Chemical liquid, method for processing object to be processed, and method for producing semiconductor device

Abstract

The present invention addresses the problem of providing a chemical liquid which is capable of selectively removing a silicon germanium-containing material having a high germanium concentration from an object to be processed comprising two kinds of silicon germanium-containing materials that have different compositions. A chemical liquid according to the present invention is used for an object to be processed comprising two silicon-germanium-containing materials that have different germanium concentrations, and removes at least a portion of a silicon-germanium-containing material that has a high germanium concentration. This chemical liquid contains a fluoride ion source, an oxidizing agent, a specific unsaturated compound that has a group represented by formula (1) R2C=CH-*, and a solvent.

Description

Chemical solution, method for treating object to be treated, and method for manufacturing semiconductor device

[0001] The present invention relates to a chemical solution, a method for treating an object to be treated, and a method for manufacturing a semiconductor device.

[0002] As semiconductor devices become increasingly miniaturized, there is an increasing demand for highly efficient and accurate chemical etching and cleaning processes during the semiconductor device manufacturing process. In particular, when multiple materials exist on a substrate, it is desirable to be able to selectively remove a specific material.

[0003] For example, Patent Document 1 discloses a composition for selectively etching a silicon-germanium alloy layer in the presence of a silicon layer, the composition containing 5 to 15 mass % of an oxidizing agent, 5 to 20 mass % of a fluoride ion source, a specific compound having a hydroxy group or a carboxylic acid group, and water.

[0004] International Publication No. 2022 / 043165

[0005] Depending on the application, it may be necessary to selectively remove at least a portion of silicon-germanium (SiGe)-containing materials with a high germanium (Ge) concentration from a workpiece having a plurality of SiGe-containing materials with different compositions. The present inventors have studied the composition specifically disclosed in Patent Document 1 and found that the selective removal of SiGe-containing materials according to the Ge concentration is insufficient and that improvement is necessary.

[0006] Therefore, an object of the present invention is to provide a chemical solution capable of selectively removing SiGe-containing materials with a high Ge concentration from a workpiece having two types of SiGe-containing materials with different Ge concentrations. Another object of the present invention is to provide a method for treating a workpiece using the chemical solution and a method for manufacturing a semiconductor device.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A chemical solution used on a workpiece having two silicon-germanium-containing materials with different germanium concentrations, for removing at least a portion of the silicon-germanium-containing materials with a high germanium concentration, the chemical solution comprising a fluoride ion source, an oxidizing agent, a specific unsaturated compound having a group represented by formula (1) described below, and a solvent. [2] The chemical solution according to [1], wherein the specific unsaturated compound has at least one selected from the group consisting of an ester bond, an ether bond, an amide group, an amino group, and a hydroxy group. [3] The chemical solution according to [1] or [2], wherein the specific unsaturated compound has a polyethylene glycol structure. [4] The chemical solution according to any one of [1] to [3], wherein the specific unsaturated compound has a plurality of groups represented by formula (1). [5] The chemical solution according to any one of [1] to [4], wherein the solvent contains a water-soluble organic solvent. [6] The chemical solution according to [5], wherein the content of the water-soluble organic solvent is 30 mass% or more relative to the total mass of the chemical solution. [7] The chemical solution according to [5] or [6], wherein the water-soluble organic solvent is selected from the group consisting of alcohol solvents, carboxylic acid solvents, ether solvents, and sulfoxide solvents. [8] The chemical solution according to any one of [5] to [7], wherein the water-soluble organic solvent is a carboxylic acid solvent. [9] The chemical solution according to any one of [1] to [8], wherein the content of the fluoride ion source is less than 5.0 mass% with respect to the total mass of the chemical solution.

[10] The chemical solution according to any one of [1] to [9], wherein the standard oxidation-reduction potential of the oxidizing agent is 1.3 V or higher.

[11] The chemical solution according to any one of [1] to

[10] , wherein the oxidizing agent is periodic acid.

[12] The chemical solution according to any one of [1] to

[10] , wherein the oxidizing agent is hydrogen peroxide.

[13] The chemical solution according to any one of [1] to

[12] , which is used for two silicon-germanium-containing materials having different germanium concentrations and a workpiece having a silicon-containing material.

[14] A method for treating a workpiece, which includes contacting a workpiece having two silicon-germanium-containing materials having different germanium concentrations with the chemical solution according to any one of [1] to

[13] , and removing at least a portion of the silicon-germanium-containing material having a high germanium concentration.

[15] A method for manufacturing a semiconductor device, comprising the method for treating an object to be treated according to

[14] .

[0009] According to the present invention, a chemical solution capable of selectively removing a SiGe-containing material with a high Ge concentration from a workpiece having two types of SiGe-containing materials with different compositions can be provided. Furthermore, according to the present invention, a method for treating a workpiece using the chemical solution and a method for manufacturing a semiconductor device can be provided.

[0010] 1 is a cross-sectional view showing an embodiment of an object to be treated, and FIG. 2 is an example of a cross-sectional view showing an object to be treated after being treated by a method for treating an object to be treated of the present invention.

[0011] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0013] In this specification, the term "SiGe-containing material" refers to a material containing Si and Ge elements, and is preferably a material composed essentially of only Si and Ge elements. "Composed essentially of only Si and Ge elements" means that the total content of Si and Ge elements is 90 atomic % or more with respect to all atoms of the material. A material composed essentially of only Si and Ge elements may contain other elements (e.g., C, N, O, B, and P) as long as the total content of Si and Ge elements is within the above range. The total content of Si and Ge elements in the SiGe-containing material is preferably 90 to 100 mass %, more preferably 99 to 100 mass %, and even more preferably 99.9 to 100 mass %, with respect to the total mass of the SiGe-containing material. In the SiGe-containing material, the content of Ge element (Ge / (Si+Ge)) relative to the total content of Si element and Ge element is preferably 60 atomic % or less, more preferably 50 atomic % or less, and even more preferably 45 atomic % or less. The lower limit of the content of Ge element relative to the total content of Si element and Ge element is preferably 5 atomic % or more, more preferably 25 atomic % or more. In this specification, "silicon (Si)-containing material" refers to a material containing Si element that is different from the above-mentioned SiGe-containing material and does not substantially contain Ge element. "Substantially not containing Ge element" means that the content of Ge element is less than 5 atomic % (preferably 0 atomic %) with respect to all atoms of the material. The Si-containing material is preferably a material composed substantially only of Si element. "Composed substantially only of Si element" means that the content of Si element is 90 atomic % or more with respect to all atoms of the material. In a material substantially composed of only Si element, other elements (e.g., C element, N element, O element, B element, P element, etc., excluding Ge element) may be contained as long as the content of Si element is within the above range.

[0014] In this specification, the bonding direction of a divalent group (e.g., -COO-) is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", the compound may be "X-O-CO-Z" or "X-CO-O-Z". In this specification, when there are multiple substituents and linking groups, etc. (hereinafter referred to as substituents, etc.) represented by specific symbols, or when multiple substituents, etc. are specified simultaneously, unless otherwise specified, this means that the respective substituents, etc. may be the same or different from each other. The same applies to the specification of the number of substituents, etc.

[0015] In this specification, "ppm" means "parts-per-million (10 －６ ) and "ppb" stands for "parts-per-billion (10 －９ ) and "ppt" stands for "parts-per-trillion (10 －１２ In this specification, 1 Å (angstrom) corresponds to 0.1 nm.

[0016] Unless otherwise specified, each component of the drug solution described in this specification may be ionized in the drug solution or may form a salt.

[0017] The chemical solution of the present invention is used for a workpiece having two SiGe-containing materials with different Ge concentrations, and removes at least a portion of the SiGe-containing material with a higher Ge concentration, and includes a fluoride ion source, an oxidizing agent, a specific unsaturated compound having a group represented by formula (1) described below, and a solvent.

[0018] Although the reason why the chemical solution having the above-described configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is achieved. In other words, even if the effect is achieved by a mechanism other than the one described below, it is still within the scope of the present invention. A chemical solution containing a fluoride ion source, an oxidizing agent, and a chemical solution can oxidize SiGe-containing materials, solubilize them in a solvent, and remove them from the workpiece. It is speculated that the group represented by formula (1) in the specific unsaturated compound contained in the chemical solution of the present invention selectively adsorbs to SiGe-containing materials with a low Ge concentration, suppressing solubilization. As a result, when the chemical solution of the present invention is used on a workpiece having two SiGe-containing materials with different Ge concentrations, it is believed that at least a portion of the SiGe-containing material with a high Ge concentration can be selectively removed. Hereinafter, the ability to more selectively remove SiGe-containing materials with a high Ge concentration from a workpiece having two SiGe-containing materials with different compositions is also simply referred to as "the effect of the present invention being superior."

[0019] Depending on the application, the chemical solution of the present invention may also preferably have excellent SiGe selective solubility. In this specification, "SiGe selective solubility" refers to the ability to selectively remove SiGe-containing materials relative to Si-containing materials when used on a workpiece having two SiGe-containing materials with different Ge concentrations and a Si-containing material. The chemical solution of the present invention is likely to exhibit excellent SiGe selective solubility by virtue of the specific unsaturated compound being adsorbed to the Si-containing materials.

[0020] [Fluoride Ion Source] The chemical solution of the present invention contains a fluoride ion source. The fluoride ion source is a fluoride ion source that generates fluoride ions (F － The fluoride ion source may be in the form of fluoride ions or fluorine-containing ions in the chemical solution. Examples of fluorine-containing ions include bifluoride ions (HF ２ － ), SiF ６ ２－ , TiF ６ ２－ , ZrF ６ ２－ , P.F. ６ －, and BF ４ － The fluoride ion source is often a salt of a fluoride ion or a fluorine-containing ion with a cation. Cations preferably contained in the fluoride ion source include H ＋ , Li ＋ , Na ＋ , K. ＋ , and NH ４ ＋ are mentioned, and H ＋ is preferred.

[0021] Examples of fluoride ion sources include hydrofluoric acid (HF) and ammonium fluoride (NH ４ F), hexafluorosilicic acid and its salts (H ２ SiF ６ , Na ２ SiF ６ etc.), fluoroboric acid (tetrafluoroboric acid) and its salts (HBF ４ , K.B.F. ４ , N.H. ４ BF ４ etc.), hexafluorotitanic acid and its salts (H ２ TiF ６ ), hexafluorozirconic acid and its salts (H ２ ZrF ６ ), and hexafluorophosphate and its salts (HPF ６ ), hydrofluoric acid or ammonium fluoride is preferred, and hydrofluoric acid is more preferred.

[0022] The fluoride ion source may be used alone or in combination of two or more. The content of the fluoride ion source is preferably 10.0 mass% or less, more preferably less than 5.0 mass%, further preferably 3.0 mass% or less, and particularly preferably 1.5 mass% or less, relative to the total mass of the chemical solution, in order to achieve better effects of the present invention. The content of the fluoride ion source is preferably 0.001 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.2 mass% or more, relative to the total mass of the chemical solution. A solution containing a fluoride ion source may be used as the fluoride ion source. When a solution containing a fluoride ion source is used as the fluoride ion source, the content of the fluoride ion source is the content of the fluoride ion source contained in the solution.

[0023] [Oxidizing Agent] The chemical solution of the present invention contains an oxidizing agent. The standard oxidation-reduction potential of the oxidizing agent is preferably 1.0 V or higher, more preferably 1.3 V or higher, and even more preferably 1.5 V or higher, in terms of achieving better effects of the present invention. The upper limit of the standard oxidation-reduction potential of the oxidizing agent is not particularly limited, but is preferably 4.0 V or lower, more preferably 2.5 V or lower. The standard oxidation-reduction potential is based on a standard hydrogen electrode.

[0024] Examples of the oxidizing agent include hydrogen peroxide, and peroxides such as peracetic acid, performic acid, perpropionic acid, and salts thereof; perhalogen acid compounds such as periodic acid, perchloric acid, and salts thereof; oxide halides such as iodic acid, chloric acid, hypochlorous acid, and salts thereof; nitric acid compounds such as nitric acid, cerium nitrate, and iron nitrate; persulfates, persulfates, persulfates, peroxodisulfate, and peroxodisulfate; persulfides; percarbonates; perboric acid and salts thereof; permanganates; isocyanuric acid compounds such as isocyanuric acid, trichloroisocyanuric acid, and salts thereof; cerium compounds; and ferricyanides such as potassium ferricyanide. In terms of obtaining superior effects of the present invention, peroxides or perhalogen acid compounds are preferred, and perhalogen acid compounds are more preferred. The periodic acid may include metaperiodic acid (HIO ４ ), and orthoperiodic acid (H ５ IO ６) are included. Among them, the oxidizing agent is preferably periodic acid (standard oxidation-reduction potential 1.6 V), hydrogen peroxide (standard oxidation-reduction potential 1.8 V), peracetic acid (standard oxidation-reduction potential 1.4 V), performic acid, or perpropionic acid, and periodic acid or hydrogen peroxide is more preferred. Note that the chemical solution may contain a component formed by a reaction between the oxidizing agent and a solvent described below. For example, when the chemical solution contains hydrogen peroxide, an acidic compound (e.g., sulfuric acid), and acetic acid, part of the hydrogen peroxide may react with the acetic acid to generate peracetic acid, and the peracetic acid may function as the oxidizing agent.

[0025] The oxidizing agent may be used alone or in combination of two or more. The content of the oxidizing agent is preferably 0.01 to 20 mass %, more preferably 0.01 to 15 mass %, even more preferably 0.1 to 10 mass %, and particularly preferably 0.5 to 7 mass %, relative to the total mass of the chemical solution, in terms of more excellent effects of the present invention. Furthermore, the content of the oxidizing agent in the chemical solution is preferably 0.1 to 5 mass %, more preferably 0.5 to 3 mass %, and even more preferably 0.5 to 1.5 mass %, in terms of more excellent SiGe selective solubility.

[0026] [Solvent] The chemical solution of the present invention contains a solvent. Examples of the solvent include water and an organic solvent. The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent refers to an organic solvent having a solubility in water (100 g) at 25°C of 20 g / 100 g or more. In terms of achieving better effects of the present invention, the solvent preferably contains a water-soluble organic solvent, and more preferably contains water and a water-soluble organic solvent.

[0027] Examples of the organic solvent include alcohol-based solvents, carboxylic acid-based solvents, ether-based solvents, sulfoxide-based solvents, ester-based solvents, ketone-based solvents, sulfone-based solvents, amide-based solvents, and nitrile-based solvents. The organic solvent is preferably selected from the group consisting of alcohol-based solvents, carboxylic acid-based solvents, ether-based solvents, and sulfoxide-based solvents, and more preferably a carboxylic acid-based solvent.

[0028] Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, t-butyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, 2-pentanol, t-pentyl alcohol, hexanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, 4-penten-2-ol, tetrahydrofurfuryl alcohol, furfuryl alcohol, and benzyl alcohol, and polyols such as glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, hexylene glycol, pinacol, and 1,3-cyclopentanediol.

[0029] Examples of carboxylic acid solvents include formic acid, acetic acid, and propionic acid.

[0030] Examples of ether solvents include dialkyl ethers such as diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, and cyclohexyl methyl ether; glycol ethers such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol propyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; and cyclic ethers such as tetrahydrofuran and 1,4-dioxane.

[0031] An example of a sulfoxide solvent is dimethyl sulfoxide (DMSO).

[0032] Examples of ester solvents include chain esters such as ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropanoate, propylene glycol monomethyl ether acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol diacetate, and propylene glycol diacetate, and cyclic esters such as propylene carbonate, ethylene carbonate, and diethyl carbonate.

[0033] Examples of solvents other than those mentioned above include ketone solvents such as acetone, dimethyl ketone (propanone), cyclobutanone, cyclopentanone, cyclohexanone, methyl ethyl ketone (2-butanone), 5-hexanedione, methyl isobutyl ketone, 1,4-cyclohexanedione, 1,3-cyclohexanedione, and cyclohexanone; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide; sulfone solvents such as sulfolane, 3-methylsulfolane, and 2,4-dimethylsulfolane; and nitrile solvents such as acetonitrile.

[0034] Among these, the water-soluble organic solvent preferably contains at least one selected from the group consisting of formic acid, acetic acid, propionic acid, and ethylene glycol monobutyl ether (EGBE), more preferably contains at least one selected from the group consisting of acetic acid, propionic acid, and EGBE, and even more preferably contains acetic acid.

[0035] The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the chemical solution, from the viewpoint of more excellent effects of the present invention. The upper limit is less than 100% by mass, preferably 99.5% by mass or less, and more preferably 99% by mass or less. When the chemical solution of the present invention contains a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 60% by mass or more, relative to the total mass of the chemical solution, from the viewpoint of more excellent effects of the present invention. Furthermore, the content of the water-soluble organic solvent is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of more excellent effects of the present invention.

[0036] [Specific Unsaturated Compound] The chemical solution of the present invention contains a specific unsaturated compound having a group represented by formula (1). ２ C=CH-* In formula (1), each R independently represents a hydrogen atom, a carboxylic acid group, or a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group represented by R include aliphatic hydrocarbon groups and aromatic hydrocarbon groups, with aliphatic hydrocarbon groups being preferred. The hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 2 to 20, and even more preferably 4 to 12. The aliphatic hydrocarbon group may be linear, branched, or cyclic, with linear or branched being preferred, and linear being more preferred. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl or alkenyl groups being preferred. Examples of the aromatic hydrocarbon group include phenyl groups, naphthyl groups, and anthryl groups, with phenyl groups being preferred. R is preferably a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent, with a hydrogen atom or an alkyl group having 4 to 12 carbon atoms which may have a substituent being more preferred. Examples of the substituent that the hydrocarbon group may have include a hydroxy group, a carboxylic acid group, an amide group, an amino group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and an alkylene glycol structure-containing group, and a hydroxy group, a carboxylic acid group, or an alkylene glycol structure-containing group is preferred. * indicates a bonding position.

[0037] The alkylene glycol structure-containing group is a group having an alkylene glycol structure, and specifically, for example, R Ｘ１ -(OL Ｘ１ ) ｓ -L Ｘ２ - is an example of a group represented by R Ｘ１represents a hydrogen atom or a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred, and an alkyl group or an alkenyl group being more preferred. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12. Examples of the substituent that the hydrocarbon group may have include a hydroxy group, a carboxylic acid group, an amide group, and an amino group. R Ｘ１ is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrogen atom. Ｘ１ each independently represents an alkylene group which may have a hydroxy group. The alkylene group is preferably linear or branched, more preferably linear. The number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. s represents an integer of 1 or more, preferably an integer of 2 or more. In other words, the alkylene glycol structure-containing group is also preferably a polyalkylene glycol structure-containing group. The upper limit of s is preferably 60 or less, more preferably 30 or less, and even more preferably 10 or less. L Ｘ２ represents a single bond or a divalent linking group. Examples of the divalent linking group include —O—, —CO—, an alkylene group, an alkenylene group, and groups formed by combining these groups.

[0038] In terms of achieving better effects of the present invention, the specific unsaturated compound preferably has a plurality of groups represented by formula (1). Specifically, the specific unsaturated compound preferably has two or more groups represented by formula (1), more preferably has 2 to 8 groups, and even more preferably has 3 to 6 groups.

[0039] The specific unsaturated compound has an ester bond (—CO—O—), an ether bond (—O—), an amide group (—CO—NR Ｎ ２ ), amino group (—NR Ｎ ２It is preferable that R has at least one bond selected from the group consisting of an ester bond and an ether bond, and it is even more preferable that R has an ether bond. Ｎ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent.

[0040] The specific unsaturated compound preferably has an alkylene glycol structure, more preferably a polyalkylene glycol structure, as a structure containing an ether bond. The alkylene group in the alkylene glycol structure and polyalkylene glycol structure is preferably linear or branched, more preferably linear. The number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. In particular, the specific unsaturated compound preferably has a polyethylene glycol structure in which the alkylene group is an ethylene group.

[0041] Examples of the specific unsaturated compound include compounds represented by formulas (2) to (4), with compounds represented by formula (3) or (4) being preferred, and compounds represented by formula (4) being more preferred. ２ C=CH-R １ Formula (3) R ２ C=CH-L １ -(OL ２ ) ｎ -R ２ Formula (4) {R ２ C=CH-L １ -(OL ２ ) ｎ -L ３} ｍ -X

[0042] In formulas (2) to (4), R is the same as R in formula (1).

[0043] In formula (2), R １represents an alkyl group which may have a hydroxy group or a cyclic ether group, an alkenyl group which may have a hydroxy group or a cyclic ether group, or a carboxylic acid group. The alkyl group and alkenyl group may be linear, branched, or cyclic, and are preferably linear or branched, and more preferably linear. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12, and even more preferably 3 to 10. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12, and even more preferably 3 to 10. The alkenyl group preferably has 1 or more carbon-carbon double bonds, and may have 2 or more carbon-carbon double bonds. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. When the alkyl group and alkenyl group have a hydroxy group or a cyclic ether group, the number of hydroxy groups or cyclic ether groups is preferably 1 to 3, and more preferably 1. R １ Among these, alkyl groups having 2 to 12 carbon atoms or alkenyl groups having 2 to 12 carbon atoms are preferred.

[0044] In formula (3), L １ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, -O-, -CO-, and a group formed by combining these. The alkylene group and alkenylene group are preferably linear or branched, and more preferably linear. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 12, and even more preferably 3 to 10. The alkenylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 12, and even more preferably 3 to 10. L １ is preferably -alkylene group-, -alkylene group-CO-, -alkenylene group-, or -alkenylene group-CO-.

[0045] In formula (3), L ２ each independently represents an alkylene group which may have a hydroxyl group. The alkylene group is preferably linear or branched, more preferably linear. The alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.２ may be the same or different, but are preferably the same.

[0046] In formula (3), n represents an integer of 1 or more. n is preferably 2 or more, and more preferably 3 or more. The upper limit of n is preferably 60 or less, more preferably 30 or less, and even more preferably 10 or less.

[0047] In formula (3), R ２ represents a hydrogen atom, a hydroxy group, or a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups, with aliphatic hydrocarbon groups being preferred. The hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 12. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups or alkenyl groups being preferred. Examples of the aromatic hydrocarbon group include phenyl groups, naphthyl groups, and anthryl groups, with phenyl groups being preferred. Examples of the substituent that the hydrocarbon group may have include hydroxy groups, carboxylic acid groups, amide groups, and amino groups. R ２ is preferably a hydrogen atom, a hydroxy group, or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, a hydroxy group, or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a hydrogen atom or a hydroxy group.

[0048] In formula (4), L １ , L ２ , and n are the L in formula (3), respectively. １ , L ２ , and n. In formula (4), there are multiple L １ , L ２ , and n may be the same or different from each other.

[0049] In formula (4), L ３ each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include L in formula (3). １ Examples of the group represented by the formula (I) include the divalent linking groups exemplified above.３ is preferably a single bond, —O—, or an alkylene group, more preferably a single bond, —O—, or an alkylene group having 1 to 4 carbon atoms.

[0050] In formula (4), X represents an m-valent linking group. Examples of the m-valent linking group include m-valent hydrocarbon groups which may have a substituent. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups, with aliphatic hydrocarbon groups being preferred. The hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 12, and even more preferably 3 to 8. When m is 4 and the hydrocarbon group has 1 carbon atom, the m-valent hydrocarbon group represents a carbon atom. Examples of the substituent that the hydrocarbon group may have include a hydroxy group, a carboxylic acid group, an amide group, an amino group, an alkoxy group, and a polyalkylene glycol structure-containing group, with a hydroxy group or a polyalkylene glycol structure-containing group being preferred. The polyalkylene glycol structure-containing group is as described above. When the hydrocarbon group has a polyalkylene glycol structure-containing group, it is preferable that the number of carbon atoms excluding the carbon number of the polyalkylene glycol structure-containing group satisfies the preferred range described above. When the m-valent hydrocarbon group has a substituent, the number of substituents is preferably 1 to 4, more preferably 1 to 3.

[0051] In formula (4), m represents an integer of 3 or greater. m is preferably an integer of 3 to 8, more preferably an integer of 3 to 6, and even more preferably 3 or 4.

[0052] The compound represented by formula (4) is preferably a compound represented by formula (5): H—(C(W)H) ｔ In formula (5), each W is independently a hydroxy group, a polyalkylene glycol structure-containing group, or R ２ C=CH-L １ -(OL ２ ) ｎ -L ３ -, provided that three or more of the t Ws are R ２ C=CH-L １ -(OL ２ ) ｎ -L３ - represents a group represented by the formula: t represents an integer of 3 or more, preferably an integer of 3 to 10, more preferably an integer of 4 to 8, and still more preferably an integer of 4 to 6. Of the t Ws, R ２ C=CH-L １ -(OL ２ ) ｎ -L ３ The number of groups represented by - is 3 or more, preferably 3 to 8, more preferably 3 to 6, and even more preferably 3 or 4.

[0053] Examples of unsaturated compounds include unsaturated fatty acids such as linolenic acid, oleic acid, and sorbic acid; polyalkylene glycol alkenylene ethers such as polyoxyethylene oleyl ether; polyalkylene glycol unsaturated fatty acid esters such as polyethylene glycol oleate and polyethylene glycol linoleate; and sorbitol unsaturated fatty acid esters such as polyoxyalkylene sorbitol tetraoleate, sorbitol tetraoleate, sorbitol trioleate, sorbitol dioleate, and sorbitol monooleate. Examples of the specific unsaturated compound include sorbitan unsaturated fatty acid esters such as sorbitan monooleate, sorbitan trioleate, polyoxyalkylene sorbitan tetraoleate, and polyoxyalkylene sorbitan trioleate, oleamide, ethylene glycol monoallyl ether, allyl methyl ether, glycerol α,α'-diallyl ether (glycerol diallyl ether), pentaerythritol tetraallyl ether, ethylene glycol monovinyl ether, maleic acid, 3-phenyl-2-propen-1-ol, and 1,2-epoxy-5-hexene. Commercially available specific unsaturated compounds can also be used. Examples of commercially available products include Emulgen 408, Emulgen 430, Rheodol 430V, Rheodol 440V, Rheodol 460V, and EMANON 4110 (all manufactured by Kao Corporation), and Sanicol M-700, Sanicol DMT-4715, and Sanicol MMT-200 (all manufactured by Sanyo Chemical Industries, Ltd.).

[0054] The specific unsaturated compound may be used alone or in combination of two or more. The content of the specific unsaturated compound is preferably 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, and even more preferably 0.01 to 1% by mass, based on the total mass of the chemical solution, in terms of more excellent effects of the present invention.

[0055] [Corrosion inhibitor] The chemical solution of the present invention may further contain a corrosion inhibitor. Note that the corrosion inhibitor is a component different from the components described above. The corrosion inhibitor is preferably a heterocyclic compound. The heterocyclic compound may be either an aromatic heterocyclic compound or an aliphatic heterocyclic compound, with aromatic heterocyclic compounds being preferred. The heterocyclic compound may be either a monocyclic or polycyclic compound, with monocyclic compounds being preferred. The heterocyclic compound preferably has 4 to 20 ring atoms, more preferably 5 to 10, even more preferably 5 to 8, and particularly preferably 5. The heterocyclic compound may have a substituent. Examples of the substituent include a hydroxy group, a carboxylic acid group, an amino group, an alkyl group, an aryl group, an alkoxy group, an acyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, a mercapto group, an imidazolyl group, and a halogen atom. If possible, the substituent may further have a hydroxy group, a carboxylic acid group, an amino group, a mercapto group, and a halogen atom as a substituent. The number of heteroatoms contained as ring member atoms in the heterocyclic compound is 1 or more, and from the viewpoint of better effects of the present invention, it is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 or 3. The heterocyclic compound preferably contains a nitrogen atom, an oxygen atom, or a sulfur atom as the heteroatom, and more preferably contains a nitrogen atom. That is, the heterocyclic compound is preferably a nitrogen-containing heterocyclic compound.

[0056] The nitrogen-containing heterocyclic compound is preferably an azole or a derivative thereof. An azole is a five-membered aromatic heterocyclic compound containing a nitrogen atom. The number of nitrogen atoms contained in the azole is preferably 1 to 4, and more preferably 1 to 3. Examples of the azole include pyrrole, in which one of the atoms constituting the azole ring is a nitrogen atom; imidazole and pyrazole, in which two of the atoms constituting the azole ring are nitrogen atoms; thiazole, in which one of the atoms constituting the azole ring is a nitrogen atom and the other is a sulfur atom; triazole, in which three of the atoms constituting the azole ring are nitrogen atoms; and tetrazole, in which four of the atoms constituting the azole ring are nitrogen atoms.

[0057] The azole derivatives include azoles having a substituent. Examples of the substituent include the substituents that the heterocyclic compounds described above may have. The alkyl group and aryl group may further have the substituents described above as substituents. When the azole has two or more substituents, two substituents may be bonded to each other to form a ring that may have a substituent. The ring may be either an aromatic ring or an aliphatic ring, and an aromatic ring is preferred. Examples of rings formed by bonding the substituents to each other include a benzene ring, an azole ring, a thiophene ring, a furan ring, and a pyridine ring. Examples of the substituent that the ring may have include the substituents that the azole may have.

[0058] Examples of imidazole and its derivatives include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole, 4-hydroxyimidazole, 2,2'-biimidazole, 4-imidazolecarboxylic acid, histamine, and benzimidazole, with imidazole being preferred. Examples of pyrazole and its derivatives include pyrazole, 2,4-dimethylpyrazole, 3,5-dimethylpyrazole, benzopyrazole, and 2-mercaptobenzopyrazole, with pyrazole being preferred. Examples of thiazole and its derivatives include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole, with thiazole being preferred. Examples of triazole and derivatives thereof include 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-1H-triazole, 1,2,3-triazole, 1-methyl-1,2,3-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxybenzotriazole, 5-methylbenzotriazole, and 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, of which 1,2,4-triazole, 3-methyl-1,2,4-triazole, or 3-amino-1,2,4-1H-triazole is preferred, and 1,2,4-triazole is more preferred. Examples of tetrazole and its derivatives include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyltetrazole, 5-aminotetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, and 1-(2-dimethylaminoethyl)-5-mercaptotetrazole, with 5-aminotetrazole being preferred.

[0059] Of the azoles and derivatives thereof, imidazole, pyrazole, triazole, or derivatives thereof are preferred, triazole or derivatives thereof are more preferred, and 1,2,4-triazole is even more preferred.

[0060] The content of the anticorrosive agent is preferably 0.01 to 10 mass %, more preferably 0.05 to 5 mass %, and even more preferably 0.5 to 2 mass %, based on the total mass of the chemical solution.

[0061] [Other Additives] The chemical solution may contain other additives in addition to those described above. Examples of other additives include amine compounds, silane compounds, surfactants, antifoaming agents, basic compounds, and acidic compounds. Note that all of these components are compounds different from the above-mentioned fluoride ion source, oxidizing agent, solvent, specific unsaturated compound, and corrosion inhibitor.

[0062] <Amine Compound> The chemical solution may contain an amine compound. The amine compound is preferably a compound in which one or more hydrogen atoms of ammonia are substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent. The amine compound is also preferably an alkanolamine compound having at least one hydroxy group as the substituent.

[0063] The alkyl group which may have a substituent may be either linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms. Examples of the substituent which the alkyl group may have include a halogen atom, a cyano group, an amino group, and a hydroxy group, with an amino group or a hydroxy group being preferred. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 2,3-hydroxypropyl group, a 2-aminoethyl group, and a 3-aminopropyl group. Examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group, a furyl group, a p-hydroxyphenyl group, and a p-chlorophenyl group.

[0064] Examples of the amine compound include methylamine, dimethylamine, trimethylamine, ethylamine, ethanolamine, diethylamine, diethanolamine, propylamine, diisopropanolamine, N-(3-aminopropyl)diethanolamine, and bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane, with diisopropanolamine or N-(3-aminopropyl)diethanolamine being preferred.

[0065] The content of the amine compound is preferably 0.01 to 1 mass %, more preferably 0.02 to 0.1 mass %, based on the total mass of the chemical solution.

[0066] <Silane Compound> The chemical solution may contain a silane compound. The silane compound is preferably a low-molecular-weight compound, and the molecular weight of the silane compound (when the silane compound has a molecular weight distribution, the weight-average molecular weight) is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. The lower limit is often 50 or more, and preferably 80 or more. The silane compound is not particularly limited as long as it is a compound having a silicon atom, but a compound having a hydrolyzable silyl group (a silyl group in which a hydrolyzable group is bonded to a silicon atom) is preferred. The silane compound is preferably an alkoxysilane or chlorosilane, more preferably an alkoxysilane, further preferably a dialkoxysilane or trialkoxysilane, and particularly preferably a trialkoxysilane.

[0067] The silane compound has an amino group (—NR Ｎ ２ It is also preferred that R Ｎ each independently represents a hydrogen atom or an optionally substituted hydrocarbon group (preferably having 1 to 6 carbon atoms). It is preferable that the amino group is not directly bonded to a silicon atom.

[0068] Among them, the silane compound is preferably a compound represented by formula (S). (R Ｓ ) ｄ Si(H) ｅ (X) ４－ｄ－ｅ (S)

[0069] In formula (S), d represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1. e represents an integer of 0 to 2, and preferably 0. d+e represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

[0070] In formula (S), R Ｓ is -NR Ｎ１ ２ , a cyclic ether group, —O—, and —NR Ｎ２ represents a hydrocarbon group which may have a group or structure selected from the group consisting of -. Ｓ If there are multiple R Ｓ The groups represented by R may be the same or different. ｓ Ga-NR Ｎ１ ２ , a cyclic ether group, —O—, and —NR Ｎ２ When the compound contains a group or structure selected from the group consisting of —O— and —NR, the number of groups or structures selected from the group consisting of —NR— and —NR— is preferably 1 or 2. Ｎ２ It is preferable that - is not adjacent to a silicon atom. Ｎ１ and R Ｎ２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with an epoxy group being preferred.

[0071] R ＳThe number of carbon atoms in the hydrocarbon group represented by the formula (I) is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 6. The hydrocarbon group is preferably an alkyl group, an alkenyl group, or an aryl group, and more preferably an alkyl group. The alkyl group may be linear, branched, or cyclic, but is preferably linear. The number of carbon atoms in the linear or branched alkyl group is preferably 1 to 18, and more preferably 1 to 6. Examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. The number of carbon atoms in the cyclic alkyl group (cycloalkyl group) is preferably 3 to 18, more preferably 3 to 12, and even more preferably 3 to 6. Examples of cycloalkyl groups include cyclopropyl and cyclohexyl groups. The alkenyl group preferably has 2 to 12 carbon atoms, and more preferably 2 to 6. Examples of the alkenyl group include a vinyl group and an allyl group. The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group.

[0072] In formula (S), X represents a hydrolyzable group. When a plurality of Xs are present, the groups represented by the plurality of Xs may be the same or different, and are preferably the same. Examples of the hydrolyzable group include an alkoxy group and a halogen atom. The number of carbon atoms in the alkyl group in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferred. X is preferably an alkoxy group, and more preferably an alkoxy group having 1 to 3 carbon atoms.

[0073] Examples of the silane compound include the compounds described in paragraphs

[0070] to

[0081] of WO 2017 / 217320 and the compounds described in paragraphs

[0056] to

[0066] of JP 2009-242604 A, the contents of which are incorporated herein by reference.

[0074] The silane compound may be used alone or in combination of two or more. The content of the silane compound is preferably 0.01 to 10 mass %, more preferably 0.05 to 5 mass %, and even more preferably 0.01 to 3.5 mass %, based on the total mass of the chemical solution.

[0075] <Surfactant> The chemical solution may contain a surfactant. The surfactant is a compound different from the specific unsaturated compound described above. Examples of surfactants include cationic surfactants, anionic surfactants, and amphoteric surfactants. The surfactant often has at least one hydrophobic group selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. The total carbon number of the surfactant is preferably 16 to 100.

[0076] Examples of cationic surfactants include primary to tertiary alkylamine salts (e.g., monostearyl ammonium chloride, distearyl ammonium chloride, tristearyl ammonium chloride, etc.) and modified aliphatic polyamines (e.g., polyethylene polyamine, etc.).

[0077] Examples of anionic surfactants include sulfonic acid surfactants having a sulfonic acid group, sulfate ester surfactants having a sulfate ester group, phosphonic acid surfactants having a phosphonic acid group, and phosphate ester surfactants having a phosphate ester group. Examples of anionic surfactants include the compounds exemplified in paragraphs

[0116] to

[0123] of WO 2022 / 044893, the contents of which are incorporated herein by reference.

[0078] The content of the surfactant is preferably 0.01 to 1% by mass, more preferably 0.02 to 0.1% by mass, based on the total mass of the chemical solution.

[0079] <Antifoaming agent> The chemical solution may contain an antifoaming agent. Surfactants may cause foaming depending on how they are used. Therefore, it is preferable that the chemical solution containing a surfactant contains an antifoaming agent that suppresses the generation of foaming, shortens the lifespan of the generated foam, and suppresses residual foam. The antifoaming agent is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include silicone-based antifoaming agents, fatty acid ester-based antifoaming agents, and long-chain aliphatic alcohol-based antifoaming agents. Among these, silicone-based antifoaming agents are preferred because of their superior effect of suppressing residual foam. It should be noted that the antifoaming agent does not include compounds contained in the above-mentioned surfactants.

[0080] <Basic Compound> The chemical solution may contain a basic compound. The basic compound is a compound different from the above-mentioned components. The basic compound is a compound that exhibits alkaline (pH greater than 7.0) in an aqueous solution. Examples of the basic compound include organic basic compounds and inorganic basic compounds.

[0081] Examples of organic basic compounds include quaternary ammonium salts, amine oxide compounds, nitro compounds, nitroso compounds, oxime compounds, ketoxime compounds, aldoxime compounds, lactam compounds, and isocyanide compounds. Note that the organic basic compounds are compounds different from the heterocyclic compounds described above. Examples of inorganic basic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, and ammonia or salts thereof.

[0082] The content of the basic compound is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.5 to 10% by mass, based on the total mass of the chemical solution.

[0083] [Physical properties of chemical solution] <pH> The pH of the chemical solution is preferably 0.5 to 9, more preferably 1 to 7. The pH of the chemical solution can be measured using a known pH meter by a method in accordance with JIS Z8802-1984. The measurement temperature is 25°C.

[0084] <Metal Content> The content (measured as ion concentration) of metals (e.g., metal elements Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) contained as impurities in the chemical solution is preferably 5 mass ppm or less, more preferably 1 mass ppm or less. In particular, the metal content is more preferably a value lower than 1 mass ppm, that is, a mass ppb order or less, particularly preferably 100 mass ppb or less, and most preferably less than 10 mass ppb. The lower limit is preferably 0.

[0085] <Insoluble Particles> The drug solution of the present invention preferably does not substantially contain insoluble particles. The term "insoluble particles" refers to particles of inorganic solids or organic solids that do not dissolve in the drug solution and ultimately exist as particles. The term "substantially does not contain insoluble particles" refers to a measurement composition obtained by diluting the drug solution 10,000 times with a solvent contained in the drug solution, and the number of particles with a particle size of 50 nm or more contained in 1 mL of the measurement composition is 40,000 or less. The number of particles contained in the measurement composition can be measured in the liquid phase using a commercially available particle counter. Commercially available particle counters include those manufactured by Rion and PMS. A representative example of the former is the KS-19F, and a representative example of the latter is the Chem20. To measure larger particles, devices such as the KS-42 series and LiQuilaz II S series can be used. Examples of insoluble particles include particles of inorganic solids such as silica (including colloidal silica and fumed silica), alumina, zirconia, ceria, titania, germania, manganese oxide, and silicon carbide; and particles of organic solids such as polystyrene, polyacrylic resin, and polyvinyl chloride. Methods for removing insoluble particles from the chemical solution include, for example, purification treatments such as filtering. Furthermore, it is preferable that the chemical solution does not contain abrasive grains.

[0086] <Coarse particles> The chemical solution may contain coarse particles, but the content thereof is preferably low. Coarse particles refer to particles having a diameter (particle size) of 1 μm or more when the particle shape is considered to be a sphere. The coarse particles contained in the chemical solution include particles such as dust, dirt, organic solids, and inorganic solids contained as impurities in the raw material, as well as particles such as dust, dirt, organic solids, and inorganic solids brought in as contaminants during the preparation of the chemical solution, and which ultimately exist as particles without dissolving in the chemical solution.

[0087] The content of coarse particles in the chemical solution is preferably 100 or less, more preferably 50 or less, particles with a particle size of 1 μm or more per mL of the chemical solution. The lower limit is preferably 0 or more, more preferably 0.01 or more, per mL of the chemical solution. The content of coarse particles present in the chemical solution can be measured in the liquid phase using a commercially available measuring device that uses a light scattering liquid particle measuring method with a laser as a light source.

[0088] [Method for Producing the Chemical Solution] The chemical solution of the present invention can be produced by a known method. The method for producing the chemical solution of the present invention will be described in detail below.

[0089] <Solution Preparation Step> Examples of methods for preparing the chemical solution of the present invention include a method of mixing the above-mentioned components. The order and / or timing of mixing the above-mentioned components are not particularly limited, and examples include a method of sequentially adding a fluoride ion source, an oxidizing agent, a specific unsaturated compound, and, if necessary, any optional components to a container containing a solvent, and then stirring to mix. Alternatively, the solution may be prepared by adjusting the pH of the mixed solution by adding a pH adjuster. When adding the components to a container, they may be added all at once, or may be added in multiple divided portions.

[0090] The stirring device and stirring method used to prepare the chemical solution may be a known device such as a stirrer or disperser. Examples of the stirrer include an industrial mixer, a portable stirrer, a mechanical stirrer, and a magnetic stirrer. Examples of the disperser include an industrial disperser, a homogenizer, an ultrasonic disperser, and a bead mill.

[0091] The mixing of the components in the chemical solution preparation step, the purification treatment described below, and the storage of the produced chemical solution are preferably carried out at 40° C. or lower, more preferably at 30° C. or lower. The lower limit is preferably 5° C. or higher, more preferably 10° C. or higher. By preparing, treating, and / or storing the chemical solution within the above temperature range, the performance can be maintained stably for a long period of time.

[0092] The drug solution of the present invention may be prepared as a kit in which the raw materials are divided into a plurality of parts. When the drug solution of the present invention is prepared as a kit, the raw materials may be mixed in a predetermined ratio at the time of use or before use to obtain the drug solution of the present invention. The drug solution may also be prepared as a concentrated solution. In this case, the diluted solution obtained by diluting with a dilution liquid before use is used. In other words, the kit may include the drug solution in the form of a concentrated solution and the dilution liquid.

[0093] (Purification) It is preferable to perform a purification treatment in advance on one or more of the raw materials used to prepare the chemical solution. Furthermore, if necessary, the chemical solution may be subjected to a purification treatment. The degree of purification is preferably such that the raw material has a purity of 99% by mass or more, and more preferably such that the purity of the raw solution has a purity of 99.9% by mass or more. The upper limit is preferably 99.9999% by mass or less.

[0094] Examples of purification methods include passing the raw material through an ion exchange resin or a reverse osmosis membrane (RO) membrane, reprecipitation, distillation of the raw material, and filtering. Any filter conventionally used for filtration can be used without particular limitation. Examples of materials constituting the filter include filters made of fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyallylsulfone (PAS), and polyolefin resins (including high-density or ultra-high molecular weight) such as polyethylene and polypropylene (PP). Among these materials, materials selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesins (including PTFE and PFA), and polyamide resins (including nylon) are preferred, with fluororesin filters being more preferred. Filtering the raw material using a filter made of these materials can effectively remove highly polar foreign matter that is likely to cause defects.

[0095] The purification treatment may be carried out by combining two or more of the above purification methods, or may be carried out multiple times.

[0096] (Container) The container for containing the above-mentioned chemical solution, concentrated solution, or kit is not particularly limited, and any known container can be used as long as corrosiveness by the liquid is not a problem. Specific examples of the container include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd. In addition, for the purpose of preventing impurities from being mixed (contaminated) into the raw materials and chemical solution, it is also preferable to use a multilayer container whose inner wall has a six-layer structure made of six types of resin, or a multilayer container whose inner wall has a seven-layer structure made of six types of resin. Examples of such containers include, but are not limited to, the containers described in JP 2015-123351 A. In addition, the containers exemplified in paragraphs

[0121] to

[0124] of WO 2022 / 004217 can also be used as containers, and the contents of these containers are incorporated herein by reference.

[0097] The interior of these containers is preferably washed before filling with the chemical solution. The liquid used for washing is preferably one that has a reduced amount of metal impurities. After production, the chemical solution may be bottled in a container such as a gallon bottle or a coated bottle, and then transported and stored.

[0098] To prevent changes in the components of the drug solution during storage, the inside of the container may be purged with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. A gas with a low moisture content is particularly preferred. During transportation and storage, the drug solution may be stored at room temperature, or the temperature may be controlled within the range of -20°C to 20°C to prevent deterioration.

[0099] The method for producing the chemical solution may further include a static elimination step of eliminating static electricity from the chemical solution.

[0100] [Uses] The chemical solution of the present invention is used for processing semiconductor substrates. More specifically, it is preferably used for semiconductor devices. "For semiconductor devices" means that it is used during the manufacture of semiconductor devices. The chemical solution can be used in the manufacturing process of semiconductor devices, and can be used to process, for example, SiGe-containing materials, Si-containing materials, insulating films, resist films, anti-reflective films, etching residues, and ashing residues (hereinafter simply referred to as "residues") present on a substrate. The chemical solution may also be used to process semiconductor substrates after chemical mechanical polishing. The chemical solution of the present invention can be suitably used as a liquid (etchant) for removing at least a portion of the SiGe-containing material with the higher Ge concentration from a workpiece containing two SiGe-containing materials with different Ge concentrations.

[0101] [Workpiece] The workpiece to be treated with the chemical solution of the present invention is a workpiece having two SiGe-containing materials with different Ge concentrations. By using the chemical solution of the present invention on the workpiece, at least a portion of the SiGe-containing material with a high Ge concentration can be selectively removed relative to the SiGe-containing material with a low Ge concentration. In the workpiece, the elemental ratio of Si and Ge elements in the SiGe-containing material with a high Ge concentration (Ge / (Si+Ge)) relative to the total content of Si and Ge elements in the SiGe-containing material is preferably 25 to 60 atomic %, more preferably 35 to 50 atomic %. In the workpiece, the elemental ratio of Ge elements in the SiGe-containing material with a low Ge concentration (Ge / (Si+Ge)) relative to the total content of Si and Ge elements is preferably 5 to 35 atomic %, more preferably 10 to 30 atomic %. In addition, in the workpiece, the difference between the Ge element content in the SiGe-containing material with a high Ge concentration and the Ge element content in the SiGe-containing material with a low Ge concentration is preferably 5 atomic % or more, and more preferably 10 atomic % or more.

[0102] The workpiece is not particularly limited as long as it has two SiGe-containing materials with different Ge concentrations. Typically, two SiGe-containing materials with different Ge concentrations are disposed on a substrate. In this specification, "on a substrate" includes any of the front, back, side, and grooves of the substrate. Furthermore, "a predetermined material is disposed on a substrate" includes cases where a predetermined material is directly present on the surface of the substrate, as well as cases where a predetermined material is present on the substrate via another layer. Furthermore, "two SiGe-containing materials with different Ge concentrations are disposed on a substrate" refers to any form of existence as long as two SiGe-containing materials with different Ge concentrations are simultaneously present on the substrate. For example, the two SiGe-containing materials may be in contact with each other, or may be in contact via another layer or member. Alternatively, the two SiGe-containing materials may be present on the same substrate but not in contact with each other. The form of the SiGe-containing materials on the substrate may be any of a film, wiring, plate, column, and particle. If the SiGe-containing materials are in a film form, their thickness is not particularly limited, and may be, for example, 1 to 50 nm. The SiGe inclusions may be located on only one or both major surfaces of the substrate, may be located over the entire major surface of the substrate, or may be located over a portion of the major surface of the substrate, or the substrate may have three or more SiGe inclusions with different Ge concentrations.

[0103] The workpiece may further contain Si-containing materials. By using the chemical solution of the present invention on a workpiece having a Si-containing material and two SiGe-containing materials with different Ge concentrations, at least a portion of the SiGe-containing material can be selectively removed relative to the Si-containing material. In many cases, the at least a portion of the SiGe-containing material is a portion or all of the SiGe-containing material with a high Ge concentration. The form of the Si-containing material on the substrate may be any of a film, a wiring, a plate, a column, and a particle.

[0104] The size, thickness, shape, and layer structure of the substrate are not particularly limited and can be appropriately selected as desired. The substrate may be either a single layer or a multilayer. Examples of the substrate include metal substrates, semiconductor substrates, conductive substrates other than metal, metal oxide substrates, glass substrates, and resin substrates, with semiconductor substrates being preferred. Examples of semiconductor substrates include 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 constituting the semiconductor substrate include silicon, germanium, and III-V group compounds such as GaAs, as well as combinations thereof.

[0105] 1 , the form of the workpiece may be, for example, a workpiece 200 including a substrate 202 and first SiGe-containing materials 204 and second SiGe-containing materials 206 alternately stacked on the substrate 202. The first SiGe-containing materials 204 and the second SiGe-containing materials 206 have different Ge concentrations, with the Ge concentration of the first SiGe-containing materials 204 being higher than the Ge concentration of the second SiGe-containing materials. Note that while FIG. 1 shows an embodiment in which the workpiece 200 includes a plurality of first SiGe-containing materials 204 and second SiGe-containing materials 206, only one layer of either or both of the plurality of first SiGe-containing materials 204 and the plurality of second SiGe-containing materials 206 may be present. 1 shows portions on the substrate 202 where neither the first SiGe inclusions 204 nor the second SiGe inclusions 206 are present, but such portions may be covered with either the first SiGe inclusions 204 or the second SiGe inclusions 206. In FIG. 1, the first SiGe inclusions 204 are disposed directly on the substrate 202, but they may be disposed via another layer. The second SiGe inclusions 206 may be supported by another material (not shown).

[0106] The workpiece may include, in addition to the SiGe-containing and Si-containing materials, other layers and / or structures as desired. For example, the substrate may include one or more components selected from the group consisting of metal wiring, a metal hard mask, a gate electrode, a source electrode, a drain electrode, an insulating layer, a ferromagnetic layer, and a non-magnetic layer. The substrate may include an exposed integrated circuit structure. The integrated circuit structure may include, for example, interconnect mechanisms such as metal wiring and dielectric materials. Examples of metals and alloys used in the interconnect mechanisms include aluminum, copper-aluminum alloys, copper, nickel, nickel silicide, cobalt, cobalt silicide, ruthenium, platinum, gold, titanium, tantalum, tungsten, titanium nitride, and tantalum nitride. The substrate may include one or more layers of a material selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

[0107] The method for manufacturing the workpiece is not particularly limited. For example, the workpiece may be manufactured by forming an insulating film on a substrate, disposing a SiGe-containing material and / or a Si-containing material on the insulating film by a method such as a sputtering method, a chemical vapor deposition (CVD) method, or a molecular beam epitaxy (MBE) method, and then performing a planarization process such as CMP.

[0108] Examples of applications of the object to be treated include DRAM (Dynamic Random Access Memory), FRAM (registered trademark) (Ferroelectric Random Access Memory), MRAM (Magnetoresistive Random Access Memory), PRAM (Phase Change Random Access Memory), logic circuits, and processors. Among these, the object to be treated is preferably one used for manufacturing semiconductor elements. In other words, the chemical solution is preferably used in a process for manufacturing semiconductor elements. As an element obtained by applying a chemical solution to a workpiece, a field effect transistor (FET) is preferred, and a gate-all-around-FET (GAA-FET) is more preferred. That is, the workpiece is preferably one obtained during the manufacturing process of a GAA-FET.

[0109] [Method for treating a workpiece] A method for treating a workpiece using the chemical solution of the present invention can be a method of contacting the workpiece with the chemical solution of the present invention. By contacting the workpiece with the chemical solution, SiGe-containing materials with a high Ge concentration in the workpiece are selectively removed (etched). Furthermore, when the workpiece has two SiGe-containing materials and a Si-containing material with different Ge concentrations, the SiGe-containing materials in the workpiece can also be selectively removed (etched) by appropriately adjusting the composition of the chemical solution.

[0110] Methods for contacting the workpiece with the chemical solution include, for example, immersing the workpiece in the chemical solution contained in a tank, spraying the chemical solution onto the workpiece, flowing the chemical solution over the workpiece, and combinations of these methods, and the method of immersing the workpiece in the chemical solution is preferred.

[0111] Furthermore, in order to further increase the treatment speed with the chemical solution, a mechanical stirring method may be used, such as a method of circulating the chemical solution above the workpiece, a method of passing or spraying the chemical solution above the workpiece, or a method of stirring the chemical solution by ultrasonic waves or megasonics.

[0112] The treatment time using the chemical solution can be adjusted as appropriate. The treatment time (contact time between the chemical solution and the object to be treated) is preferably 0.5 to 60 minutes, more preferably 1 to 20 minutes. The temperature of the chemical solution during treatment is preferably 10 to 100°C, more preferably 15 to 60°C.

[0113] When processing the workpiece, only a portion or all of the SiGe-containing material with a high Ge concentration in the workpiece may be removed. Alternatively, a portion of the Si-containing material with a low Ge concentration in the workpiece may be intentionally or unavoidably removed. The workpiece 200 shown in FIG. 2 is one example of the workpiece 200 shown in FIG. 1 after being processed by this processing method. In this case, the dissolution rate of the second SiGe-containing material 206 with a low Ge concentration is sufficiently lower than that of the first SiGe-containing material 204 with a high Ge concentration, and a portion of the first SiGe-containing material 204 is dissolved from the side, forming a recess.

[0114] The present processing method may include a rinsing step in which the object to be processed is rinsed with a rinsing liquid, as needed. For example, after the object to be processed is brought into contact with the chemical solution, a rinsing step may be further performed. 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 ammonium hydroxide, hydrogen peroxide and water (SC-1), 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 0.01 to 10 mass% citric acid solution), sulfuric acid (preferably 1 to 10 % by mass aqueous sulfuric acid), ammonia water (preferably 0.01 to 10% by mass aqueous ammonia), isopropyl alcohol (IPA), hypochlorous acid aqueous solution (preferably 1 to 10% by mass aqueous hypochlorous acid), aqua regia (preferably aqua regia corresponding to a volume ratio of "37% by mass hydrochloric acid:60% by mass nitric acid" of "2.6:1.4" to "3.4:0.6"), ultrapure water, nitric acid (preferably 0.001 to 1% by mass nitric acid), perchloric acid (preferably 0.001 to 1% by mass perchloric acid), oxalic acid aqueous solution (preferably 0.01 to 10% by mass aqueous oxalic acid), acetic acid (preferably 0.01 to 10% by mass aqueous acetic acid or acetic acid stock solution), or periodic acid aqueous solution (preferably 0.5 to 10% by mass aqueous periodic acid. Examples of periodic acid include orthoperiodic acid and metaperiodic acid). Hydrofluoric acid, nitric acid, perchloric acid, and hydrochloric acid are referred to as HF, HNO ３ , HClO ４ HCl and ozone water are intended to be aqueous solutions in which ozone, carbon dioxide, and hydrogen ... ３ , CO ２ , and H ２ In the present invention, an aqueous solution of

[0115] The rinse treatment may be carried out by contacting the workpiece with a rinse liquid. The above-described method of contacting the workpiece with a chemical liquid may also be applied as a method of contacting the workpiece with a rinse liquid.

[0116] The rinsing step may be followed by a drying step, if necessary. The drying method is not particularly limited, and 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, and combinations thereof.

[0117] [Method for Manufacturing a Semiconductor Device] The above-described method for processing a workpiece can be suitably applied to a method for manufacturing a semiconductor device. The above-described processing method may be performed before or after other processes performed on the substrate. The above-described cleaning method may be incorporated into other processes, or the above-described processing method may be incorporated into other processes. Examples of other processes include processes for forming structures such as metal wiring, gate structures, source structures, drain structures, insulating films, ferromagnetic layers, and nonmagnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and modification), resist formation processes, exposure processes, removal processes, heat treatment processes, cleaning processes, and inspection processes.

[0118] The above processing method may be performed at any stage of a back end process (BEOL: Back end of the line), a middle process (MOL: Middle of the line), or a front end process (FEOL: Front end of the line), and is preferably performed in a front end process or a middle process.

[0119] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples. Furthermore, all of the components used in the examples and comparative examples were classified as semiconductor grade or equivalent high purity grade.

[0120] [Preparation of Chemical Solutions] The components (fluoride ion source, oxidizing agent, solvent, specific unsaturated compound, and other optional components) shown in the table below were mixed so that the content of each component was the value shown in the table below, to prepare chemical solutions for each of the Examples and Comparative Examples. The components used in preparing the chemical solutions are as follows.

[0121] [Unsaturated compounds] Rheodol 430V (Kao Corporation) Rheodol 440V (Kao Corporation) Rheodol 460V (Kao Corporation) Ethylene glycol monoallyl ether Allyl methyl ether Emulgen 430 (Kao Corporation) EMANON 4110 (Kao Corporation) Linolenic acid Oleic acid Oleamide Emulgen 408 (Kao Corporation) Glycerol diallyl ether Surfynol 104E (comparison compound, Nissin Chemical Industry Co., Ltd.)

[0122] [Other ingredients] HF (hydrogen fluoride, fluoride ion source) Periodic acid (oxidizing agent, standard redox potential 1.6 V) Hydrogen peroxide (oxidizing agent, standard redox potential 1.8 V) 1,2,4-triazole (corrosion inhibitor) (OMe) ３ MeSi (silane compound), Takesurf (Takesurf A-47-Q, manufactured by Takemoto Yushi Co., Ltd., surfactant), APDA (N-(3-aminopropyl)diethanolamine, amine compound), sulfuric acid (acidic compound), ammonia (basic compound), acetic acid (solvent), propionic acid (solvent), EGBE (ethylene glycol monobutyl ether, solvent)

[0123] [Evaluation] According to the procedure described below, the solubility of each chemical solution was measured for a SiGe-containing material with a high Ge concentration, a SiGe-containing material with a low Ge concentration, and a Si-containing material, and the etching selectivity was evaluated.

[0124] A substrate with a 20 nm thick layer of a high Ge concentration SiGe-containing material (SiGe40, Si:Ge = 60:40 (element ratio)), a 30 nm thick layer of a low Ge concentration SiGe-containing material (SiGe25, Si:Ge = 75:25 (element ratio)), and a 100 nm thick layer of polysilicon (Si), a Si-containing material, were prepared. Each of these substrates was cut into a 2 x 2 cm square to prepare test specimens. The SiGe40 test specimen was immersed in the chemical solution (25°C) of the example or comparative example for 5 seconds. The SiGe25 test specimen was immersed in the chemical solution (25°C) of the example or comparative example for 1 minute. The Si test specimen was immersed in the chemical solution (25°C) of the example or comparative example for 2 minutes. Before and after the immersion, the film thicknesses of SiGe40, SiGe25, and Si were measured using an optical film thickness meter, Ellipsometer M-2000 (manufactured by JA Woollam). From the measured change in film thickness before and after immersion, the dissolution rate (Å / min) of each film when using each chemical solution was calculated. From the calculated dissolution rate of each film, the solubility and etching selectivity of each chemical solution for each film were evaluated based on the following evaluation criteria.

[0125] (Etching property of SiGe 40) H: Dissolution rate is 1300 Å / min or more M: Dissolution rate is 500 Å / min or more and less than 1300 Å / min L: Dissolution rate is less than 500 Å / min

[0126] (Etching property of SiGe25) H: Dissolution rate is 500 Å / min or more M: Dissolution rate is 150 Å / min or more and less than 500 Å / min L: Dissolution rate is 50 Å / min or more and less than 150 Å / min LL: Dissolution rate is less than 50 Å / min

[0127] (Si etching ability) H: Dissolution rate is 5 Å / min or more L: Dissolution rate is less than 5 Å / min

[0128] (Etching selectivity of SiGe40 relative to SiGe25) H: The ratio of the dissolution rate of SiGe40 to the dissolution rate of SiGe25 is 30 or more. M: The ratio of the dissolution rate of SiGe40 to the dissolution rate of SiGe25 is 7 or more and less than 30. L: The ratio of the dissolution rate of SiGe40 to the dissolution rate of SiGe25 is less than 7. In practice, the etching selectivity of SiGe40 relative to SiGe25 is preferably M or H, and more preferably H, in that SiGe inclusions with a high Ge concentration can be selectively removed.

[0129] (Etching selectivity of SiGe 40 relative to Si) H: The ratio of the dissolution rate of SiGe 40 to the dissolution rate of Si is 200 or more L: The ratio of the dissolution rate of SiGe 40 to the dissolution rate of Si is less than 200 When applied to a workpiece having two SiGe-containing materials with different Ge concentrations and a Si-containing material, the etching selectivity of SiGe 40 relative to Si is preferably H, in that the SiGe-containing material (especially the SiGe-containing material with a high Ge concentration) can be selectively removed.

[0130] [Results] The composition of each chemical solution and the evaluation results are shown in the table below. In the table below, the "SiGe40 / SiGe25" column shows the evaluation results of the etching selectivity of SiGe40 relative to SiGe25, and the "SiGe40 / Si" column shows the evaluation results of the etching selectivity of SiGe40 relative to Si. In the table below, when a chemical solution contains multiple water-soluble organic solvents, for example, the description "A+B" in the type column and "a+b" in the content column means that the chemical solution contains a mass % of solvent A and b mass % of solvent B. In the table below, the "Formula" column shows the formula corresponding to the structure of each unsaturated compound from the above-mentioned formulas (2) to (4). Table 2 is a continuation of Table 1, Table 4 is a continuation of Table 3, and Table 6 is a continuation of Table 5. For example, the chemical solution of Example 1 contains 0.41 mass % HF, 5 mass % periodic acid, 0.02 mass % Rheodol 430V, 1 mass % 1,2,4-triazole, 50 mass % acetic acid, 20 mass % propionic acid, and the remainder water.

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137] From the above table, it was confirmed that the chemical solution of the present invention can selectively remove SiGe-containing material with a high Ge concentration from a processing object having two types of SiGe-containing material with different compositions.

[0138] Comparisons between Example 6 and Example 9, and between Example 14 and Example 15, confirmed that the effects of the present invention were more excellent when the content of the water-soluble organic solvent was 40 mass% or more, relative to the total mass of the chemical solution. Comparisons between Example 6 and Example 8, and between Example 13 and Example 14, confirmed that the effects of the present invention were more excellent when the content of the water-soluble organic solvent was 80 mass% or less, relative to the total mass of the chemical solution. Comparisons between Examples 1 and 11 to 13 confirmed that the effects of the present invention were more excellent when the unsaturated compound had a plurality of groups represented by formula (1). Comparisons between Examples 16 to 26 confirmed that the effects of the present invention were more excellent when the oxidizing agent was periodic acid. Comparisons between Examples 16 to 26 and Comparative Example 2 confirmed that the chemical solution of the present invention also had excellent SiGe selective solubility.

[0139] A test specimen containing both a SiGe40 layer and a SiGe25 layer was prepared, and the test specimen was immersed in the chemical solution (25°C) of the example or comparative example. The ratio of the dissolution rates of SiGe40 and SiGe25 was calculated according to the method described above. Results equivalent to those shown in the table above were obtained.

[0140] 200 Processed object 202 Substrate 204 First SiGe-containing material 206 Second SiGe-containing material

Claims

1. A chemical solution used for treating a workpiece having two silicon-germanium-containing materials with different germanium concentrations, for removing at least a portion of the silicon-germanium-containing material with a higher germanium concentration, the chemical solution comprising: a fluoride ion source; an oxidizing agent; a specific unsaturated compound having a group represented by formula (1); and a solvent. ２ C=CH-* In formula (1), each R independently represents a hydrogen atom, a carboxylic acid group, or a hydrocarbon group which may have a substituent. * represents a bonding position.

2. The chemical solution according to claim 1, wherein the specific unsaturated compound has at least one selected from the group consisting of an ester bond, an ether bond, an amide group, an amino group, and a hydroxy group.

3. The medicinal solution according to claim 1 or 2, wherein the specific unsaturated compound has a polyethylene glycol structure.

4. The chemical solution according to claim 1 or 2, wherein the specific unsaturated compound has a plurality of groups represented by formula (1).

5. The chemical solution according to claim 1 or 2, wherein the solvent comprises a water-soluble organic solvent.

6. The chemical solution according to claim 5, wherein the content of the water-soluble organic solvent is 30 mass % or more based on the total mass of the chemical solution.

7. The chemical solution according to claim 5, wherein the water-soluble organic solvent is selected from the group consisting of alcohol-based solvents, carboxylic acid-based solvents, ether-based solvents, and sulfoxide-based solvents.

8. The chemical solution according to claim 7, wherein the water-soluble organic solvent is a carboxylic acid-based solvent.

9. The chemical solution according to claim 1 or 2, wherein the content of the fluoride ion source is less than 5.0 mass % based on the total mass of the chemical solution.

10. The chemical solution according to claim 1 or 2, wherein the oxidizing agent has a standard oxidation-reduction potential of 1.3 V or higher.

11. The chemical solution according to claim 1 or 2, wherein the oxidizing agent is periodic acid.

12. The chemical solution according to claim 1 or 2, wherein the oxidizing agent is hydrogen peroxide.

13. The chemical solution according to claim 1 or 2, which is used for treating an object having two silicon-germanium-containing materials with different germanium concentrations and a silicon-containing material.

14. A method for treating an object, comprising contacting the object, which has two silicon-germanium-containing materials with different germanium concentrations, with the chemical solution according to claim 1 or 2, and removing at least a portion of the silicon-germanium-containing material with the higher germanium concentration.

15. A method for manufacturing a semiconductor device, comprising the method for processing an object according to claim 14.

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