Processing liquid, processing liquid container

Abstract

To provide a processing liquid that can improve the smoothness of a processed portion when etching SiGe, and a processing liquid container for the processing liquid.SOLUTION: A processing liquid includes a fluoride ion source, an oxidizing agent, and an additive, and the additive is one or more selected from the group consisting of predetermined compounds.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a treatment liquid and a treatment liquid container. [Background technology]

[0002] 2. Description of the Related Art As semiconductor devices become increasingly miniaturized, there is an increasing demand for highly efficient and accurate processing, such as etching or cleaning, using processing liquids during the semiconductor device manufacturing process. For example, Patent Document 1 discloses "an etching solution suitable for selectively removing silicon-germanium relative to silicon from a microelectronic device, comprising water, an oxidizing agent, a water-miscible organic solvent, a fluoride ion source, and optionally, a surfactant (Claim 1)." [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2019-50365 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors evaluated the processing liquid (etching liquid) described in Patent Document 1 and found that there was room for improvement in the smoothness of the SiGe (silicon germanium) surface after etching the SiGe with the processing liquid.

[0005] In view of the above circumstances, an object of the present invention is to provide a processing liquid capable of improving the smoothness of a processed portion when etching SiGe. Another object of the present invention is to provide a treatment liquid container for the treatment liquid. [Means for solving the problem]

[0006] As a result of intensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0007] [1] a source of fluoride ions; An oxidizing agent; An additive, The treatment liquid, wherein the additive is at least one selected from the group consisting of polyvinyl alcohol, polystyrene sulfonic acid and its salts, nitrogen-containing polymers other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acids and their salts, alkyldiphenyletherdisulfonic acids and their salts, phenolsulfonic acid-formalin condensates and their salts, arylphenolsulfonic acid-formalin condensates and their salts, polyoxyethylene alkylethersulfonic acids and their salts, polyoxyethylene alkylethercarboxylic acids and their salts, polyoxyethylene alkylether phosphoric acids and their salts, polyoxyethylene alkylphenylether phosphoric acids and their salts, lauryldimethylaminoacetic acid betaine, dimethyllaurylamine oxide, silicon compounds, alkylamines, aromatic amines, nitrogen-containing heterocyclic compounds, amino acids other than cysteine, quaternary ammonium salts having 16 or less carbon atoms, and boron-containing compounds. [2] the additive contains a nitrogen atom-containing polymer other than the polyethyleneimine, The treatment liquid according to [1], wherein the nitrogen atom-containing polymer other than polyethyleneimine is at least one member selected from the group consisting of polyvinylpyrrolidone, polyallylamine, polyvinylamine, polyacrylamide, dimethylamine-epihalohydrin polymers, hexadimethrine salts, polydiallylamine, polydimethyldiallylammonium salts, poly(4-vinylpyridine), polyornithine, polylysine, polyarginine, polyhistidine, polyvinylimidazole, and polymethyldiallylamine. [3] The additive contains at least one of the alkylnaphthalenesulfonic acid and a salt thereof, The treatment liquid according to [1] or [2], wherein the alkylnaphthalenesulfonic acid and its salt are at least one selected from the group consisting of propylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, and dibutylnaphthalenesulfonic acid. [4] The additive contains at least one of the alkyl diphenyl ether disulfonic acid and a salt thereof, The treatment liquid according to any one of [1] to [3], wherein the alkyl diphenyl ether disulfonic acid or a salt thereof is dodecyl diphenyl ether disulfonic acid. [5] The additive contains at least one of the polyoxyethylene alkyl ether sulfonic acid and a salt thereof, The treatment liquid according to any one of [1] to [4], wherein the polyoxyethylene alkyl ether sulfonic acid is 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. [6] The additive contains at least one of the polyoxyethylene alkyl ether carboxylic acid and a salt thereof, The treatment liquid according to any one of [1] to [5], wherein the polyoxyethylene alkyl ether carboxylic acid is 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. [7] The additive contains at least one of the polyoxyethylene alkyl ether phosphate and a salt thereof, The treatment liquid according to any one of [1] to [6], wherein the polyoxyethylene alkyl ether phosphate is polyoxyethylene lauryl ether phosphate. [8] The additive contains the silicon compound, The treatment liquid according to any one of [1] to [7], wherein the silicon compound is at least one selected from the group consisting of alkoxysilanes, silanol compounds, oximesilanes, disilazanes, and siloxanes. [9] The treatment liquid according to [8], wherein the alkoxysilane is at least one selected from the group consisting of tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, 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)propyltrimethoxysilane.

[10] The treatment liquid according to [8] or [9], wherein the silanol compound is at least one selected from the group consisting of trimethylsilanol, dimethylsilanediol, diphenylsilanediol, silanetriol, 3-aminopropylsilanetriol, methylsilanetriol, 2-methyl-2-propylsilanetriol, methylacetatesilanetriol, 2-(chloroethyl)acetatesilanetriol, and 3-(hydroxypropyl)silanetriol.

[11] The treatment liquid according to any one of [8] to

[10] , wherein the oxime silane is at least one selected from the group consisting of di(ethylaldoxime)silane, mono(ethylaldoxime)silane, tris(ethylaldoxime)silane, tetra(ethylaldoxime)silane, methyltris(methylethylketoxime)silane, methyltosyl(acetoxime)silane, methyltris(methylisobutylketoxime)silane, dimethyldi(methylethylketoxime)silane, trimethyl(methylethylketoxime)silane, tetra(methylethylketoxime)silane, tetra(methylisobutylketoxime)silane, vinyltris(methylethylketoxime)silane, methylvinyldi(methylethylketoxime)silane, methylvinyldi(cyclohexanonexime)silane, vinyltris(methylisobutylketoxime)silane, and phenyltris(methylethylketoxime)silane.

[12] The treatment liquid according to any one of [8] to

[11] , wherein the disilazane is hexamethyldisilazane.

[13] The treatment liquid according to any one of [8] to

[12] , wherein the siloxane is at least one selected from the group consisting of hexamethyldisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.

[14] The additive contains the alkylamine, The treatment liquid according to any one of [1] to

[13] , wherein the alkylamine is at least one selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylethylenediamine, hexamethylenediamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, stearylamine, cyclohexylamine, phenethylamine, and m-xylylenediamine.

[15] The additive contains the aromatic amine, 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.

[16] The additive contains the nitrogen-containing heterocyclic compound, The treatment liquid according to any one of [1] to

[15] , wherein the nitrogen-containing heterocyclic compound is at least one selected from the group consisting of pyrrolidine, piperidine, piperazine, morpholine, pyrrole, pyrazole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, thiazole, 4-dimethylaminopyridine, and laurylpyridinium chloride.

[17] The additive contains an amino acid other than cysteine, The treatment solution according to any one of [1] to

[16] , wherein the amino acid other than cysteine ​​is one or more selected from the group consisting of alanine, arginine, asparagine, aspartic acid, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.

[18] The additive contains a quaternary ammonium salt having 16 or less carbon atoms, The treatment liquid according to any one of [1] to

[17] , wherein the quaternary ammonium salt having 16 or less carbon atoms is at least one selected from the group consisting of tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, methyltripropylammonium salt, methyltributylammonium salt, ethyltrimethylammonium salt, dimethyldiethylammonium salt, benzyltrimethylammonium salt, and (2-hydroxyethyl)trimethylammonium salt.

[19] The additive contains the boron-containing compound, The treatment liquid according to any one of [1] to

[18] , wherein the boron-containing compound is boric acid.

[20] The treatment liquid according to [1], wherein the additive is at least one selected from the group consisting of alkyldiphenyletherdisulfonic acid and phenolsulfonic acid-formaldehyde condensates. 〔twenty one〕 The treatment liquid according to any one of [1] to

[20] , further comprising an organic solvent. 〔twenty two〕 The organic solvent may be 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, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, glycerol, sulfolane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monobenzyl ether, diethylene glycol

[21] The treatment liquid according to

[21] , wherein the dimethyl ether is at least one selected from the group consisting of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoisopropyl ether, dipropylene monobutyl ether, dipropylene glycol diisopropyl ether, 1-methoxy-2-butanol, 2-methoxy-1-butanol, 2-methoxy-2-methylbutanol, 1,1-dimethoxyethane, 2-(2-butoxyethoxy)ethanol, methanol, ethanol, isopropanol, and 1-butanol. 〔twenty three〕 The treatment liquid according to

[21] or

[22] , wherein the organic solvent is at least one selected from the group consisting of propylene glycol and sulfolane. 〔twenty four〕 The treatment liquid according to any one of [1] to

[23] , wherein the oxidizing agent is a peroxide. 〔twenty five〕 The treatment liquid according to any one of [1] to

[24] , wherein the content of the oxidizing agent is less than 10 mass % based on the total mass of the treatment liquid.

[26] The treatment liquid according to any one of [1] to

[25] , which is used for a workpiece containing SiGe and removes at least a part of the SiGe contained in the workpiece.

[27] A treatment solution that is used on a workpiece containing SiGe and removes at least a portion of the SiGe contained in the workpiece, The treatment solution according to any one of [1] to

[26] , wherein the element ratio of Si to Ge in the SiGe is within a range of Si:Ge=95:5 to 50:50.

[28] Cu, Co, W, AlO x , AlN, AlO x N y , WO x , Ti, TiN, ZrO x , HfO x and TaO x The treatment solution according to any one of [1] to

[27] above, which is used for a treatment target containing a metal hard mask containing one or more of the above. Note that x is a number expressed as 1 to 3 and y is a number expressed as 1 to 2.

[29] A treatment liquid container having a container and the treatment liquid according to any one of [1] to

[28] contained in the container, The container has a gas venting mechanism for adjusting the pressure inside the container. Effect of the Invention

[0008] According to the present invention, it is possible to provide a processing liquid capable of improving the smoothness of a processed area when etching SiGe. The present invention can also provide a treatment liquid container for the treatment liquid. [Brief description of the drawings]

[0009] [Figure 1] 11 is a schematic cross-sectional view of an upper portion of a treatment liquid container to which a gas venting cap is applied. FIG. [Diagram 2] FIG. 2 is a cross-sectional view showing one embodiment of a workpiece. [Diagram 3] 1 is an example of a cross-sectional view showing a workpiece after being treated by the present treatment method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0012] In the present invention, "ppm" stands for "parts-per-million (10 -6 ) and "ppb" stands for "parts-per-billion (10 -9 )" and "ppt" stands for "parts-per-trillion (10 -12 )".

[0013] In this specification, "room temperature" is "25°C".

[0014] In this specification, the pH of the treatment solution is a value measured at room temperature (25° C.) using F-51 (product name) manufactured by Horiba, Ltd.

[0015] In this specification, unless otherwise specified, when there is a molecular weight distribution, the molecular weight is the weight average molecular weight. In this specification, the weight average molecular weight of a resin (polymer) is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0016] The components of the processing liquid referred to in this specification may be ionized in the processing liquid.

[0017] In the present specification, the term "salt" refers to a compound having a cationic nitrogen atom (N + Examples of salts of compounds containing fluoride, chloride, bromide, iodide, hydroxide, nitrate, and sulfate of the compound. Such salts may form salts with two or more kinds of anions. However, when the salt is an additive, it is also preferable that the salt is other than fluoride. Examples of salts of compounds containing a sulfonic acid group, a phosphoric acid group, a carboxylate group, etc. include alkali metal salts such as lithium salts, sodium salts, and potassium salts of the compounds, alkaline earth metal salts such as calcium salts, and ammonium salts, etc. Such salts may form salts with two or more kinds of cations. In the polymer, only a part or all of the groups capable of forming a salt may form a salt.

[0018] [Processing liquid] The treatment liquid of the present invention contains a fluoride ion source, an oxidizing agent, and an additive. The additives are at least one selected from the group consisting of polyvinyl alcohol, polystyrene sulfonic acid and its salts, nitrogen atom-containing polymers other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acid and its salts, alkyldiphenyletherdisulfonic acid and its salts, phenolsulfonic acid-formalin condensates and its salts, arylphenolsulfonic acid-formalin condensates and its salts, polyoxyethylene alkylethersulfonic acid, polyoxyethylene alkylethercarboxylic acid, polyoxyethylene alkylphosphoric acid, polyoxyethylene alkylphenyletherphosphoric acid, lauryldimethylaminoacetic acid betaine, dimethyllaurylamine oxide, silicon compounds, alkylamines, aromatic amines, nitrogen-containing heterocyclic compounds, amino acids other than cysteine, quaternary ammonium salts having 16 or less carbon atoms, and boron-containing compounds. Hereinafter, at least one additive selected from the above group is also referred to as a "specific additive".

[0019] The inventors have selected a component that exhibits properties that are effective in improving the smoothness of the treated area as a specific additive, and believe that the problem of the present invention has been solved by including such a specific additive in the treatment liquid. The treatment liquid of the present invention also has excellent selectivity for dissolving SiGe. For example, the treatment liquid of the present invention has excellent solubility for SiGe, while also having excellent anticorrosive properties for Si (silicon). Hereinafter, the ability of the treatment liquid of the present invention to provide good smoothness to the treated area when etching SiGe, excellent solubility in SiGe, and / or excellent corrosion resistance to Si is also referred to as the excellent effect of the present invention.

[0020] The components contained in the processing liquid of the present invention will be described in detail below.

[0021] <Fluoride ion source> The treatment liquid contains a source of fluoride ions. The fluoride ion source is a source of fluoride ions (F -and / or HF2 - It is a component that releases fluorine atoms (ions such as It is believed that the fluoride ions may assist in the removal of oxides of silicon and / or germanium formed under the action of an oxidizing agent, as described below. Examples of fluoride ion sources include hydrofluoric acid (HF), ammonium fluoride (NH4F), fluoroborates (KBF4, NH4BF4, etc.), fluoroboric acid, tetrabutylammonium tetrafluoroborate, aluminum hexafluoride, sodium fluoride, potassium fluoride, AlF2, LiF4, CaF3, NaHF6, NH4HF2, KHF2, H2SiF6, and R 1 NR 2 R 3 R 4 Examples of the compound represented by F include: Above R 1 NR 2 R 3 R 4 F, R 1 , R 2 , R 3 , and R 4 R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 1 , R 2 , R 3 , and R 4 The total number of carbon atoms in R is preferably 1 to 12. 1 NR 2 R 3 R 4 Examples of the compound represented by F include tetramethylammonium fluoride, tetraethylammonium fluoride, methyltriethylammonium fluoride, and tetrabutylammonium fluoride. The fluoride ion source is preferably hydrofluoric acid or ammonium fluoride.

[0022] The content of the fluoride ion source is not particularly limited, but in terms of better effects of the present invention, it is preferably 0.001 to 10 mass %, more preferably 0.01 to 5 mass %, and even more preferably 0.1 to 3 mass %, relative to the total mass of the treatment liquid. The fluoride ion source may be used alone or in combination of two or more. When two or more fluoride ion sources are used, the total amount thereof is preferably within the above range.

[0023] <Oxidizing agent> 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. Oxidizing agents include, for example, peroxides, persulfides (eg, monopersulfides and dipersulfides), percarbonates, acids thereof, and salts thereof. Among them, the oxidizing agent is preferably a peroxide (a compound containing one or more peroxy groups (-OO-)). The peroxide may be a peroxy acid (peracetic acid, perbenzoic acid, and salts thereof, etc.). Other suitable oxidizing agents include, for example, oxide halides (such as iodic acid, periodic acid, and their salts), perboric acid, perborates, permanganates, cerium compounds, and ferricyanides (such as potassium ferricyanide).

[0024] More specific examples of the oxidizing agent include peracetic acid, hydrogen peroxide, periodic acid, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and urea-hydrogen peroxide adduct. Among these, the oxidizing agent is preferably peracetic acid or hydrogen peroxide.

[0025] The content of the oxidizing agent is not particularly limited, but in terms of the superior effect of the present invention, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, based on the total mass of the treatment liquid. The upper limit of the content is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably less than 10% by mass, based on the total mass of the treatment liquid. The oxidizing agent may be used alone or in combination with two or more kinds. When two or more kinds of oxidizing agents are used, the total amount thereof is preferably within the above range.

[0026] <Specific additives (additives)> The treatment liquid contains one or more specific additives. The specific additive is a component selected from the group consisting of polyvinyl alcohol, polystyrene sulfonic acid and its salts, nitrogen-containing polymers other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acids and their salts, alkyldiphenyletherdisulfonic acids and their salts, phenolsulfonic acid-formalin condensates and their salts, arylphenolsulfonic acid-formalin condensates and their salts, polyoxyethylene alkylethersulfonic acids, polyoxyethylene alkylethercarboxylic acids, polyoxyethylene alkylphosphoric acids, polyoxyethylene alkylphenyletherphosphoric acids, lauryldimethylaminoacetic acid betaine, dimethyllaurylamine oxide, silicon compounds, alkylamines, aromatic amines, nitrogen-containing heterocyclic compounds, amino acids other than cysteine, quaternary ammonium salts having 16 or less carbon atoms, and boron-containing compounds. The above-mentioned fluoride ion source and oxidizing agent are not included in the specific additives.

[0027] Among them, the specific additive is preferably at least one selected from the group consisting of polyvinyl alcohol, polystyrene sulfonic acid and its salts, nitrogen atom-containing polymers other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acids and their salts, alkyldiphenyletherdisulfonic acids and their salts, phenolsulfonic acid-formalin condensates and their salts, arylphenolsulfonic acid-formalin condensates and their salts, polyoxyethylene alkylethersulfonic acids and their salts, polyoxyethylene alkylethercarboxylic acids and their salts, polyoxyethylene alkylether phosphoric acids and their salts, polyoxyethylene alkylphenylether phosphoric acids and their salts, alkylamines, aromatic amines, nitrogen-containing heterocyclic compounds, amino acids other than cysteine, quaternary ammonium salts having 16 or less carbon atoms, and boron-containing compounds; More preferred is one or more selected from the group consisting of alkyldiphenyletherdisulfonic acid and phenolsulfonic acid-formaldehyde condensates.

[0028] The content of the specific additive is not particularly limited, but in terms of better effects of the present invention, it is preferably 0.001 to 10 mass %, more preferably 0.01 to 5 mass %, and even more preferably 0.1 to 3 mass %, relative to the total mass of the treatment liquid. The specific additive may be used alone or in combination of two or more. When two or more specific additives are used, the total amount thereof is preferably within the above range. Each specific additive will be described below.

[0029] (Polyvinyl alcohol) Polyvinyl alcohol is a polymer containing repeat units of the formula -CH2-CH(OH)-. When polyvinyl alcohol contains repeating units other than -CH2-CH(OH)-, it is preferred that the content (molar ratio) of the repeating unit represented by -CH2-CH(OH)- is the greatest among all the types of repeating units. The content of the repeating unit represented by -CH2-CH(OH)- in polyvinyl alcohol is preferably from 51 to 100 mol %, more preferably from 75 to 100 mol %, based on the total repeating units of the polymer. The weight average molecular weight of the polyvinyl alcohol is preferably 400 to 50,000.

[0030] (Polystyrene sulfonic acid and its salts) Polystyrene sulfonic acid is a polymer that contains repeat units based on styrene sulfonic acid. The salt of polystyrene sulfonic acid is a polymer in which some or all of the sulfonic acid groups of the repeating units based on styrene sulfonic acid in the polystyrene sulfonic acid are converted into salts (alkali metal salts such as sodium salts, alkaline earth metal salts, ammonium salts, etc.). In other words, polystyrene sulfonic acid and its salts are polymers containing styrene sulfonic acid-based repeating units (a general term for repeating units based on styrene sulfonic acid and repeating units in which the sulfonic acid group of the repeating units based on styrene sulfonic acid is in the form of a salt). When polystyrene sulfonic acid and salts thereof contain repeating units other than styrene sulfonic acid repeating units, it is preferred that the content (molar ratio) of styrene sulfonic acid repeating units is the greatest among all types of repeating units. The content of styrenesulfonic acid-based repeating units in polystyrenesulfonic acid and salts thereof is preferably from 51 to 100 mol %, more preferably from 75 to 100 mol %, based on the total repeating units of the polymer. The weight average molecular weight of polystyrene sulfonic acid and its salts is preferably 400 to 50,000.

[0031] (Nitrogen-containing polymers other than polyethyleneimine) The nitrogen atom-containing polymer other than polyethyleneimine is preferably other than the specific additives mentioned above. The nitrogen atom-containing polymer other than polyethyleneimine is a polymer that contains a repeating unit that contains a nitrogen atom (N-containing repeating unit). However, the N-containing repeating unit referred to here does not include -CH2-CH2-N<. As long as a polymer contains an N-containing repeating unit, even if it contains -CH2-CH2-N< as part of the total repeating units, the polymer falls under the category of a nitrogen atom-containing polymer other than polyethyleneimine. When the nitrogen atom-containing polymer other than polyethyleneimine also contains repeating units other than the N-containing repeating unit, it is preferred that the content (molar ratio) of the N-containing repeating unit is the greatest among all types of repeating units. The content of the N-containing repeating unit in the nitrogen atom-containing polymer other than polyethyleneimine is preferably from 51 to 100 mol %, more preferably from 75 to 100 mol %, based on the total 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.

[0032] Examples of monomers from which the N-containing repeating unit is derived include vinylpyrrolidone, allylamine, vinylamine, acrylamide, hexadimethrine salt (halide salt, hydroxide salt, nitrate salt, sulfate salt, etc.), diallylamine, dimethyldiallylammonium salt (halide salt, hydroxide salt, nitrate salt, sulfate salt, etc.), 4-vinylpyridine, ornithine, lysine, arginine, histidine, vinylimidazole, and methyldiallylamine. In addition, a repeating unit consisting of dimethylamine and epihalohydrin (preferably epichlorohydrin) may be used as the N-containing repeating unit.

[0033] The nitrogen atom-containing polymer other than polyethyleneimine is preferably at least one selected from the group consisting of polyvinylpyrrolidone, polyallylamine, polyvinylamine, polyacrylamide, dimethylamine-epihydrin polymers (preferably dimethylamine-epihalohydrin copolymers, more preferably dimethylamine-epichlorohydrin copolymers), hexadimethrine salts (halide salts, hydroxide salts, nitrate salts, sulfate salts, etc.), polydiallylamine, polydimethyldiallylammonium salts (halide salts, hydroxide salts, nitrate salts, sulfate salts, etc.), poly(4-vinylpyridine), polyornithine, polylysine, polyarginine, polyhistidine, polyvinylimidazole, and polymethyldiallylamine.

[0034] (Polyoxyethylene laurylamine) The polyoxyethylene laurylamine is preferably other than the specific additives mentioned above. Polyoxyethylene laurylamine is, for example, 12 H 25 -N[(C2H4O) PE The compound is represented by the formula "H2". "C 12 H 25 -N[(C2H4O) PE In the formula (H]2), each of the two PEs independently represents an integer of 1 to 100.

[0035] (Alkylnaphthalenesulfonic acid and its salts) The alkylnaphthalenesulfonic acid and its salts are preferably other than the specific additives mentioned above. Alkylnaphthalenesulfonic acid is "(AL-) NL R NP A compound represented by "-SO3H" is preferred. "(AL-) NL R NP In "-SO3H", NL represents an integer of 1 to 7. AL represents an alkyl group. The alkyl group may be linear or branched, and may be entirely or partially cyclic. The alkyl group preferably has 1 to 25 carbon atoms. When a plurality of AL are present, the plurality of AL may be the same or different. R NP represents a naphthalene ring group which may have a substituent other than AL- and -SO3H.

[0036] The salt of alkylnaphthalenesulfonic acid is preferably a compound in which a part or all of the sulfonic acid groups in the alkylnaphthalenesulfonic acid are in the form of a salt (an alkali metal salt such as a sodium salt, an alkaline earth metal salt, an ammonium salt, or the like).

[0037] The alkylnaphthalenesulfonic acid and its salt are preferably one or more selected from the group consisting of propylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, and dibutylnaphthalenesulfonic acid. Salts of these compounds are also preferred.

[0038] (Alkyl diphenyl ether disulfonic acid and its salts) The alkyl diphenyl ether disulfonic acid and its salts are preferably other than the specific additives previously mentioned. The alkyl diphenyl ether disulfonic acid is preferably a compound represented by the following general formula (C1).

[0039] [ka]

[0040] In the general formula (C1), AL represents an alkyl group. The alkyl group may be linear or branched, and may be entirely or partially cyclic. The alkyl group preferably has 1 to 25 carbon atoms. When a plurality of AL are present, the plurality of AL may be the same or different.

[0041] The salt of alkyldiphenyletherdisulfonic acid is preferably a compound in which some or all of the sulfonic acid groups in the alkyldiphenyletherdisulfonic acid are in the form of a salt (such as an alkali metal salt such as a sodium salt, an alkaline earth metal salt, or an ammonium salt).

[0042] Of the alkyl diphenyl ether disulfonic acids and salts thereof, dodecyl diphenyl ether disulfonic acid is preferred, as are the salts of this compound.

[0043] (Phenolsulfonic acid-formaldehyde condensate and its salts) The phenolsulfonic acid-formaldehyde condensate and its salt are preferably other than the specific additives mentioned above. A phenolsulfonic acid-formalin condensate is a polymer containing a repeating unit formed by condensing phenolsulfonic acid and formalin. The salt of a phenolsulfonic acid-formalin condensate is a polymer in which some or all of the sulfonic acid groups in the repeating units formed by condensing phenolsulfonic acid and formalin in the above-mentioned phenolsulfonic acid-formalin condensate have become salts (alkali metal salts such as sodium salts, alkaline earth metal salts, ammonium salts, etc.). In other words, phenolsulfonic acid-formalin condensates and their salts are polymers containing phenolsulfonic acid-formalin-based repeating units (a general term for repeating units formed by condensation of phenolsulfonic acid and formalin, and repeating units formed by condensation of phenolsulfonic acid and formalin in which the sulfonic acid group of the repeating units is in the form of a salt). When the phenolsulfonic acid-formalin condensate and its salt contain repeating units other than the phenolsulfonic acid-formalin repeating units, it is preferred that the content (molar ratio) of the phenolsulfonic acid-formalin repeating units is the largest among all the types of repeating units. The content of the phenolsulfonic acid-formalin type repeating unit in the phenolsulfonic acid-formalin condensate and salts thereof is preferably from 51 to 100 mol %, more preferably from 75 to 100 mol %, based on the total repeating units of the polymer. The weight average molecular weight of the phenolsulfonic acid-formalin condensate and its salt is preferably 400 to 50,000.

[0044] (Arylphenolsulfonic acid-formaldehyde condensate and its salts) The arylphenolsulfonic acid-formaldehyde condensate and its salt are preferably other than the specific additives mentioned above. Examples of the arylphenolsulfonic acid formalin condensate and its salts include polymers in which the phenolsulfonic acid in the above description of the phenolsulfonic acid formalin condensate and its salts is replaced with an arylphenolsulfonic acid. The aryl group in the arylphenolsulfonic acid may, for example, be an aryl group having 6 to 14 carbon atoms.

[0045] (Polyoxyethylene alkyl ether sulfonic acid and its salts) It is preferred that the polyoxyethylene alkyl ether sulfonic acid and its salts are other than the specific additives mentioned above. Polyoxyethylene alkyl ether sulfonic acid and its salts are, for example, "AL-O-(C2H4O) PE -SO3H" and its salts. "AL-O-(C2H4O) PE In -SO3H", 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 be entirely or partially cyclic. The alkyl group preferably has 1 to 25 carbon atoms.

[0046] The polyoxyethylene alkyl ether sulfonic acid and its salt are preferably 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. Salts of these compounds are also preferred.

[0047] (Polyoxyethylene alkyl ether carboxylic acids and their salts) The polyoxyethylene alkyl ether carboxylic acid and its salt are preferably other than the specific additives mentioned above. Polyoxyethylene alkyl ether carboxylic acids and their salts are, for example, "AL-O-(C2H4O) PE -CH2-COOH" and its salts. "AL-O-(C2H4O) PE In "-CH2-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 be entirely or partially cyclic. The alkyl group preferably has 1 to 25 carbon atoms.

[0048] The polyoxyethylene alkyl ether carboxylic acid and its salt are preferably 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. Salts of these compounds are also preferred.

[0049] (Polyoxyethylene alkyl ether phosphate and its salts) The polyoxyethylene alkyl phosphate is preferably other than the specific additives mentioned above. Polyoxyethylene alkyl ether phosphate and its salts are, for example, "AL-O-(C2H4O) PE -PO3H2" or "[AL-O-(C2H4O) PE -]2PO2H" and its salts. "AL-O-(C2H4O) PE -PO3H2" and "[AL-O-(C2H4O) PE In "-]2PO2H", 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 be entirely or partially cyclic. The alkyl group preferably has 1 to 25 carbon atoms. "AL-O-(C2H4O) PE If there are multiple -'s, there are multiple "AL-O-(C2H4O) PE -" may be the same or different.

[0050] Of the polyoxyethylene alkyl ether phosphates and salts thereof, polyoxyethylene lauryl ether phosphate is preferred, and salts of this compound are also preferred.

[0051] (Polyoxyethylene alkylphenyl ether phosphate and its salts) It is preferred that the polyoxyethylene alkylphenyl ether phosphate and its salts are other than the specific additives mentioned above. Polyoxyethylene alkylphenyl ether phosphate and its salts are, for example, "AL-Ph-O-(C2H4O) PE -PO3H2" or "[AL-Ph-O-(C2H4O) PE -]2PO2H" and its salts. "AL-Ph-O-(C2H4O) PE -PO3H2" or "[AL-Ph-O-(C2H4O) PE In "-]2PO2H", PE 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 be entirely or partially cyclic. The alkyl group preferably has 1 to 25 carbon atoms. "AL-Ph-O-(C2H4O) PEIf there are multiple -'s, there are multiple "AL-Ph-O-(C2H4O) PE -" may be the same or different.

[0052] (Silicon compounds) The silicon compound is preferably other than the specific additives mentioned above. A silicon compound is a compound that contains a silicon atom (Si). The silicon compound is preferably at least one selected from the group consisting of alkoxysilane, silanol compound, oximesilane, disilazane, and siloxane.

[0053] Alkoxysilane The alkoxysilane is preferably other than the specific additives previously mentioned. An alkoxysilane is, for example, a compound having at least one (preferably 1 to 6) group represented by "alkyl group -O-" that is directly bonded to a silicon atom. Alkoxysilane is "(AL 2 -O-) S1 SiR Si S2 " is preferred. "(AL 2 -O-) S1 SiR Si S2 In the formula, S1 represents an integer of 1 to 4. S2 represents an integer of 0 to 3. However, S1+S2 is 4. AL 2 represents an alkyl group. The alkyl group may be linear or branched, and may be entirely or partially cyclic. The alkyl group preferably has 1 to 5 carbon atoms. R Si is a hydrogen atom or "AL 2represents a substituent other than -O-" and. Examples of the substituent include an alkyl group (preferably 1 to 10 carbon atoms), an aryl group (preferably 6 to 15 carbon atoms), an aminoalkyl group (preferably 1 to 10 carbon atoms), an aminoalkoxyaminoalkyl group (preferably 1 to 12 carbon atoms), a halogen atom, or a group consisting of a combination thereof. In addition, it is also preferable that the substituents as a whole satisfy the requirement that they are an organic group having 1 to 15 carbon atoms. AL 2 and / or R Si If there are multiple, there are multiple ALs. 2 and / or R Si may be the same or different.

[0054] In addition, alkoxysilanes are Si [-Si(-O-AL 2 ) S3 R Si S4 ]2". "L Si [-Si(-O-AL 2 ) S3 R Si S4 ]2” Medium, L Si represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group (preferably having 1 to 10 carbon atoms). S3 represents an integer of 1 to 3. S4 represents an integer of 0 to 2. However, one "-Si(-O-AL 2 ) S3 R Si S4 " In this case, S3 + S4 is 3. "L Si [-Si(-O-AL 2 ) S3 R Si S4 ]2" in AL 2 and R Si "(AL 2 -O-) S1 SiR Si S2 " in AL 2and R Si are synonymous with each other. AL 2 , R Si , S3, and / or S4, if there are multiple ALs 2 , R Si , S3, and / or S4 may each be the same or different.

[0055] The alkoxysilane is preferably one or more selected from the group consisting of tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, 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)propyltrimethoxysilane.

[0056] Silanol compounds The silanol compound is, for example, a compound having at least one (preferably 1 to 6) hydroxyl group directly bonded to a silicon atom. However, the silanol compound does not have an alkoxy group directly bonded to a silicon atom. The silanol compound is SJ S5 Si(OH) S6 " is preferred. "R SJ S5 Si(OH) S6 In the above, 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. Examples of the substituent include an alkyl group (preferably 1 to 10), an alkenyl group (preferably 2 to 10), an aryl group (preferably having 6 to 15 carbon atoms), an amino group, an acetyl group, a halogen atom, and a group consisting of a combination thereof. It is also preferable that the substituents as a whole satisfy the requirement that they are an organic group having 1 to 15 carbon atoms. R SJ If there are multiple, there are multiple R SJ may be the same or different.

[0057] The silanol compound is preferably at least one selected from the group consisting of trimethylsilanol, dimethylsilanediol, diphenylsilanediol, silanetriol, 3-aminopropylsilanetriol, methylsilanetriol, 2-methyl-2-propylsilanetriol, methylacetatesilanetriol, 2-(chloroethyl)acetatesilanetriol, and 3-(hydroxypropyl)silanetriol.

[0058] Oximesilane Preferably, the oxime silane is other than the specific additives previously mentioned. Oximesilane is a compound that bonds directly to silicon atoms (-ON=CR OX A compound having at least one (preferably 1 to 6) groups represented by "R OX Each of R independently represents a hydrogen atom or an organic group. OX may be bonded to each other to form a ring, provided that two R OX At least one of these is other than a hydrogen atom. The organic group is preferably an alkyl group. The alkyl group may be linear or branched, and may be entirely or partially cyclic. The alkyl group preferably has 1 to 25 carbon atoms. Two R OX When two ROX The group by which they are bonded to each other is preferably an alkylene group (preferably having 2 to 15 carbon atoms). However, the oxime silane does not have a group represented by an alkoxy group and / or a hydroxyl group directly bonded to a silicon atom.

[0059] Oximesilane is a SK S7 Si(-ON=CR OX 2) S8 " is preferred. "R SK S7 Si(-ON=CR OX 2) S8 In the above, S7 represents an integer of 0 to 4. S8 represents an integer of 1 to 4. However, S7+S8 is 4. R SK is a hydrogen atom, an alkoxy group, or a hydroxyl group, "-ON=CR OX The substituent represents a substituent other than a group represented by "2". Examples of the substituent include an alkyl group (preferably having 1 to 10 carbon atoms), an alkenyl group (preferably having 2 to 10 carbon atoms), an aryl group (preferably having 6 to 15 carbon atoms), an amino group, an acetyl group, a halogen atom, and groups consisting of combinations thereof. In addition, it is also preferable that the substituent as a whole satisfies the requirement that it is an organic group having 1 to 15 carbon atoms. R OX As mentioned above. R SK and / or R OX If there are multiple, there are multiple R SK and / or R OX may be the same or different.

[0060] The oxime silane is preferably one or more selected from the group consisting of di(ethylaldoxime)silane, mono(ethylaldoxime)silane, tris(ethylaldoxime)silane, tetra(ethylaldoxime)silane, methyltris(methylethylketoxime)silane, methyltosyl(acetoxime)silane, methyltris(methylisobutylketoxime)silane, dimethyldi(methylethylketoxime)silane, trimethyl(methylethylketoxime)silane, tetra(methylethylketoxime)silane, tetra(methylisobutylketoxime)silane, vinyltris(methylethylketoxime)silane, methylvinyldi(methylethylketoxime)silane, methylvinyldi(cyclohexanonexime)silane, vinyltris(methylisobutylketoxime)silane, and phenyltris(methylethylketoxime)silane.

[0061] Disilazane The disilazane is preferably other than the specific additives previously mentioned. Disilazane is, for example, SL 3Si-NH-SiR SL It is a compound represented by "3". R SK is a hydrogen atom, an alkoxy group, or a hydroxyl group, "-ON=CR OX The substituent represents a substituent other than a group represented by "2". Examples of the substituent include an alkyl group (preferably having 1 to 10 carbon atoms), an alkenyl group (preferably having 2 to 10 carbon atoms), an aryl group (preferably having 6 to 15 carbon atoms), an amino group, an acetyl group, a halogen atom, and groups consisting of combinations thereof. In addition, it is also preferable that the substituent as a whole satisfies the requirement that it is an organic group having 1 to 15 carbon atoms. However, disilazanes are alkoxy groups that are directly bonded to silicon atoms, such as "-ON=CR OX 2" and / or hydroxyl groups.

[0062] The disilazane is preferably hexamethyldisilazane.

[0063] Siloxane The siloxane is preferably other than the specific additives previously mentioned. The siloxane compound is, for example, SM 3Si(-O-SiR SN 2-) S9 R SO " is a compound represented by the formula: "R SM 3Si(-O-SiR SN 3-) S9 R SO In the formula, S9 represents an integer of 1 or more, and an integer of 1 to 10 is preferable. Three R's SM , 2 x S9 R SN , and R SO are each independently a hydrogen atom, an alkoxy group, or a hydroxyl group, and "-ON=CR OX It represents a substituent other than a group represented by "2". Examples of the substituent include an alkyl group (preferably 1 to 10), an alkenyl group (preferably 2 to 10), an aryl group (preferably having 6 to 15 carbon atoms), an amino group, an acetyl group, a halogen atom, and a group consisting of a combination thereof. In addition, it is also preferable that the substituent as a whole satisfies the requirement that it is an organic group having 1 to 15 carbon atoms. Also, three R SM One of them and R SO may be bonded to each other to form a divalent linking group. When a divalent linking group is formed, the divalent linking group is preferably -O-.

[0064] The siloxane is preferably at least one selected from the group consisting of hexamethyldisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.

[0065] (Alkylamine) Preferably, the alkylamine is other than the specific additives previously mentioned. An alkylamine is a compound containing at least one partial structure represented by "alkyl group-N." The alkyl group may have a substituent. However, it is preferable that the alkylamine is not any of the specific additives described above, the nitrogen-containing heterocyclic compounds described below, and amino acids 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 are represented by the formula "R N 2N(-L N -NR LN -) XN R N " is preferred. "R N 2N(-L N -NR LN -) XN R N " In this example, XN represents an integer between 0 and 6. Three R's N , and XN R LN each independently represents a hydrogen atom or an alkyl group which may have a substituent. The alkyl group in the alkyl group which may have a substituent may be linear or branched, and may be entirely or partially of a cyclic structure. The alkyl group preferably has 1 to 120 carbon atoms. The substituent in the alkyl group which may have a substituent is preferably an aryl group (preferably having 6 to 15 carbon atoms), an aminoalkyl group (preferably having 1 to 5 carbon atoms), or a combination thereof. The substituent is also preferably other than a carboxy group. The alkyl group which may have a substituent preferably has 1 to 20 carbon atoms in total. xnL N each independently represents an alkylene group having 1 to 8 carbon atoms. However, if XN is 0, then 3 R N At least one of the groups is an alkyl group which may have the above-mentioned substituent.

[0066] The alkylamine is preferably at least one selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylethylenediamine, hexamethylenediamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, stearylamine, cyclohexylamine, phenethylamine, and m-xylylenediamine.

[0067] (Aromatic amines) The aromatic amine is preferably other than the specific additives previously mentioned. An aromatic amine is a compound containing at least one partial structure represented by “aromatic ring group-N.” The aromatic ring group may have a substituent. However, it is preferable that the aromatic amine is not any of the specific additives described above, the nitrogen-containing heterocyclic compounds described below, and amino acids 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. Aromatic amines are classified as "R N 2Aromatic ring group which may have a N-substituent is preferred. "R N In "2N-substituted or optionally substituted aromatic ring group," two R N each independently represents a hydrogen atom or a substituent other than an alkyl group. The substituent in the aromatic ring group which may have a substituent is preferably an alkyl group (preferably having 1 to 20 carbon atoms), an aryl group (preferably having 6 to 15 carbon atoms), an aminoalkyl group (preferably having 1 to 5 carbon atoms), or a combination thereof. The aromatic ring group which may have a substituent preferably has 1 to 20 carbon atoms in total. The aromatic ring group which may have a substituent preferably has 5 to 15 carbon atoms and may contain a heteroatom as a ring member atom.

[0068] The aromatic amine is preferably at least one selected from the group consisting of aniline and toluidine.

[0069] (Nitrogen-containing heterocyclic compounds) The nitrogen-containing heterocyclic compound is preferably other than the specific additives mentioned above. The nitrogen-containing heterocyclic compound is a compound having a heterocyclic structure with at least one (preferably 1 to 4) nitrogen atom as a ring member atom. The nitrogen atom which is a member atom of the heterocyclic structure is a cationic nitrogen atom (N + ) may also be used. The heterocyclic structure may have a heteroatom (such as an oxygen atom or a sulfur atom) as a ring member atom in addition to the nitrogen atom. The heterocyclic structure may be a monocyclic or polycyclic ring. In the case of a monocyclic ring, a 5- to 8-membered ring is preferable. In the case of a polycyclic ring, the total number of rings is preferably 2 to 5, and each ring is preferably a 5- to 8-membered ring. The heterocyclic structure may or may not have aromaticity. In addition, when the heterocyclic structure is polycyclic, rings having aromaticity may be condensed with each other, rings not having aromaticity may be condensed with each other, or a ring having aromaticity and a ring not having aromaticity may be condensed with each other. The heterocyclic structure preferably has 3 to 20 ring atoms. The heterocyclic structure may contain a substituent (primary to tertiary amino group, etc.). The nitrogen-containing heterocyclic compound may have only one or more of the above heterocyclic structures in the entire compound. 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.

[0070] The nitrogen-containing heterocyclic compound is preferably at least one selected from the group consisting of pyrrolidine, piperidine, piperazine, morpholine, pyrrole, pyrazole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, thiazole, 4-dimethylaminopyridine, and laurylpyridinium chloride.

[0071] (Amino acids other than cysteine) The amino acid other than cysteine ​​is preferably other than the specific additives mentioned above. The amino acid other than cysteine ​​is preferably a compound containing a carboxy group and a primary or secondary amino group. The amino acid other than cysteine ​​is preferably one or more selected from the group consisting of alanine, arginine, asparagine, aspartic acid, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.

[0072] (Quaternary ammonium salts with 16 or less carbon atoms) The quaternary ammonium salt having 16 or less carbon atoms is preferably other than the specific additives mentioned above. Quaternary ammonium salts with 16 or less carbon atoms do not include pyridinium salts. Quaternary ammonium salts with 16 or less carbon atoms are, for example, T 4N + T - " is a compound represented by the formula: "R T 4N + T - " In the four R T are each independently N + represents an organic group in which the atom directly bonded to is a carbon atom. 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 a substituent may be linear or branched, and may be entirely or partially of a cyclic structure. The alkyl group preferably has 1 to 110 carbon atoms. The substituent in the optionally substituted alkyl group is preferably a hydroxyl group or an aryl group (preferably having 6 to 10 carbon atoms). The aryl group in the above-mentioned aryl group which may have a substituent preferably has 6 to 12 carbon atoms. The substituent in the optionally substituted aryl group is preferably a hydroxyl group or an alkyl group (preferably having 1 to 10 carbon atoms). T - is F - The above counter anions are other than OH. - is preferred. However, "R T 4N + T - The total number of carbon atoms contained in the compound represented by the formula "is 16 or less, and preferably 4 to 16.

[0073] The quaternary ammonium salt having 16 or less carbon atoms is preferably at least one selected from the group consisting of tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, methyltripropylammonium salt, methyltributylammonium salt, ethyltrimethylammonium salt, dimethyldiethylammonium salt, benzyltrimethylammonium salt, and (2-hydroxyethyl)trimethylammonium salt.

[0074] (Boron-containing compounds) The boron-containing compound is preferably other than the specific additives previously mentioned. A boron-containing compound is a compound that contains a boron atom (B). The boron atom-containing compound is preferably a compound having "-OH" directly bonded to a 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.

[0075] <Organic solvent> The treatment liquid preferably contains an organic solvent. Examples of organic solvents include alcohol-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents (including, for example, (poly)alkylene glycols substituted at both ends with alkyl groups or amino groups), sulfone-based solvents, sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents. Examples of alcohol-based solvents include alkanediols (including, for example, alkylene glycols), alkoxyalcohols (including, for example, glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and low molecular weight alcohols containing a ring structure.

[0076] It is also preferred that the organic solvent is other than an acetate-based solvent. It is also preferable that the treatment liquid does not substantially contain an acetate-based solvent, and for example, it is also preferable that the content of the acetate-based solvent is 0 to 1% by mass relative to the total mass of the treatment liquid.

[0077] Examples of the organic solvent include 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, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, glycerol, sulfolane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, monopropyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol monoisopropyl ether, dipropylene Glycol One or more selected from the group consisting of monobutyl ether, dipropylene glycol diisopropyl ether, 1-methoxy-2-butanol, 2-methoxy-1-butanol, 2-methoxy-2-methylbutanol, 1,1-dimethoxyethane, 2-(2-butoxyethoxy)ethanol, methanol, ethanol, isopropanol, and 1-butanol are preferred, and one or more selected from the group consisting of propylene glycol and sulfolane are more preferred.

[0078] The content of the organic solvent is not particularly limited, but in terms of better effects of the present invention, it is preferably 1 to 70 mass % relative to the total mass of the treatment liquid, more preferably 10 to 60 mass %, and even more preferably 20 to 45 mass %. The organic solvent may be used alone or in combination of two or more. When two or more organic solvents are used, the total amount thereof is preferably within the above range.

[0079] <Water> The treatment liquid preferably contains water. The water is not particularly limited, and examples thereof include distilled water, ion-exchanged water, and pure water.

[0080] The water content in the treatment liquid is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, and even 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.

[0081] <Method of manufacturing the treatment liquid> The method for producing the treatment liquid is not particularly limited, and a known method can be used. For example, a method in which water, a fluoride ion source, an oxidizing agent, and a specific additive are mixed in a predetermined amount can be used. When mixing the above components, other optional components may be mixed together as necessary. In addition, when producing the treatment liquid, the treatment liquid may be purified by filtering using a filter, if necessary.

[0082] The pH of the treatment liquid is preferably less than 7, and more preferably less than 4, in that the effects of the present invention are more excellent. In order to adjust the pH, the treatment liquid may contain a pH adjuster, which may include acid compounds (inorganic acids or organic acids, etc.) and base compounds (inorganic bases or organic bases, etc.) other than the above-mentioned components.

[0083] <Treatment liquid container and method for providing treatment liquid> The treatment solution may be stored in a container until use. Such a container and the processing liquid contained in the container are collectively referred to as a processing liquid container. The processing liquid is taken out from the stored processing liquid container and used. It is also preferable that the processing liquid is transported as a processing liquid container and provided between the manufacturer and the user, or between the storage location and the usage location, etc.

[0084] The container preferably has a degassing mechanism for adjusting the pressure (internal pressure) in the container. The degassing mechanism is a mechanism that, when gas is generated from the processing liquid due to a rise in temperature of the processing liquid inside the container and / or decomposition of some components of the processing liquid during storage of the processing liquid storage body, releases the generated gas from inside the container to the outside, thereby keeping the internal pressure within a certain range without excessively increasing it. An example of the gas venting mechanism is a check valve. It is also preferable to provide the container with a degassing mechanism by adopting a degassing cap equipped with a degassing mechanism as the cap of the container. In other words, it is also preferable that the container of the treatment liquid storage body has a degassing cap equipped with a degassing mechanism that adjusts the pressure inside the container. From the standpoint of ease of handling the processing liquid, it is preferable that the processing liquid be provided between the manufacturer and the user, or between the storage location and the usage location, by a method using such a processing liquid container.

[0085] An example of a gas release cap is a cap provided with a valve (preferably a check valve) that releases gas inside the container to the outside when a certain level of pressure (internal pressure) or more is applied to the cap. As another example, FIG. 1 illustrates a schematic cross-sectional view of the upper part of a treatment liquid container to which a gas venting cap is applied. The treatment liquid container 100 has a container including a cap (gas release cap) composed of a cap body 102, a waterproof breathable membrane 104, and a breathable layer 106, and a container body 108 sealed by the cap. The treatment liquid container 100 further has a treatment liquid 110 contained in the container body 108. The dashed arrow indicates a virtual flow path 112 for gas generated from the treatment liquid 110. The gas generated from the treatment liquid 110 permeates the waterproof breathable membrane 104 and is then released to the outside of the container through the breathable layer 106 and the gap between the cap body 102 and the container body 108, thereby preventing the internal pressure from increasing excessively due to the gas generated from the treatment liquid.

[0086] The waterproof breathable membrane 104 is a membrane with high gas permeability, which allows gas to pass through but not liquid. The ventilation layer 106 is a layer provided to allow gas that has permeated the waterproof breathable membrane 104 to be rapidly transported to the outside. The ventilation layer 106 is formed of, for example, a porous body (polyethylene foam, etc.). The ventilation layer 106 may be omitted. Although not shown in the drawings, it is also preferable that the cap body 102 and the container body 108 are formed with a structure for fixing the cap to the container body in a covered state (for example, a structure for fixing the cap body 102 to the container body 108 by screwing it). It is preferable that the above structure is a structure that does not prevent gas from being released to the outside.

[0087] The container (particularly the container body) is preferably one that has a high degree of cleanliness inside the container and has little elution of impurities for semiconductor applications. Examples of containers that can be used include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Plastics Industry Co., Ltd. The inner wall of the container (particularly the container body) is preferably made of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a different resin. It is also preferable that the inner wall of the container (particularly the container body) is made of a metal that has been treated to prevent rust and metal elution, such as stainless steel, Hastelloy, Inconel, or Monel.

[0088] The different resin is preferably a fluororesin (perfluororesin). By using a container whose inner wall is a fluororesin, the occurrence of a problem such as elution of ethylene or propylene oligomers can be suppressed compared to a container whose inner wall is a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin. An example of a container whose inner wall is a fluororesin is FluoroPure PFA composite drum manufactured by Entegris, Inc. In addition, containers described on page 4 or the like of JP-A-3-502677, page 3 or the like of WO 2004 / 016526, and pages 9 and 16 or the like of WO 99 / 46309 can also be used.

[0089] Furthermore, in addition to the above-mentioned fluororesins, quartz and electrolytically polished metal materials (that is, metal materials that have been electrolytically polished) are also preferably used for the inner wall of the container (particularly the container body). The metal material used in producing the electrolytically polished metal material preferably contains at least one element selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is more than 25 mass% based on the total mass of the metal material, and examples of such metal material include stainless steel and nickel-chromium alloys. The total content of chromium and nickel in the metal material is preferably 30 mass % or more based on 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 mass % or less with respect to the total mass of the metal material.

[0090] The stainless steel is not particularly limited, and any known stainless steel can be used. Among them, an alloy containing 8 mass % or more of nickel is preferable, and an austenitic stainless steel containing 8 mass % or more of nickel is more preferable. Examples of austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content 8 mass%, Cr content 18 mass%), SUS304L (Ni content 9 mass%, Cr content 18 mass%), SUS316 (Ni content 10 mass%, Cr content 16 mass%), and SUS316L (Ni content 12 mass%, Cr content 16 mass%).

[0091] The nickel-chromium alloy is not particularly limited, and any known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75 mass % and a chromium content of 1 to 30 mass % is preferable. Examples of nickel-chromium alloys include Hastelloy (trade name, the same applies below), Monel (trade name, the same applies below), and Inconel (trade name, the same applies below). More specifically, examples of nickel-chromium alloys include Hastelloy C-276 (Ni content: 63 mass%, Cr content: 16 mass%), Hastelloy-C (Ni content: 60 mass%, Cr content: 17 mass%), and Hastelloy C-22 (Ni content: 61 mass%, Cr content: 22 mass%). Furthermore, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, or cobalt, in addition to the above-mentioned alloy, as necessary.

[0092] The method for electrolytically polishing the metal material is not particularly limited, and any known method can be used. For example, the methods described in paragraphs

[0011] to

[0014] of JP 2015-227501 A and paragraphs

[0036] to

[0042] of JP 2008-264929 A can be used.

[0093] The metal material is preferably buffed. The method of buffing is not particularly limited, and known methods can be used. The size of the abrasive grains used for finishing the buffing is not particularly limited, but #400 or less is preferred because it tends to reduce the unevenness of the surface of the metal material. It is preferable that the buffing is carried out before the electrolytic polishing. The metal material may be treated by one or a combination of two or more of multiple steps of buffing using different grit sizes of polishing abrasive grains, acid washing, and magnetic fluid polishing.

[0094] The inside of these containers (container body, cap, etc.) is preferably washed before filling with the treatment liquid. The liquid used for washing is preferably one that has a reduced amount of metal impurities. After production, the treatment solution may be bottled in containers such as gallon bottles or coated bottles for transport or storage.

[0095] In order to prevent the components of the treatment solution from changing during storage, the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) with a purity of 99.99995% by volume or more. In particular, a gas with a low moisture content is preferable. In addition, the treatment solution may be transported and stored at room temperature, but the temperature may be controlled to a range of -20°C to 20°C to prevent deterioration.

[0096] The above-mentioned processing solution may be prepared as a kit in which the raw materials are divided into a plurality of parts. The treatment liquid may be prepared as a concentrated liquid. When the treatment liquid is a concentrated liquid, the concentration ratio is appropriately determined depending on the composition, but is preferably 5 to 2000 times. In other words, the concentrated liquid is used after being diluted 5 to 2000 times.

[0097] [Method of processing the object] <Item to be processed> The processing solution of the present invention is preferably applied to a method for processing a workpiece containing SiGe (hereinafter, also simply referred to as "the processing method"). In this processing method, it is preferable to remove (etch) at least a part of the SiGe contained in the object to be processed.

[0098] SiGe is a material consisting of a combination of silicon (Si) and germanium (Ge), and can be preferably used 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 mass%, more preferably 99 to 100 mass%, and even more preferably 99.9 to 100 mass%, based on the total mass of SiGe. In addition, the element ratio of silicon (Si) to germanium (Ge) in SiGe (the ratio of the atom % occupied by Si atoms to the atom % occupied by Ge atoms in SiGe, Si:Ge) is preferably 99:1 to 30:70, more preferably 95:5 to 50:50, and further preferably 85:15 to 65:35.

[0099] The form of the workpiece is not particularly limited as long as it contains SiGe. For example, as shown in FIG. 2, the workpiece may be a workpiece 200 containing a substrate 202, and SiGe 204 and other materials 206 alternately stacked on the substrate 202. 2 shows an embodiment in which the workpiece 200 contains a plurality of SiGe 204 and a plurality of other materials 206, but one or both of the plurality of SiGe 204 and the plurality of other materials 206 may be present in only one layer. Also, in FIG. 2, there are shown areas on the substrate 202 where neither the SiGe 204 nor the other materials 206 are present, but such areas may be covered with the SiGe 204. In FIG. 2, the SiGe 204 is directly disposed on the substrate 202, but it may be disposed via another layer. The other material 206 may be any material other than SiGe. Also, the plurality of other materials 206 may be different layers. In particular, it is preferable that the processing object 200 contains at least one other material 206 that is silicon (Si).

[0100] The type of substrate contained in the workpiece is not particularly limited, and examples thereof include various substrates such as semiconductor wafers, glass substrates for photomasks, glass substrates for liquid crystal displays, glass substrates for plasma displays, substrates for FEDs (Field Emission Displays), substrates for optical disks, substrates for magnetic disks, and substrates for magneto-optical disks. Examples of materials that may be used for the semiconductor substrate include silicon, Group III-V compounds such as GaAs, or any combination thereof. Of these, the substrate is preferably made of silicon (Si). The size, thickness, shape, layer structure, etc. of the substrate are not particularly limited and can be appropriately selected as desired.

[0101] The workpiece may contain a metal hard mask. For example, the workpiece 200 shown in FIG. 2 may further contain a metal hard mask. Metal hard masks include, for example, Cu, Co, W, and AlO x , AlN, AlO x N y , WO x , Ti, TiN, ZrO x , HfO x and TaO x (wherein x is a number expressed by 1 to 3, and y is a number expressed by 1 to 2.) Metal hard masks are Cu, Co, W, and AlO x , AlN, AlO x N y , WO x , Ti, TiN, ZrO x , HfO x and TaO x The content of any one or more of these is preferably 30 to 100 mass %, more preferably 60 to 100 mass %, and even more preferably 95 to 100 mass %, based on the total mass.

[0102] The form of the SiGe and / or other materials contained in the workpiece is not particularly limited, and may be, for example, any of a film form, a wiring form, and a particulate form. When SiGe and / or other materials are in the form of a film, there are no particular limitations on the thickness, which may be appropriately selected depending on the application, and is, for example, 1 to 50 nm. The SiGe and / or other material may be disposed on only one major surface of the substrate, or on both major surfaces, and the SiGe and / or other material may be disposed over the entire major surface of the substrate, or over a portion of the major surface of the substrate.

[0103] The workpiece may contain various layers and / or structures as desired in addition to SiGe and / or other materials. For example, the substrate may contain metal wiring, gate electrodes, source electrodes, drain electrodes, insulating layers, ferromagnetic layers, and / or non-magnetic layers. The substrate may contain exposed integrated circuit structures, such as interconnect features, such as metal wiring and dielectric materials. Metals and alloys used in the interconnect features include, for example, aluminum, copper aluminum alloys, 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.

[0104] The method for manufacturing the object to be processed is not particularly limited. For example, an insulating film is formed on a substrate, and SiGe or the like is disposed on the insulating film by a sputtering method, a chemical vapor deposition (CVD) method, a molecular beam epitaxy (MBE) method, or the like, and then a planarization process such as CMP is performed to manufacture the object to be processed shown in FIG. 2.

[0105] <Processing method> The method for treating an object of the present invention includes a method in which an object containing at least SiGe is brought into contact with the treatment liquid to dissolve the SiGe. The method of contacting the object to be treated with the treatment liquid is not particularly limited, and examples thereof include a method of immersing the object to be treated in the treatment liquid contained in a tank, a method of spraying the treatment liquid on the object to be treated, a method of flowing the treatment liquid on the object to be treated, and any combination thereof. Among these, the method of immersing the object to be treated in the treatment liquid is preferred.

[0106] Additionally, mechanical agitation methods may be used to further enhance the cleaning ability of the treatment solution. Examples of mechanical stirring methods include a method of circulating the treatment liquid above the workpiece, a method of passing or spraying the treatment liquid above the workpiece, and a method of stirring the treatment liquid by ultrasonic or megasonic means.

[0107] The contact time between the object to be treated and the treatment liquid can be appropriately adjusted. 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 solution during treatment is not particularly limited, but is preferably from 20 to 75°C, more preferably from 20 to 60°C.

[0108] By carrying out this treatment, mainly SiGe in the treatment object is dissolved. The dissolution rate of SiGe is, for example, preferably 10 Å / min or more, more preferably 40 to 300 Å / min, further preferably 50 to 200 Å / min, and particularly preferably 70 to 150 Å / min.

[0109] When the workpiece contains other materials (e.g., silicon) in addition to SiGe, the other materials may or may not be dissolved together with the SiGe by this process. When the other materials are dissolved, they may be dissolved intentionally or unavoidably. In the case where the other materials are not intentionally dissolved, it is preferable that the amount of the other materials that is unavoidably dissolved is small. When a material is not intentionally dissolved, the amount of the material that is inevitably dissolved is small, this is also referred to as the component having excellent resistance to the material. For example, it is preferable that the treatment liquid has excellent component resistance to silicon. The dissolution rate of silicon in this treatment is preferably less than 10 Å / min, more preferably 0.01 to 5 Å / min, further preferably 0.01 to 1 Å / min, and particularly preferably 0.01 to 0.5 Å / min.

[0110] In this processing method, the SiGe contained in the processing object may be partially or entirely dissolved. The object to be processed 200 shown in FIG. 3 is one form of the object to be processed 200 shown in FIG. 2 after being processed by this processing method. In this case, in the processing object 200, the other material 206 is a material (such as silicon) that is not intentionally dissolved, and a part of the SiGe 204 is dissolved from the side surface to form a recess. In addition, in the workpiece 200 having the configuration shown in FIG. 2, if the other material 206 is a material that is not intentionally dissolved and if all of the SiGe 204 is dissolved by this processing method, it is also preferable that the other material 206 is supported by other materials not shown.

[0111] The present processing method may, if necessary, include a rinsing step in which the object to be processed is rinsed with a rinsing liquid. For example, after the object to be treated is brought into contact with the treatment liquid, a rinsing step may be further carried out.

[0112] Examples of the rinse liquid include water, hydrofluoric acid (preferably 0.001 to 1 mass% hydrofluoric acid), hydrochloric acid (preferably 0.001 to 1 mass% hydrochloric acid), hydrogen peroxide solution (preferably 0.5 to 31 mass% hydrogen peroxide solution, more preferably 3 to 15 mass% hydrogen peroxide solution), a mixture of hydrofluoric acid and hydrogen peroxide solution (FPM), a mixture of sulfuric acid and hydrogen peroxide solution (SPM), a mixture of ammonia water and hydrogen peroxide solution (APM), a mixture of hydrochloric acid and hydrogen peroxide solution (HPM), carbon dioxide water (preferably 10 to 60 mass ppm carbon dioxide water), ozone water (preferably 10 to 60 mass ppm ozone water), hydrogen water (preferably 10 to 20 mass ppm hydrogen water), a citric acid solution (preferably a 0.01 to 10 mass% citric acid solution), sulfuric acid (preferably a 1 to 10 mass% sulfuric acid solution), ammonia, Preferred is niacinnamoyl water (preferably 0.01 to 10 mass% ammonia water), isopropyl alcohol (IPA), an aqueous hypochlorous acid solution (preferably a 1 to 10 mass% aqueous hypochlorous acid solution), aqua regia (preferably an aqua regia solution corresponding to a volume ratio of "37 mass% hydrochloric acid:60 mass% nitric acid" of "2.6:1.4" to "3.4:0.6"), ultrapure water, nitric acid (preferably 0.001 to 1 mass% nitric acid), perchloric acid (preferably 0.001 to 1 mass% perchloric acid), an aqueous oxalic acid solution (preferably a 0.01 to 10 mass% aqueous oxalic acid solution), acetic acid (preferably a 0.01 to 10 mass% aqueous acetic acid solution or an undiluted acetic acid solution), or an aqueous periodic acid solution (preferably a 0.5 to 10 mass% aqueous periodic acid solution. Examples of periodic acid include orthoperiodic acid and metaperiodic acid).

[0113] The composition of the APM is preferably within the range of "ammonia water: hydrogen peroxide water: water = 1:1:1" to "ammonia water: hydrogen peroxide water: water = 1:3:45" (mass ratio), for example. The composition of the FPM is preferably within the range of "hydrofluoric acid:hydrogen peroxide:water=1:1:1" to "hydrofluoric acid:hydrogen peroxide:water=1:1:200" (mass ratio), for example. The composition of the SPM is preferably within the range of "sulfuric acid:hydrogen peroxide:water=3:1:0" to "sulfuric acid:hydrogen peroxide:water=1:1:10" (mass ratio), for example. The composition of HPM is preferably within the range of "hydrochloric acid:hydrogen peroxide:water=1:1:1" to "hydrochloric acid:hydrogen peroxide:water=1:1:30" (mass ratio), for example. Note that these preferred composition ratios are intended to mean composition ratios in which ammonia water is 28 mass% ammonia water, hydrofluoric acid is 49 mass% hydrofluoric acid, sulfuric acid is 98 mass% sulfuric acid, hydrochloric acid is 37 mass% hydrochloric acid, and hydrogen peroxide solution is 30 mass% hydrogen peroxide solution. The volume ratio is based on the volume at room temperature. The description of a preferred range of ["A:B:C=x:y:z" to "A:B:C=X:Y:Z"] indicates that it is preferable to satisfy at least one (preferably two, and more preferably all) of the ranges of ["A:B=x:y" to "A:B=X:Y"], ["B:C=y:z" to "B:C=Y:Z"], and ["A:C=x:z" to "A:C=X:Z"]. It should be noted that hydrofluoric acid, nitric acid, perchloric acid, and hydrochloric acid refer to aqueous solutions in which HF, HNO3, HClO4, and HCl are dissolved in water, respectively. Ozone water, carbon dioxide water, and hydrogen water refer to aqueous solutions in which O3, CO2, and H2 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 also contain an organic solvent.

[0114] A specific example of the rinsing step is a method in which a rinsing liquid is brought into contact with the object to be treated. The contact may be performed by immersing the substrate in the rinse liquid contained in a tank, spraying the rinse liquid onto the substrate, flowing the rinse liquid onto the substrate, or any combination of these methods.

[0115] The treatment time (contact time between the rinse liquid and the object to be treated) is not particularly limited, but is, for example, 5 seconds to 5 minutes. The temperature of the rinse liquid during the treatment is not particularly limited, but is generally preferably 16 to 60° C., more preferably 18 to 40° C. When SPM is used as the rinse liquid, the temperature is preferably 90 to 250° C.

[0116] In addition, the present processing method may include a drying step in which a drying process is carried out after the rinsing step, if necessary. The drying method is not particularly limited, but examples thereof include spin drying, flowing a dry gas over the substrate, heating the substrate with a heating means such as a hot plate or an infrared lamp, IPA (isopropyl alcohol) vapor drying, Marangoni drying, Rotagoni drying, or a combination thereof. Drying times vary depending on the particular method used, but are typically on the order of 30 seconds to several minutes.

[0117] The present processing method may be used for cleaning the object to be processed. More specifically, for example, the treatment liquid may be used for cleaning purposes in which the treatment liquid is applied to a substrate after dry etching as the treatment target, and dry etching residues on the substrate are removed. At this time, the dry etching residue may or may not contain SiGe. Furthermore, the object to be processed may or may not contain SiGe in a form other than a dry etching residue. In such cleaning applications, a cleaning method for applying a treatment liquid to a workpiece includes, for example, a method of contacting the workpiece with the treatment liquid. Specifically, the method may be the same as the method of contacting the workpiece with the treatment liquid described in the above-mentioned method for dissolving SiGe. After the cleaning process, a rinsing step and / or a drying process may be performed as described in the above method for dissolving SiGe. Additionally, the cleaning process may be performed simultaneously with the method of dissolving SiGe described above.

[0118] The treatment method using the treatment liquid may be carried out in combination with other steps in the manufacturing method of a semiconductor device, before or after the other steps. The treatment method may be incorporated into the other steps during the implementation of the treatment method, or the treatment method may be incorporated into the other steps. Other processes include, for example, processes for forming each structure such as metal wiring, gate structure, source structure, drain structure, insulating layer, ferromagnetic layer and / or non-magnetic layer (layer formation, etching, chemical mechanical polishing, modification, etc.), resist formation process, exposure process and removal process, heat treatment process, cleaning process, and inspection process. This processing method may be performed in a back end process (BEOL: Back end of the line) or in a front end process (FEOL: Front end of the line). The target to which the treatment liquid is applied may be, 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), or PRAM (Phase change Random Access Memory), or may be a logic circuit or a processor, etc. EXAMPLES

[0119] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0120] [Preparation of processing solution] Each compound (fluoride ion source, oxidizing agent, additive, organic solvent) and water shown in the table below were mixed so that the content of each compound was the value shown in the table, to prepare a treatment solution to be applied to each test. In addition, all components (the remainder) in the treatment liquid other than the above-mentioned compounds are water. Unless otherwise specified, each polymer used as an additive contains only a representative repeating unit for constituting the polymer of that name. For example, the polyvinyl alcohol used in the examples contains only a repeating unit represented by -CH2-CH(OH)-. Also, the phenolsulfonic acid-formalin condensate used in the examples contains only a repeating unit formed by condensation of phenolsulfonic acid and formalin. All of the raw materials used were of semiconductor grade and were further purified as required.

[0121] [Test X] <Testing and Evaluation> A substrate on which silicon germanium (Si:Ge=75:25 (element ratio)) was laminated to a thickness of 100 nm and a substrate on which polysilicon was laminated to a thickness of 100 nm were prepared, and each of these substrates was cut into a 2 x 2 cm square to obtain a test specimen. The test specimen was immersed in the treatment liquid (25° C.) of the Example or Comparative Example for 10 minutes. The thickness of the films (silicon germanium film and polysilicon film) before and after immersion was measured using an optical film thickness meter Ellipsometer M-2000 (JA Woollam Co., Ltd.), and the dissolution rate (Å / min) was calculated. The higher the solubility in silicon germanium, the better, and the lower the solubility in polysilicon, the better. Furthermore, the surface of the silicon germanium film after immersion was observed using an atomic force microscope (AFM Dimension Icon, manufactured by Bruker) to determine the surface roughness Ra, and the surface roughness of the silicon germanium film after the treatment was evaluated. The evaluation criteria are as follows: In each evaluation, the closer to A, the better the evaluation.

[0122] (SiGe ER (dissolution rate for silicon germanium)) A:70Å / min or more B: 50 Å / min or more, less than 70 Å / min C: 40 Å / min or more and less than 50 Å / min D: 10 Å / min or more and less than 40 Å / min E: Less than 10Å / min

[0123] (Si ER (dissolution rate for polysilicon)) A: Less than 0.5Å / min B: 0.5 Å / min or more, less than 1 Å / min C: 1 Å / min to less than 5 Å / min D: 5Å / min or more

[0124] (SiGe surface roughness (surface roughness of silicon germanium film after processing)) A: Ra (surface roughness) is 0.30 nm or less B: Ra is greater than 0.30 nm and less than 0.40 nm C: Ra is greater than 0.40 nm and less than 0.60 nm D: Ra is greater than 0.60 nm and less than 1.00 nm E:Ra is more than 1.00 nm

[0125] <Result> The formulations of the treatment solutions used in the series of tests X and the results are shown in Table 1. In Table 1, the "Amount (%)" column indicates the content (mass %) of each component relative to the entire treatment liquid. In the "Fluoride ion source" column, NH4F means NH4F (ammonium fluoride).

[0126] [Table 1]

[0127] [Table 2]

[0128]

Table 3

[0129]

Table 4

[0130]

Table 5

[0131]

Table 6

[0132]

Table 7

[0133]

Table 8

[0134]

Table 9

[0135]

Table 10

[0136]

Table 11

[0137]

Table 12

[0138] [Table 13]

[0139] [Table 14]

[0140] [Table 15]

[0141] [Table 16]

[0142] [Table 17]

[0143] [Table 18]

[0144] [Table 19]

[0145] [Table 20]

[0146] From the results shown in the table, it was confirmed that the problems of the present invention can be solved by using the treatment liquid of the present invention.

[0147] In addition, the specific additive is preferably one or more selected from the group consisting of polyvinyl alcohol, polystyrene sulfonic acid and its salts, nitrogen atom-containing polymers other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acid and its salts, alkyldiphenyletherdisulfonic acid and its salts, phenolsulfonic acid-formalin condensates and its salts, arylphenolsulfonic acid-formalin condensates and its salts, polyoxyethylene alkylethersulfonic acid, polyoxyethylene alkylethercarboxylic acid, polyoxyethylene alkylphosphoric acid, polyoxyethylene alkylphenyletherphosphoric acid, alkylamine, nitrogen-containing heterocyclic compound, amino acid other than cysteine, quaternary ammonium salts having 16 or less carbon atoms, and boron-containing compounds, and more preferably one or more selected from the group consisting of alkyldiphenyletherdisulfonic acid and phenolsulfonic acid-formalin condensates (see comparison of the results of Examples 155, 248 to 398).

[0148] It was confirmed that in order to obtain a more excellent effect of the present invention, it is preferable that the treatment liquid contains an organic solvent (see, for example, a comparison of the results of Example 24 with those of Examples 154 to 200). Among them, it was confirmed that the organic solvent is preferably one or more selected from the group consisting of ethylene glycol, propylene glycol, butyl diglycol, and sulfolane, and more preferably one or more selected from the group consisting of propylene glycol and sulfolane (see, for example, comparison of the results of Examples 154 to 200).

[0149] It was confirmed that the content of the oxidizing agent is preferably 5 to 15 mass % relative to the total mass of the treatment liquid in order to obtain a more excellent effect of the present invention (see, for example, a comparison of the results of Example 155 and Example 554).

[0150] It was confirmed that the content of the organic solvent is preferably 20 to 45 mass % relative to the total mass of the treatment liquid in order to obtain a more excellent effect of the present invention (see, for example, a comparison of the results of Example 155 and Example 570).

[0151] [Test Y] The dissolution rate of silicon germanium and the surface roughness of the silicon germanium film after treatment were evaluated in the same manner as in Test X, except that the treatment liquid used was fixed to the treatment liquid of Example 202 in Test X and the ratio of silicon to germanium (Si:Ge (element ratio)) in the silicon germanium was changed. The results are shown in the table below. The "SiGe ratio" column in the table indicates the ratio of silicon to germanium (Si:Ge (element ratio)) in the silicon germanium film subjected to the test.

[0152] [Table 21]

[0153] From the results shown in the table, it was confirmed that the ratio of silicon to germanium (Si:Ge (element ratio)) of SiGe treated with the treatment liquid is preferably 95:5 to 50:50, and more preferably 85:15 to 65:35, in terms of superior effects of the present invention.

[0154] [Test Z] Two 20 L HDPE (high density polyethylene) bottles were prepared, and 15 L of the treatment solution of Example 202 in Test X was poured into each of these bottles. One of the two bottles was covered with a gas release cap shown in Figure 1 that could be screwed onto the bottle and fixed. The other bottle was covered with a cap that did not have a gas release mechanism and could be screwed onto the bottle and fixed. The two bottles obtained were left to stand at room temperature (25°C) for 30 days, after which the appearance of each bottle was observed. As a result, no change in appearance was observed in the bottle capped with the gas release cap. On the other hand, it was confirmed that the bottle capped with the cap without the gas release mechanism was bulging. From these results, it has been confirmed that it is preferable to store and / or provide the processing liquid in the form of a processing liquid container in which the processing liquid is contained in a container having a gas venting cap. [Explanation of symbols]

[0155] 100 Processing liquid container 102 Cap body 104 Waterproof breathable membrane 106 Ventilation layer 108 Bottle body 110 Processing liquid 112 Channel 200 Processing object 202 Substrate 204 SiGe 206 Other Materials

Claims

1. a source of fluoride ions; An oxidizing agent; An additive, the additive is at least one selected from the group consisting of a nitrogen atom-containing polymer other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acid and its salt, phenolsulfonic acid-formalin condensate and its salt, arylphenolsulfonic acid-formalin condensate and its salt, polyoxyethylene alkyl ether sulfonic acid and its salt, polyoxyethylene alkyl ether carboxylic acid and its salt, and aromatic amine, A processing solution that is used on a workpiece containing SiGe and removes at least a portion of the SiGe contained in the workpiece, the nitrogen atom-containing polymer other than polyethyleneimine is at least one selected from the group consisting of polyallylamine, polyvinylamine, dimethylamine-epihalohydrin polymer, hexadimethrine salt, polydiallylamine, polydimethyldiallylammonium salt, poly(4-vinylpyridine), polyornithine, polylysine, polyarginine, polyhistidine, polyvinylimidazole, and polymethyldiallylamine; The alkyl naphthalene sulfonic acid is at least one selected from the group consisting of triisopropyl naphthalene sulfonic acid and dibutyl naphthalene sulfonic acid, The polyoxyethylene alkyl ether sulfonic acid is at least one selected from the group consisting of polyoxyethylene oleyl ether sulfonic acid and polyoxyethylene octyldodecyl ether sulfonic acid, the polyoxyethylene alkyl ether carboxylic acid is polyoxyethylene dodecyl ether carboxylic acid, The treatment liquid, wherein the aromatic amine is toluidine.

2. A fluoride ion source; An oxidizing agent; A treatment liquid containing an additive, the oxidizing agent is a peroxide, The content of the oxidizing agent is 5 to 15% by mass based on the total mass of the treatment liquid, the additive is at least one selected from the group consisting of polyvinyl alcohol, polystyrene sulfonic acid and its salts, nitrogen atom-containing polymers other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acids and their salts, alkyldiphenyletherdisulfonic acids and their salts, phenolsulfonic acid-formalin condensates and their salts, arylphenolsulfonic acid-formalin condensates and their salts, polyoxyethylene alkylethersulfonic acids and their salts, polyoxyethylene alkylethercarboxylic acids and their salts, polyoxyethylene alkylether phosphoric acids and their salts, polyoxyethylene alkylphenylether phosphoric acids and their salts, lauryldimethylaminoacetic acid betaine, dimethyllaurylamine oxide, silicon compounds, aromatic amines, nitrogen-containing heterocyclic compounds, amino acids other than cysteine, and boron-containing compounds; the silicon compound is at least one selected from the group consisting of alkoxysilanes, oximesilanes, and disilazanes; A processing liquid that is used on a workpiece containing SiGe and removes at least a portion of the SiGe contained in the workpiece.

3. A fluoride ion source; An oxidizing agent; An additive, Contains no organic solvents the additive is at least one selected from the group consisting of polyvinyl alcohol, polystyrene sulfonic acid and its salts, nitrogen-containing polymers other than polyethyleneimine, cetyltrimethylammonium chloride, stearyltrimethylammonium bromide, polyoxyethylene laurylamine, alkylnaphthalenesulfonic acids and their salts, alkyldiphenyletherdisulfonic acids and their salts, phenolsulfonic acid-formalin condensates and their salts, arylphenolsulfonic acid-formalin condensates and their salts, polyoxyethylene alkylethersulfonic acids and their salts, polyoxyethylene alkylethercarboxylic acids and their salts, polyoxyethylene alkylether phosphoric acids and their salts, polyoxyethylene alkylphenylether phosphoric acids and their salts, lauryldimethylaminoacetic acid betaine, dimethyllaurylamine oxide, silicon compounds, alkylamines, aromatic amines, and nitrogen-containing heterocyclic compounds; A processing liquid that is used on a workpiece containing SiGe and removes at least a portion of the SiGe contained in the workpiece.

4. the additive contains a nitrogen atom-containing polymer other than the polyethyleneimine, The treatment liquid according to claim 2 or 3, wherein the nitrogen atom-containing polymer other than polyethyleneimine is at least one selected from the group consisting of polyvinylpyrrolidone, polyallylamine, polyvinylamine, polyacrylamide, dimethylamine-epihalohydrin polymers, hexadimethrine salts, polydiallylamine, polydimethyldiallylammonium salts, poly(4-vinylpyridine), polyornithine, polylysine, polyarginine, polyhistidine, polyvinylimidazole, and polymethyldiallylamine.

5. The additive contains at least one of the alkylnaphthalenesulfonic acid and a salt thereof, The treatment liquid according to any one of claims 2 to 4, wherein the alkylnaphthalenesulfonic acid is at least one selected from the group consisting of propylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, and dibutylnaphthalenesulfonic acid.

6. The additive contains at least one of the alkyl diphenyl ether disulfonic acid and a salt thereof, The treatment liquid according to any one of claims 2 to 5, wherein the alkyl diphenyl ether disulfonic acid is dodecyl diphenyl ether disulfonic acid.

7. The additive contains at least one of the polyoxyethylene alkyl ether sulfonic acid and a salt thereof, The treatment liquid according to any one of claims 2 to 6, wherein the polyoxyethylene alkyl ether sulfonic acid is 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.

8. The additive contains at least one of the polyoxyethylene alkyl ether carboxylic acid and a salt thereof, The treatment liquid according to any one of claims 2 to 7, wherein the polyoxyethylene alkyl ether carboxylic acid is 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.

9. The additive contains at least one of the polyoxyethylene alkyl ether phosphate and a salt thereof, The treatment liquid according to any one of claims 2 to 8, wherein the polyoxyethylene alkyl ether phosphate is polyoxyethylene lauryl ether phosphate.

10. The additive contains the silicon compound, The treatment liquid according to claim 3 , wherein the silicon compound is at least one selected from the group consisting of alkoxysilanes, silanol compounds, oximesilanes, disilazanes, and siloxanes.

11. The treatment liquid according to claim 2 or 10, wherein the alkoxysilane is at least one selected from the group consisting of tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, 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)propyltrimethoxysilane.

12. The treatment liquid according to claim 10, wherein the silanol compound is at least one selected from the group consisting of trimethylsilanol, dimethylsilanediol, diphenylsilanediol, silanetriol, 3-aminopropylsilanetriol, methylsilanetriol, 2-methyl-2-propylsilanetriol, methylacetatesilanetriol, 2-(chloroethyl)acetatesilanetriol, and 3-(hydroxypropyl)silanetriol.

13. The treatment liquid according to any one of claims 2 and 10 to 12, wherein the oxime silane is at least one selected from the group consisting of di(ethylaldoxime)silane, mono(ethylaldoxime)silane, tris(ethylaldoxime)silane, tetra(ethylaldoxime)silane, methyltris(methylethylketoxime)silane, methyltosyl(acetoxime)silane, methyltris(methylisobutylketoxime)silane, dimethyldi(methylethylketoxime)silane, trimethyl(methylethylketoxime)silane, tetra(methylethylketoxime)silane, tetra(methylisobutylketoxime)silane, vinyltris(methylethylketoxime)silane, methylvinyldi(methylethylketoxime)silane, methylvinyldi(cyclohexanonexime)silane, vinyltris(methylisobutylketoxime)silane, and phenyltris(methylethylketoxime)silane.

14. The treatment liquid according to any one of claims 2 and 10 to 13, wherein the disilazane is hexamethyldisilazane.

15. The treatment liquid according to claim 10, wherein the siloxane is at least one selected from the group consisting of hexamethyldisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.

16. The additive contains the alkylamine, The treatment liquid according to claim 3, wherein the alkylamine is at least one selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylethylenediamine, hexamethylenediamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, stearylamine, cyclohexylamine, phenethylamine, and m-xylylenediamine.

17. The additive contains the aromatic amine, The treatment liquid according to any one of claims 2 to 16, wherein the aromatic amine is at least one selected from the group consisting of aniline and toluidine.

18. the additive contains the nitrogen-containing heterocyclic compound, The treatment liquid according to any one of claims 2 to 17, wherein the nitrogen-containing heterocyclic compound is at least one selected from the group consisting of pyrrolidine, piperidine, piperazine, morpholine, pyrrole, pyrazole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, thiazole, 4-dimethylaminopyridine, and laurylpyridinium chloride.

19. The additive contains an amino acid other than cysteine, 3. The treatment solution according to claim 2, wherein the amino acid other than cysteine ​​is at least one selected from the group consisting of alanine, arginine, asparagine, aspartic acid, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.

20. The additive contains the boron-containing compound, The treatment solution according to claim 2 , wherein the boron-containing compound is boric acid.

21. The treatment liquid according to any one of claims 2 to 20, wherein the additive is at least one selected from the group consisting of alkyldiphenyletherdisulfonic acids and phenolsulfonic acid-formalin condensates.

22. The treatment liquid according to claim 1 or 2, further comprising an organic solvent.

23. The organic solvent may be 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, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, glycerol, sulfolane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monobenzyl ether, diethylene glycol di The treatment liquid according to claim 22, which is at least one selected from the group consisting of methyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol diisopropyl ether, 1-methoxy-2-butanol, 2-methoxy-1-butanol, 2-methoxy-2-methylbutanol, 1,1-dimethoxyethane, 2-(2-butoxyethoxy)ethanol, methanol, ethanol, isopropanol, and 1-butanol.

24. The treatment liquid according to claim 22 or 23, wherein the organic solvent is at least one selected from the group consisting of propylene glycol and sulfolane.

25. The treatment liquid according to claim 1 or 3, wherein the oxidizing agent is a peroxide.

26. The treatment liquid according to any one of claims 1 to 25, wherein the content of the oxidizing agent is less than 10 mass % based on the total mass of the treatment liquid.

27. A processing solution that is used on a workpiece containing SiGe and removes at least a portion of the SiGe contained in the workpiece, The treatment liquid according to any one of claims 1 to 26, wherein the element ratio of Si to Ge in the SiGe is within a range of Si:Ge=95:5 to 50:

50.

28. The treatment solution according to any one of claims 1 to 27, which is used for a treatment target including a metal hard mask containing one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx. Here, x is a number from 1 to 3, and y is a number from 1 to 2.

29. A treatment liquid container having a container and the treatment liquid according to any one of claims 1 to 28 contained in the container, The container has a gas venting mechanism for adjusting the pressure inside the container.

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