the following general formula (C1).
  • AL represents an alkyl group.
  • the alkyl group may be linear or branched, and may have a cyclic structure in whole or in part.
  • the alkyl group preferably has 1 to 25 carbon atoms.
  • the plurality of ALs may be the same or different from each other.
  • the alkyldiphenyl ether disulfonic acid salt is in the form in which some or all of the sulfonic acid groups in the above alkyldiphenyl ether disulfonic acid are salts (alkali metal salt such as sodium salt, alkaline earth metal salt, ammonium salt, etc.). Compound is preferred.
  • alkyldiphenyl ether disulfonic acid and its salt are preferably dodecyldiphenyl ether disulfonic acid.
  • a salt of this compound is also preferred.
  • the phenol sulfonic acid formalin condensate and a salt thereof are preferably other than the specific additives described above.
  • the phenol sulfonic acid formalin condensate is a polymer containing a repeating unit in the form of a condensation of phenol sulfonic acid and formalin.
  • the salt of the phenol sulfonic acid formalin condensate is a salt (like a sodium salt) of a part or all of the sulfonic acid groups of the repeating unit in the form of condensation of phenol sulfonic acid and formalin in the above phenol sulfonic acid formalin condensate.
  • the content (molar ratio) of the phenol sulfonic acid formaline-based repeating unit among all kinds of repeating units is high. The maximum is preferable.
  • the content of the phenol sulfonic acid formalin-based repeating unit in the phenol sulfonic acid formalin condensate and its salt 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 phenol sulfonic acid formalin condensate and a salt thereof is preferably 400 to 50,000.
  • the arylphenol sulfonic acid formalin condensate and a salt thereof are preferably other than the specific additives described above.
  • Examples of the arylphenol sulfonic acid formalin condensate and its salt include a polymer in which the phenol sulfonic acid in the above description of the phenol sulfonic acid formalin condensate and its salt is replaced with the arylphenol sulfonic acid.
  • Examples of the aryl group in the arylphenol sulfonic acid include an aryl group having 6 to 14 carbon atoms.
  • the polyoxyethylene alkyl ether sulfonic acid and its salt are preferably other than the specific additives described above.
  • the polyoxyethylene alkyl ether sulfonic acid and its salt are, for example, a compound represented by "AL-O- (C 2 H 4 O) PE- SO 3 H" and a salt thereof.
  • A-O- (C 2 H 4 O) PE- SO 3 H PE represents an integer of 1 or more, and an integer of 1 to 100 is preferable.
  • AL represents an alkyl group.
  • the alkyl group may be linear or branched, and may have a cyclic structure in whole or in part.
  • the alkyl group preferably has 1 to 25 carbon atoms.
  • the polyoxyethylene alkyl ether sulfonic acid and a salt thereof are preferably at least one selected from the group consisting of polyoxyethylene lauryl ether sulfonic acid, polyoxyethylene oleyl ether sulfonic acid, and polyoxyethylene octyldodecyl ether sulfonic acid. .. Salts of these compounds are also preferred.
  • the polyoxyethylene alkyl ether carboxylic acid and its salt are preferably other than the specific additives described above.
  • the polyoxyethylene alkyl ether carboxylic acid and its salt are, for example, a compound represented by "AL-O- (C 2 H 4 O) PE- CH 2- COOH” and a salt thereof.
  • A-O- (C 2 H 4 O) PE- CH 2- COOH PE represents an integer of 1 or more, and an integer of 1 to 100 is preferable.
  • AL represents an alkyl group.
  • the alkyl group may be linear or branched, and may have a cyclic structure in whole or in part.
  • the alkyl group preferably has 1 to 25 carbon atoms.
  • the polyoxyethylene alkyl ether carboxylic acid and a salt thereof are preferably at least one selected from the group consisting of polyoxyethylene lauryl ether carboxylic acid, polyoxyethylene dodecyl ether carboxylic acid, and polyoxyethylene tridecyl ether carboxylic acid. .. Salts of these compounds are also preferred.
  • polyoxyethylene alkyl ether phosphoric acid and its salt The polyoxyethylene alkyl phosphoric acid is preferably other than the specific additives described above.
  • Polyoxyethylene alkyl ether phosphoric acid and its salts are, for example, "AL-O- (C 2 H 4 O) PE- PO 3 H 2 " or "[AL-O- (C 2 H 4 O) PE- ].
  • PE is an integer of 1 or more.
  • AL an integer of 1 to 100 is preferable.
  • AL represents an alkyl group.
  • the alkyl group may be linear or branched, and may have a cyclic structure in whole or in part.
  • the alkyl group preferably has 1 to 25 carbon atoms.
  • the plurality of "AL-O- (C 2 H 4 O) PE- " may be the same or different.
  • polyoxyethylene alkyl ether phosphoric acid and its salt are preferably polyoxyethylene lauryl ether phosphoric acid. A salt of this compound is also preferred.
  • polyoxyethylene alkyl phenyl ether phosphoric acid and its salts The polyoxyethylene alkyl phenyl ether phosphoric acid and salts thereof are preferably other than the specific additives described above.
  • Polyoxyethylene alkylphenyl ether phosphoric acid and its salts are, for example, "AL-Ph-O- (C 2 H 4 O) PE- PO 3 H 2 " or "[AL-Ph-O- (C 2 H 4 O)”.
  • O) PE- ] 2 A compound represented by "2 PO 2 H” and a salt thereof.
  • PE is It represents an integer of 1 or more, and an integer of 1 to 100 is preferable.
  • Ph represents a benzene ring group.
  • AL represents an alkyl group.
  • the alkyl group may be linear or branched, and may have a cyclic structure in whole or in part.
  • the alkyl group preferably has 1 to 25 carbon atoms.
  • the silicon compound is preferably other than the specific additives described above.
  • the silicon compound is a compound having a silicon atom (Si). It is preferable that the silicon compound is at least one selected from the group consisting of alkoxysilane, silanol compound, oximesilane, disilazane, and siloxane.
  • Alkoxysilane is preferably other than the specific additives described above.
  • Alkoxysilane is, for example, a compound having at least one (preferably 1 to 6) groups represented by "alkyl groups-O-" that directly bond with a silicon atom.
  • Alkoxysilane compounds represented by "(AL 2 -O-) S1 SiR Si S2 " are preferred.
  • S1 represents an integer of 1-4.
  • S2 represents an integer of 0 to 3.
  • S1 + S2 is 4.
  • AL 2 represents an alkyl group.
  • the alkyl group may be linear or branched, and may have a cyclic structure in whole or in part.
  • the alkyl group preferably has 1 to 5 carbon atoms.
  • R Si denotes a hydrogen atom or an "AL 2 -O-" and other substituents.
  • substituents include an alkyl group (preferably 1 to 10), an aryl group (preferably 6 to 15 carbon atoms), an aminoalkyl group (preferably 1 to 10 carbon atoms), and an aminoalkoxyaminoalkyl group (preferably 1 to 10 carbon atoms). Is a group consisting of 1 to 12 carbon atoms), a halogen atom, or a combination thereof. It is also preferable that the substituent satisfies the requirement that it is an organic group having 1 to 15 carbon atoms as a whole. When a plurality of AL 2 and / or R Si are present, the plurality of AL 2 and / or R Si may be the same or different from each other.
  • the alkoxysilane is preferably a compound represented by "L Si [-Si (-O-AL 2) S3 R Si S4] 2 ".
  • L Si represents a single bond or a divalent linking group.
  • the divalent linking group is preferably an alkylene group (preferably 1 to 10 carbon atoms).
  • S3 represents an integer of 1 to 3.
  • S4 represents an integer of 0 to 2.
  • S3 + S4 in one "-Si (-O-AL 2 ) S3 R Si S4" is 3.
  • the alkoxysilanes are tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxysilane.
  • silanol compound is, for example, a compound having at least one (preferably 1 to 6) hydroxyl groups that directly bond with a silicon atom. However, silanol compounds do not have an alkoxy group that directly bonds to a silicon atom.
  • the silanol compound is preferably a compound represented by " RSJ S5 Si (OH) S6". In “ RSJ S5 Si (OH) S6 ", S5 represents an integer of 0 to 4. S6 represents an integer of 1 to 4. However, S5 + S6 is 4.
  • RSJ represents a hydrogen atom or a substituent that is neither an alkoxy group nor a hydroxyl group.
  • substituents examples include an alkyl group (preferably 1 to 10), an alkenyl group (preferably 2 to 10), an aryl group (preferably 6 to 15 carbon atoms), an amino group, an acetyl group, a halogen atom, and the like. , A group consisting of a combination of these can be mentioned. It is also preferable that the substituent satisfies the requirement that it is an organic group having 1 to 15 carbon atoms as a whole. When there are a plurality of R SJs , the plurality of R SJs may be the same or different.
  • the silanol compounds are trimethylsilanol, dimethylsilanediol, diphenylsilanediol, silanetriol, 3-aminopropylsilanetriol, methylsilanetriol, 2-methyl-2-propylsilanetriol, methylacetatesilanetriol, 2- (chloroethyl) acetate.
  • silanetriol and 3- (hydroxypropyl) silanetriol is preferable.
  • Oxime silane is preferably other than the specific additives described above.
  • Two ROXs attached to the same carbon atom independently represent a hydrogen atom or an organic group. Further, two ROXs bonded to the same carbon atom may be bonded to each other to form a ring. However, at least one of the two ROXs bonded to the same carbon atom is other than a hydrogen atom.
  • the organic group is preferably an alkyl group.
  • the alkyl group may be linear or branched, and may have a cyclic structure in whole or in part.
  • the alkyl group preferably has 1 to 25 carbon atoms.
  • the group to which the two ROXs are bonded to each other is preferably an alkylene group (preferably 2 to 15 carbon atoms).
  • the oxime silane does not have a group represented by an alkoxy group and / or a hydroxyl group that directly bonds with a silicon atom.
  • S8 represents an integer of 1 to 4.
  • S7 + S8 is 4.
  • substituents examples include an alkyl group (preferably 1 to 10), an alkenyl group (preferably 2 to 10), an aryl group (preferably 6 to 15 carbon atoms), an amino group, an acetyl group, a halogen atom, and the like. , A group consisting of a combination of these can be mentioned. It is also preferable that the substituent satisfies the requirement that it is an organic group having 1 to 15 carbon atoms as a whole.
  • the ROX is as described above. When a plurality of R SKs and / or R OXs are present, the plurality of R SKs and / or R OXs may be the same or different from each other.
  • Oxime silanes include di (ethylaldoxime) silane, mono (ethylaldoxime) silane, tris (ethylaldoxime) silane, tetra (ethylaldoxime) silane, methyltris (methylethylketooxime) silane, methyltosyl (acetooxime) silane, Methyltris (methylisobutylketooxime) silane, dimethyldi (methylethylketooxime) silane, trimethyl (methylethylketooxime) silane, tetra (methylethylketooxime) silane, tetra (methylisobutylketooxime) silane, vinyltris (methylethylketooxime) silane, methylvinyldi (methylethylketooxime) silane ) Silane, methylvinyldi (cyclohexanonexime) silane, vinyltris (methyl
  • Disilazan is other than the specific additives described above.
  • Disilazan is, for example, a compound represented by "R SL 3 Si-NH-SiR SL 3".
  • substituent include an alkyl group (preferably 1 to 10), an alkenyl group (preferably 2 to 10), an aryl group (preferably 6 to 15 carbon atoms), an amino group, an acetyl group, a halogen atom, and the like. , A group consisting of a combination of these can be mentioned.
  • the substituent satisfies the requirement that it is an organic group having 1 to 15 carbon atoms as a whole.
  • Hexamethyldisilazane is preferable as the disilazane.
  • Siloxane is preferably other than the specific additives described above.
  • Siloxane compound for example, "R SM 3 Si (-O-SiR SN 2 -) S9 R SO " is a compound represented by the.
  • RSM 3 Si (-O-SiR SN 3- ) S9 R SO " S9 represents an integer of 1 or more, and an integer of 1 to 10 is preferable.
  • substituents examples include an alkyl group (preferably 1 to 10), an alkenyl group (preferably 2 to 10), an aryl group (preferably 6 to 15 carbon atoms), an amino group, an acetyl group, a halogen atom, and the like. , A group consisting of a combination of these can be mentioned. It is also preferable that the substituent satisfies the requirement that it is an organic group having 1 to 15 carbon atoms as a whole. Further, one of the three R SMs and R SO may be bonded to each other to form a divalent linking group. When forming a divalent linking group, —O— is preferable as the divalent linking group.
  • the siloxane is preferably one or more selected from the group consisting of hexamethyldisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
  • Alkylation amine The alkylamine is preferably other than the specific additives described above.
  • Alkylamines are compounds containing at least one partial structure represented by an "alkyl group-N".
  • the alkyl group may have a substituent.
  • the alkylamine is preferably none of the above-mentioned specific additive, the nitrogen-containing heterocyclic compound described below, and an amino acid other than cysteine described below.
  • the molecular weight of the alkylamine is preferably 15 or more and less than 400, and more preferably 15 or more and 300 or less.
  • Alkylamines, "R N 2 N (-L N -NR LN -) XN R N" compounds represented by are preferred.
  • R N 2 N (-L N -NR LN -) XN R N in, XN is an integer of 0-6.
  • Three R N and,, XN-number of R LN each independently represent a hydrogen atom, or an optionally substituted alkyl group.
  • the alkyl group in the alkyl group which may have the above-mentioned substituent may be linear or branched, and may have a cyclic structure in whole or in part.
  • the alkyl group preferably has 1 to 120 carbon atoms.
  • the substituent in the alkyl group which may have the above-mentioned substituent is preferably an aryl group (preferably 6 to 15 carbon atoms), an aminoalkyl group (preferably 1 to 5 carbon atoms), or a group in which these are combined. .. It is also preferable that the substituent is other than a carboxy group.
  • the total number of carbon atoms of the alkyl group which may have the above-mentioned substituent is preferably 1 to 20.
  • Each of the XN L Ns independently represents an alkylene group having 1 to 8 carbon atoms. However, if XN is 0, at least one of three R N is an alkyl group which may have the substituent.
  • Alkylamines are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylethylenediamine, hexamethylenediamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, stearylamine. , Cyclohexylamine, phenethylamine, and m-xylylenediamine, one or more selected from the group is preferable.
  • Aromatic amine is preferably other than the specific additives described above.
  • Aromatic amines are compounds containing at least one partial structure represented by "aromatic ring group-N".
  • the aromatic ring group may have a substituent.
  • the aromatic amine is neither of the above-mentioned specific additive, the nitrogen-containing heterocyclic compound described below, or an amino acid other than cysteine described below.
  • the molecular weight of the aromatic amine is preferably 15 or more and less than 400, and more preferably 15 or more and 300 or less.
  • the aromatic amine is preferably a compound represented by "an aromatic ring group which may have an RN 2 N-substituted group".
  • R N aromatic ring group which may have a 2 N- substituent the two R N are each independently represent a hydrogen atom or a substituent other than an alkyl group.
  • the substituent in the aromatic ring group which may have the above-mentioned substituents is an alkyl group (preferably 1 to 20 carbon atoms), an aryl group (preferably 6 to 15 carbon atoms), and an aminoalkyl group (preferably 1 carbon number carbon number). ⁇ 5), or a group combining these is preferable.
  • the total number of carbon atoms of the aromatic ring group which may have the above substituent is preferably 1 to 20.
  • the aromatic ring group which may have a substituent preferably has 5 to 15 carbon atoms, and may contain a hetero atom as a ring member atom.
  • the aromatic amine is preferably one or more selected from the group consisting of aniline and toluidine.
  • the nitrogen-containing heterocyclic compound is preferably other than the specific additives described above.
  • the nitrogen-containing heterocyclic compound is a compound having a heterocyclic structure having at least one (preferably 1 to 4) nitrogen atoms as ring member atoms.
  • the nitrogen atom which is a ring member atom of the heterocyclic structure, may be a cationic nitrogen atom (N + ).
  • the heterocyclic structure may have a hetero atom (oxygen atom, sulfur atom, etc.) as a ring member atom in addition to the nitrogen atom.
  • the heterocyclic structure may be monocyclic or polycyclic. In the case of a single ring, a 5- to 8-membered ring is preferable.
  • the total number of rings is preferably 2 to 5, and it is also preferable that each ring is a 5 to 8-membered ring.
  • the heterocyclic structure may or may not have aromaticity. Further, when the heterocyclic structure is polycyclic, the rings having aromaticity may be fused to each other, the rings having no aromaticity may be fused to each other, or aromatic. A ring having a property and a ring having no aromaticity may be fused. The number of ring-membered atoms constituting the heterocyclic structure is preferably 3 to 20.
  • the heterocyclic structure may contain a substituent (1 to tertiary amino group, etc.).
  • the nitrogen-containing heterocyclic compound may have only one heterocyclic structure as a whole, or may have a plurality of the above heterocyclic structures.
  • the molecular weight of the nitrogen-containing heterocyclic compound is preferably 40 or more and less than 400, and more preferably 50 or more and 300 or less.
  • the nitrogen-containing heterocyclic compound is selected from the group consisting of pyrrolidine, piperidine, piperidine, morpholin, pyrrole, pyrazole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, thiazole, 4-dimethylaminopyridine, and laurylpyridinium chloride. Seeds or more are preferred.
  • Amino acids other than cysteine are preferably other than the specific additives described above.
  • the amino acid other than cysteine is preferably a compound containing a carboxy group and a primary or secondary amino group.
  • Amino acids other than cysteine consist of the group consisting of alanine, arginine, aspartic acid, aspartic acid, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine. One or more selected is preferable.
  • the quaternary ammonium salt having 16 or less carbon atoms is preferably other than the specific additives described above.
  • the quaternary ammonium salt having 16 or less carbon atoms does not contain a pyridinium salt.
  • the quaternary ammonium salt having 16 or less carbon atoms is, for example, a compound represented by " RT 4 N + ⁇ T ⁇ ".
  • "R T 4 N + ⁇ T -" in the four R T each independently, N + bonded directly to atoms represent organic groups which are carbon atoms.
  • the organic group is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • the alkyl group in the alkyl group which may have the above-mentioned substituent may be linear or branched, and may have a cyclic structure in whole or in part.
  • the alkyl group preferably has 1 to 110 carbon atoms.
  • the substituent in the alkyl group which may have the above-mentioned substituent is preferably a hydroxyl group or an aryl group (preferably 6 to 10 carbon atoms).
  • the aryl group in the aryl group which may have the above-mentioned substituent is preferably 6 to 12 carbon atoms.
  • the substituent in the aryl group which may have the above-mentioned substituent is preferably a hydroxyl group or an alkyl group (preferably having 1 to 10 carbon atoms).
  • T ⁇ represents a counter anion other than F ⁇ .
  • the counter anion is preferably OH ⁇ .
  • "R T 4 N + ⁇ T -" total number of carbon atoms contained in the compound represented by is 16 or less, preferably from 4 to 16.
  • the quaternary ammonium salts having 16 or less carbon atoms are tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, methyltripropylammonium salt, methyltributylammonium salt, ethyltrimethylammonium salt, and dimethyldiethylammonium.
  • One or more selected from the group consisting of a salt, a benzyltrimethylammonium salt, and a (2-hydroxyethyl) trimethylammonium salt is preferable.
  • the boron-containing compound is preferably other than the specific additives described above.
  • the boron-containing compound is a compound containing a boron atom (B).
  • the boron atom-containing compound is preferably a compound having "-OH" that is directly bonded to the boron atom.
  • the molecular weight of the boron-containing compound is preferably 50 or more and less than 400, and more preferably 60 or more and 300 or less.
  • the boron-containing compound is preferably boric acid.
  • the treatment liquid preferably contains an organic solvent.
  • the organic solvent include alcohol-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents (including, for example, (poly) alkylene glycols having both ends substituted with alkyl groups or amino groups), sulfone-based solvents, and the like. Examples thereof include sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents.
  • alcohol-based solvent examples include alkanediol (including, for example, alkylene glycol), alkoxyalcohol (including, for example, glycol monoether), saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and ring.
  • alkanediol including, for example, alkylene glycol
  • alkoxyalcohol including, for example, glycol monoether
  • saturated aliphatic monohydric alcohol unsaturated non-aromatic monohydric alcohol
  • ring examples include low molecular weight alcohols containing a structure.
  • the organic solvent is preferably other than the acetate solvent. Further, it is preferable that the treatment liquid does not substantially contain the acetate solvent, and for example, the content of the acetate solvent is preferably 0 to 1% by mass with respect to the total mass of the treatment liquid.
  • organic solvent examples include ethylene glycol, propylene glycol, butyl diglycol, 1,4-butanediol, tripropylene glycol methyl ether, propylene glycol propyl ether, diethylene glycol n-butyl ether, hexyloxypropylamine, and poly (oxyethylene) diamine.
  • the content of the organic solvent is not particularly limited, but is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and 20 to 45% by mass, based on the total mass of the treatment liquid, in that the effect of the present invention is more excellent. Mass% is more preferred. Only one kind of organic solvent may be used, or two or more kinds may be used. When two or more kinds of organic solvents are used, the total amount thereof is preferably within the above range.
  • the treatment liquid 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 20% by mass or more, more preferably 30% by mass or more, still more preferably 55% by mass or more, based on the total mass of the treatment liquid.
  • the upper limit is less than 100% by mass, preferably 90% by mass or less, and more preferably 80% by mass or less.
  • 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 water, a fluoride ion source, an oxidizing agent, a specific additive and the like in a predetermined amount can be mentioned. When mixing the above components, other arbitrary components may be combined and mixed, if necessary. Further, when producing the treatment liquid, the treatment liquid may be filtered and purified using a filter, if necessary.
  • the pH of the treatment liquid is preferably less than 7 and more preferably less than 4 in that the effect of the present invention is more excellent.
  • the treatment solution may contain a pH adjuster.
  • the pH adjuster include acid compounds (inorganic acids, organic acids, etc.) other than the above-mentioned components, and basic compounds (inorganic bases, organic bases, etc.).
  • 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. It is also preferable that the treatment liquid is transported as a treatment liquid container and the treatment liquid is provided from the manufacturer to the user or from the storage place to the place of use.
  • the container has a degassing mechanism for adjusting the pressure (internal pressure) in the container.
  • the degassing mechanism was generated, for example, when gas was generated from the treatment liquid due to a temperature rise of the treatment liquid inside the container during storage of the treatment liquid container and / or decomposition of some components of the treatment liquid. It is a mechanism that releases 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. Further, it is also preferable to equip the container with a degassing mechanism by adopting a degassing cap having a degassing mechanism as the cap of the container.
  • the container of the treatment liquid container has a degassing cap provided with a degassing mechanism for adjusting the pressure in the container.
  • the treatment liquid may be provided from the manufacturer to the user or from the storage place to the place of use by the method using such a treatment liquid container. preferable.
  • FIG. 1 illustrates a schematic cross-sectional view of the upper part of the processing liquid container to which the degassing cap is applied.
  • the treatment liquid container 100 has a container including a cap body 102, a waterproof ventilation film 104, a cap (gas vent cap) composed of the ventilation layer 106, and a container body 108 sealed by the cap.
  • the treatment liquid container 100 further has a treatment liquid 110 housed in the container body 108.
  • the broken line arrow is a virtual flow path 112 of the gas generated from the treatment liquid 110.
  • the gas generated from the treatment liquid 110 passes through the waterproof ventilation membrane 104 and then is discharged to the outside of the container through the ventilation layer 106 and the gap between the cap body 102 and the container body 108, and the internal pressure is generated by the gas generated from the treatment liquid. Is suppressed from rising excessively.
  • the waterproof breathable membrane 104 is a highly gas-permeable membrane that allows gas to permeate but does not allow liquid to permeate.
  • the ventilation layer 106 is a layer provided so that the gas that has permeated through the waterproof ventilation membrane 104 is quickly moved to the outside.
  • the ventilation layer 106 is formed of, for example, a porous material (polyethylene foam or the like).
  • the ventilation layer 106 may be omitted.
  • the cap body 102 and the container body 108 have a structure for fixing the container body with the lid covered by the cap (for example, the cap body 102 is screwed and fixed to the container body 108). It is also preferable that a structure that enables the formation of the structure) is formed.
  • the above structure is preferably a structure that does not prevent the gas from being released to the outside.
  • 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. In addition, it is described on pages 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. 99/46309. Containers can also 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, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is 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.
  • the metal material may be processed by combining one or two or more of a plurality of stages of buffing, acid cleaning, magnetic fluid polishing, etc., which are performed by changing the count such as the size of the abrasive grains. ..
  • 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 preferably applied to a method for treating an object to be treated containing SiGe (hereinafter, also simply referred to as "the present treatment method"). In this treatment method, it is preferable to remove (etch) at least a part of SiGe contained in the object to be treated.
  • SiGe is a material composed of a combination of silicon (Si) and germanium (Ge), and is preferably usable as a semiconductor material. SiGe may intentionally or unavoidably contain components other than silicon and germanium.
  • the total content of silicon and germanium in SiGe 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 SiGe.
  • the element ratio of silicon (Si) to germanium (Ge) in SiGe (ratio of atom% occupied by Si atoms to atom% occupied by Ge atoms in SiGe, Si: Ge) is 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 form of the object to be treated is not particularly limited as long as it contains SiGe.
  • it contains a substrate 202, SiGe204 alternately laminated on the substrate 202, and other materials 206.
  • the object to be processed 200 is mentioned.
  • FIG. 2 shows an embodiment in which the object to be treated 200 contains a plurality of SiGe204 and a plurality of other materials 206, but one or both of the plurality of SiGe204s and the plurality of other materials 206 is one layer. May only exist.
  • a portion where neither SiGe204 nor the other material 206 is present is shown on the substrate 202, and such a portion may be covered with SiGe204.
  • FIG. 2 shows an embodiment in which the object to be treated 200 contains a plurality of SiGe204 and a plurality of other materials 206, but one or both of the plurality of SiGe204s and the plurality of other materials 206 is one layer. May only exist.
  • SiGe204 is directly arranged on the substrate 202, but it may be arranged via another layer.
  • the other material 206 may be other than SiGe. Further, the plurality of other materials 206 may be in different layers. Above all, it is preferable that the object to be treated 200 contains at least one other material 206 which is silicon (Si).
  • the type of substrate contained in the object to be processed 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, and magnetism.
  • Examples thereof include various substrates such as a substrate for a disk and a substrate for a photomagnetic disk.
  • the material constituting the semiconductor substrate include group III-V compounds such as silicon and GaAs, or any combination thereof.
  • the substrate is preferably made of silicon (Si).
  • the size, thickness, shape, layer structure, and the like 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 200 shown in FIG. 2 may further contain a metal hard mask.
  • a metal hard mask for example, a metal hard containing 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 is made of 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 with respect to the total mass. 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.
  • the form of SiGe and / or other material 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.
  • its thickness is not particularly limited and may be appropriately selected depending on the intended use, for example, 1 to 50 nm.
  • the SiGe and / or other material may be arranged only on one main surface of the substrate, or may be arranged on both main surfaces. Further, SiGe and / or other materials 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.
  • the object to be treated may contain various layers and / or structures as desired, in addition to SiGe and / or other materials.
  • the substrate may contain metal wiring, a gate electrode, a source electrode, a drain electrode, an insulating layer, a ferromagnetic layer, and / or a non-magnetic layer and the like.
  • the substrate may contain exposed integrated circuit structures, such as interconnect mechanisms such as metal wiring and dielectric materials. Examples of the metal and alloy used in the interconnection mechanism include aluminum, copper-aluminum alloy, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten.
  • the substrate may contain 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 or the like 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 according to the present invention include a method in which the object to be treated containing at least SiGe is brought into contact with the treatment liquid to dissolve SiGe.
  • 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.
  • SiGe in the object to be treated is mainly dissolved.
  • the dissolution rate of SiGe is, for example, preferably 10 ⁇ / min or more, more preferably 40 to 300 ⁇ / min, further preferably 50 to 200 ⁇ / min, and particularly preferably 70 to 150 ⁇ / min.
  • the object to be treated contains other materials (for example, silicon) in addition to SiGe
  • the other materials may or may not be dissolved together with SiGe by this treatment.
  • the other material may be dissolved intentionally or unavoidably.
  • the other material is not intentionally dissolved, it is preferable that the amount of the other material inevitably dissolved is small.
  • the member resistance to the material is excellent because the amount of the material that is inevitably dissolved is small with respect to the material that is not intentionally dissolved.
  • the treatment liquid preferably has excellent member resistance to silicon.
  • the dissolution rate of silicon in this treatment is preferably less than 10 ⁇ / min, more preferably 0.01 to 5 ⁇ / min, further preferably 0.01 to 1 ⁇ / min, and particularly preferably 0.01 to 0.5 ⁇ / min. ..
  • the object to be processed 200 shown in FIG. 3 is a form after the object to be processed 200 shown in FIG. 2 is processed by this processing method.
  • the other material 206 is a material (silicon or the like) that is not intentionally dissolved, and a part of SiGe204 is dissolved from the side surface to form a recess.
  • the other material 206 is a material that is not intentionally dissolved and all of SiGe204 is dissolved by this treatment method, the other material is not dissolved.
  • Material 206 is also preferably supported by other materials (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.
  • 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 for example, in general, 16 to 60 ° C. is preferable, and 18 to 40 ° C. is more preferable.
  • the temperature is preferably 90 to 250 ° C.
  • this 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, for example, the treatment liquid may be used for a cleaning application in which the substrate after dry etching is used as an object to be processed and the dry etching residue on the substrate is removed. At this time, the dry etching residue may or may not contain SiGe. Further, the object to be treated may or may not contain SiGe in a form other than the dry etching residue.
  • 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 above-mentioned method for dissolving SiGe may be described, a rinsing step and / or a drying treatment 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, modification). Etc.), resist forming step, exposure step and removal step, heat treatment step, cleaning step, inspection step and the like.
  • the target of application of the treatment liquid is, for example, NAND, DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), ReRAM (Resistive Random Access Memory), FRAM (Registered Random Access Memory), FRAM (Registered Random Access Memory), FRAM It may be (Magnetoresistive Random Access Memory), PRAM (Phase change Random Access Memory), or the like, or it may be a logic circuit, a processor, or the like.
  • each compound fluoride ion source, oxidant, additive, organic solvent
  • water listed in the table below are mixed so that the content of each compound becomes the value shown in the table, and each test is performed.
  • the treatment liquids to be applied to each were prepared.
  • all the components (residual) other than the above compounds are water.
  • each polymer used as an additive contains only representative repeating units to make up the polymer of its name.
  • the polyvinyl alcohol used in the examples contains only the repeating unit represented by -CH 2-CH (OH)-.
  • the phenol sulfonic acid formalin condensate used in the examples contains only a repeating unit in the form of condensation of phenol sulfonic acid and formalin.
  • a semiconductor-grade high-purity raw material was used, and further purification treatment was carried out as necessary.
  • SiGe ER dissolution rate for silicon-germanium
  • Si ER dissolution rate for polysilicon
  • Ra surface roughness (surface roughness of silicon-germanium film after treatment)
  • A: Ra surface roughness is 0.30 nm or less
  • Table 1 shows the formulation and results of the treatment liquid used in the series of tests X.
  • the "Amount (%)” column indicates the content (mass%) of each component with respect to the entire treatment liquid.
  • NH4F in the "fluoride ion source” column refers to NH 4 F (ammonium fluoride).
  • the specific additive is a polyvinyl alcohol, polystyrene sulfonic acid and its salt, a nitrogen atom-containing polymer other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene, in that the effect of the present invention is more excellent.
  • the treatment liquid contains an organic solvent in that the effect of the present invention is more excellent (see comparison of results between Examples 24 and 154 to 200).
  • the organic solvent is preferably one or more selected from the group consisting of ethylene glycol, propylene glycol, butyl diglycol, and sulfolane, and one or more selected from the group consisting of propylene glycol and sulfolane. It was confirmed that it was more preferable (see comparison of results of Examples 154 to 200, etc.).
  • the content of the oxidizing agent is preferably 5 to 15% by mass with respect to the total mass of the treatment liquid in that the effect of the present invention is more excellent (results of Examples 155 and 554). See comparison etc.).
  • the content of the organic solvent is preferably 20 to 45% by mass with respect to the total mass of the treatment liquid in that the effect of the present invention is more excellent (results of Examples 155 and 570). See comparison etc.).
  • Test Y Except that the treatment liquid to be used was fixed to the treatment liquid of Example 202 in Test X and the ratio of silicon to germanium in silicon germanium (Si: Ge (element ratio)) was changed, it was shown in Test X. In the same manner as above, the dissolution rate in silicon-germanium and the surface roughness of the silicon-germanium film after treatment were evaluated. The results are shown in the table below.
  • the "SiGe ratio" column in the table shows the ratio of silicon to germanium (Si: Ge (elemental ratio)) in the silicon-germanium film used for the test.
  • the ratio of silicon to germanium (Si: Ge (elemental ratio)) of SiGe treated by the treatment liquid is preferably 95: 5 to 50:50 in that the effect of the present invention is more excellent. It was confirmed that 85:15 to 65:35 is more preferable.
  • Test Z Two HDPE (high density polyethylene) bottles having a capacity of 20 L were prepared, and 15 L of the treatment liquid of Example 202 in Test X was placed in each of these bottles.
  • One of the above two bottles was a degassing cap shown in FIG. 1 and was covered with a cap that could be screwed and fixed to the bottle.
  • the other bottle was a cap without a degassing mechanism and was capped with a cap that could be screwed into and fixed to the bottle.
  • the two obtained bottles were allowed to stand at room temperature (25 ° C.) for 30 days, and then the appearance of each bottle was observed. As a result, no change in appearance was observed in the bottle covered with the degassing cap.
  • Treatment liquid container 102
  • Cap body 104
  • Waterproof ventilation film 106
  • Ventilation layer 108
  • Bottle body 110
  • Treatment liquid 112 Flow path 200
  • Processed object 202
  • Substrate 204
  • SiGe 206
  • Other materials

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