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

Abstract

The present invention provides chemical solution which is capable of selectively removing a silicon germanium-containing material having a high germanium concentration from an object to be treated containing two kinds of silicon germanium-containing materials that have different compositions. The present invention also provides a method for treating an object to be treated and a method for manufacturing a semiconductor device using the chemical solution.　Chemical solution according to the present invention is used for an object to be treated containing two silicon-germanium-containing materials that have different germanium concentrations, and removes at least a portion of one of the silicon-germanium-containing materials that has a high germanium concentration. This chemical solution contains a fluoride ion source, an oxidizing agent, a specific unsaturated compound that has a double bond or a triple bond, and water.

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 compound having the general formula Si １－ｘ Ge ｘ As an etching solution having improved stability over time of the etching rate for a compound represented by the general formula Si １－ｘ Ge ｘ (where x is greater than 0 and less than 1), the etching solution contains periodic acid and a fluoride.

[0004] Japanese Patent Application Laid-Open No. 2020-107724

[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 a silicon-germanium-containing material having a high germanium concentration from a workpiece having two types of silicon-germanium-containing materials with different compositions. 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 to remove 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 containing a double bond or a triple bond and no amide group; and water. [2] The chemical solution according to [1], wherein the specific unsaturated compound is a compound having a group represented by formula (1a) described below. [3] The chemical solution according to [1] or [2], wherein the specific unsaturated compound is a compound containing a triple bond, and the content of the water is 70.0 mass% or less relative to the total mass of the chemical solution. [4] The chemical solution according to any one of [1] to [3], wherein the specific unsaturated compound has at least one bond selected from the group consisting of an ester bond, an ether bond, an amino group, and a hydroxy group. [5] The chemical solution according to any one of [1] to [4], wherein the specific unsaturated compound is a compound that does not have a hydrocarbon group having 18 or more carbon atoms. [6] The chemical solution according to any one of [2] to [5], wherein the specific unsaturated compound contains an aromatic ring structure having a substituent, and the substituent is at least one of a group represented by the above formula (1a) and a group represented by formula (1b) described below. [7] The chemical solution according to any one of [2] to [6], wherein in the above formula (1a), R is a hydrogen atom. [8] The chemical solution according to any one of [2] to [7], wherein the specific unsaturated compound has a plurality of groups represented by the above formula (1a). [9] The chemical solution according to any one of [1] to [8], wherein the content of the water is 95.0 mass% or more relative to the total mass of the solvent contained in 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 more.

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

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

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

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

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

[12] , and removing at least a portion of the silicon-germanium-containing material with a higher germanium concentration.

[14] A method for manufacturing a semiconductor device, comprising the method for treating a workpiece according to

[13] .

[0009] According to the present invention, a chemical solution can be provided that can selectively remove a silicon-germanium-containing material having a high germanium concentration from a workpiece having two types of silicon-germanium-containing materials with different compositions. The present invention also provides a method for treating a workpiece using the chemical solution and a method for manufacturing a semiconductor device.

[0010] 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.

[0011] 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.

[0012] In this specification, the term "silicon-germanium-containing material (SiGe-containing material)" refers to a material containing silicon (Si) and germanium (Ge), and is preferably a material composed essentially of only Si and Ge. The term "substantially" means that the total content of Si and Ge elements is 90 atomic % or more relative to the total atoms of the material. In a material composed essentially of only Si and Ge elements, other elements (e.g., carbon (C), nitrogen (N), oxygen (O), boron (B), and phosphorus (P)) may be contained 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 %, relative to the total mass of the SiGe-containing material. In the SiGe-containing material, the content of Ge element relative to the total content of Si element and Ge element (Ge / (Si+Ge)) 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.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] The chemical solution of the present invention is used for a treatment object having two silicon-germanium-containing materials with different germanium concentrations, and removes at least a portion of the silicon-germanium-containing material with a higher germanium concentration, and includes a fluoride ion source, an oxidizing agent, a specific unsaturated compound containing a double bond or a triple bond and no amide group, and water.

[0017] Although the reason why the drug solution having the above-described configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still included in the scope of the present invention.

[0018] A chemical solution containing a fluoride ion source, an oxidizing agent, and water oxidizes SiGe-containing materials, solubilizing them in a solvent and removing them from the workpiece. It is believed that the double or triple bonds in the specific unsaturated compound contained in the chemical solution of the present invention selectively adsorb to SiGe-containing materials with a low Ge concentration, thereby 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] [Specific Unsaturated Compound] The chemical solution of the present invention contains a specific unsaturated compound. The specific unsaturated compound is a compound that contains a double bond or a triple bond and does not have an amide group. The specific unsaturated compound preferably has a double bond or a triple bond at a molecular end. Furthermore, the number of double bonds and triple bonds contained in the specific unsaturated compound is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 2.

[0020] The specific unsaturated compound has an ester bond (—CO—O—), an ether bond (—O—), an amino group (—NR Ｎ ２ It 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. When the specific unsaturated compound has each of the above groups, the solubility of the specific unsaturated compound in water is improved, which is preferable.

[0021] As the structure containing an ether bond, the specific unsaturated compound preferably has an alkylene glycol structure, more preferably a polyalkylene glycol structure. 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, and even more preferably 2 or 3. Among these, the specific unsaturated compound preferably has a polyethylene glycol structure in which the alkylene group is an ethylene group.

[0022] The specific unsaturated compound also preferably has a hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 30 or less, more preferably 25 or less, even more preferably 17 or less, preferably 1 or more, more preferably 2 or more, and even more preferably 4 or more. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. 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 substituents that the hydrocarbon group may have include hydroxy groups, carboxylic acid groups, and amino groups. In terms of achieving better effects of the present invention, the specific unsaturated compound is preferably a compound having a hydrocarbon group having 17 or less carbon atoms. Note that the specific unsaturated compound preferably does not have a hydrocarbon group having 18 or more carbon atoms.

[0023] It is also preferable that the specific unsaturated compound has an aromatic ring structure which may have a substituent. The aromatic ring structure may be either an aromatic hydrocarbon ring or an aromatic heterocycle. The number of ring atoms in the aromatic ring structure is preferably 5 to 20, more preferably 5 to 12, and even more preferably 5 or 6. In order to achieve better effects of the present invention, it is preferable that the aromatic ring structure has a substituent, and that the substituent is a specific unsaturated group described below.

[0024] In terms of achieving better effects of the present invention, the specific unsaturated compound (a compound containing a double bond) is preferably a compound having at least one of a group represented by formula (1a) and a group represented by formula (1b) shown below (hereinafter, these are also collectively referred to as "specific unsaturated groups"), and more preferably a compound having a plurality of groups represented by formula (1a). The number of specific unsaturated groups in the specific unsaturated compound is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 2.

[0025] R Ｘ ２ C=C(R Ｙ )-* Formula (1a) R Ｘ２ C=C(R Ｙ )-CH ２ -* Formula (1b) In formula (1a) and formula (1b), R Ｘ R each independently represents a hydrogen atom, a carboxylic acid group, or a hydrocarbon group which may have a substituent. * represents a bonding position. Ｘ The hydrocarbon group represented by the formula (I) includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred. The hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, even more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and most preferably 1 to 3 carbon atoms.

[0026] The aliphatic hydrocarbon group may be linear, branched, or cyclic, and is preferably linear or branched. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups. Examples of the aromatic hydrocarbon group include phenyl groups, naphthyl groups, and anthryl groups. In terms of the effects of the present invention being more excellent, R Ｘ is preferably a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent, and more preferably a hydrogen atom.

[0027] Examples of the substituent that the hydrocarbon group may have include a hydroxy group, a carboxylic acid group, an amino group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and an alkylene glycol structure-containing group (hereinafter, these groups are also collectively referred to as "substituent S").

[0028] Examples of the alkylene glycol structure-containing group include 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. 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 hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Examples of the substituent that the hydrocarbon group may have include a hydroxy group, a carboxylic acid 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 number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2. The alkylene group is preferably linear or branched, and more preferably linear. 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 combining these. s represents an integer of 1 or more, preferably an integer of 2 to 60. In other words, the alkylene glycol structure-containing group is also preferably a polyalkylene glycol structure-containing group.

[0029] In the above formula (1a) and the above formula (1b), R Ｙ represents a hydrogen atom or a substituent. Ｙ The substituent represented by is not particularly limited, but examples thereof include an aliphatic hydrocarbon group, an aromatic ring group, and the above-mentioned substituent S. Ｙ is preferably a hydrogen atom or an aliphatic hydrocarbon group, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and even more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0030] The specific unsaturated compound is preferably a compound represented by any one of formulas (2) to (4). Note that the compounds represented by formulas (2) to (4) also do not have an amide group.

[0031] Y-R ２０ Formula (2) Y−L １ -(OL ２ ) ｎ -R３０ Formula (3) {Y−L １ -(OL ２ ) ｎ -L ３} ｍ -W Formula (4) In formulas (2) to (4), Y represents the specific unsaturated group (at least one of the group represented by formula (1a) and the group represented by formula (1b)).

[0032] In formula (2), R ２０ represents an aryl group which may have a hydroxy group, 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 number of carbon atoms in the aryl group is preferably 6 to 20, and more preferably 6 to 10. Examples of aryl groups include a phenyl group. The alkyl group and alkenyl group may be linear, branched, or cyclic, and are preferably linear or branched, and more preferably linear. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 2 to 12, and even more preferably 3 to 10. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and even more preferably 3 to 10. The number of carbon-carbon double bonds in the alkenyl group is 1 or more, and may be 2 or more. Examples of cyclic ether groups include an epoxy group and an oxetanyl group. When the alkyl group or alkenyl group has a hydroxy group or a cyclic ether group, the number of the hydroxy group or the cyclic ether group is preferably 1 to 3, and more preferably 1. ２０ Among these, a phenyl group which may have a hydroxy group, an alkyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms is preferred.

[0033] In formula (3), L １represents 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 the alkenylene group are preferably linear or branched. The number of carbon atoms in the alkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 or 2. The number of carbon atoms in the alkenylene group is preferably 2 to 20, more preferably 2 to 12, and even more preferably 3 to 10. L １ is preferably a single bond, -alkylene group-, -alkylene group-CO-, -alkenylene group-, or -alkenylene group-CO-, more preferably a single bond or an alkylene group.

[0034] In the above formula (3), L ２ 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 1 to 4, still more preferably 2 or 3, and particularly preferably 2. When a plurality of L ２ may be the same or different, but are preferably the same. 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.

[0035] In the above formula (3), R ３０ 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, and amino groups. R３０ is preferably a hydrogen atom, a hydroxy group, or a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a hydroxy group.

[0036] In the above formula (4), L １ , L ２ , and n are the L in formula (3), respectively. １ , L ２ , and n. In formula (4), multiple L １ , L ２ In formula (4), L and n may be the same or different. ３ each independently represents a single bond or a divalent linking group. ３ Examples of the divalent linking group represented by １ Examples of the divalent linking groups include those exemplified for L 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.

[0037] In the above formula (4), W represents an m-valent linking group. m represents an integer of 2 or more. m is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. Examples of the m-valent linking group include m-valent hydrocarbon groups which may have a substituent. The m-valent hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3. When m is 4 and the hydrocarbon group has 1 carbon atom, the m-valent hydrocarbon group represents a carbon atom. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups, with aliphatic hydrocarbon groups being preferred. When the m-valent hydrocarbon group has a substituent, the number of substituents is preferably 1 to 4, and more preferably 1 to 3. Examples of the substituent that the m-valent hydrocarbon group may have include a hydroxy group, a carboxylic acid 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. When the hydrocarbon group has a polyalkylene glycol structure-containing group, the number of carbon atoms excluding the number of carbon atoms of the polyalkylene glycol structure-containing group preferably satisfies the above-mentioned preferred range.

[0038] The specific unsaturated compound is also preferably a compound represented by formula (5). ５ -≡-R ５ Formula (5) R ５ each independently represent an aliphatic hydrocarbon group which may have a hydroxy group, and an aliphatic hydrocarbon group having a hydroxy group is preferred. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and is more preferably branched. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 2 to 12, and even more preferably 3 to 10. The number of hydroxy groups in the aliphatic hydrocarbon group is not particularly limited, and is preferably 1 to 3, and more preferably 1.

[0039] Specific examples of the specific unsaturated compounds containing a double bond include monoallyl ethers such as ethylene glycol monoallyl ether and allyl methyl ether, diallyl ethers such as glycerol α,α'-diallyl ether, polyalkylene glycol alkenylene ethers such as polyoxyethylene oleyl ether, unsaturated fatty acids such as linoleic acid, oleic acid, and sorbic acid, polyalkylene glycol unsaturated fatty acid esters such as polyethylene glycol oleate and polyethylene glycol linoleate, sorbitol unsaturated fatty acid esters such as sorbitol tetraoleate, sorbitol trioleate, sorbitol dioleate, and sorbitol monooleate, sorbitan unsaturated fatty acid esters such as sorbitan monooleate and sorbitan trioleate, 2-allylphenol, 3-phenyl-2-propen-1-ol, oleamide, pentaerythritol tetraallyl ether, ethylene glycol monovinyl ether, maleic acid, and 1,2-epoxy-5-hexene. The specific unsaturated compound may be polyoxyethylene oleyl ether, but is preferably not polyoxyethylene oleyl ether, in that the effects of the present invention are more excellent. Commercially available products include, for example, Sanicol M-700, Sanicol DMT-4715, and Sanicol MMT-200 (all manufactured by Sanyo Chemical Industries, Ltd.), Emulgen 409PV, Emulgen 408, Emulgen 430, Rheodol 430V, Rheodol 440V, Rheodol 460V, and EMANON 4110 (all manufactured by Kao Corporation).

[0040] Of the specific unsaturated compounds, specific examples of compounds containing a triple bond include acetylene glycol and acetylene glycol derivatives such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol, 3,5-dimethyl-1-hexyne-3-ol, and ethylene oxide adducts (EO adducts) of these. Furthermore, examples of commercially available products include Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol 104PA, Surfynol 104PG-50, Surfynol 104S, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol SE, Surfynol SE-F, Surfynol PSA-336, Surfynol 2502 (all of which are part of the "Surfynol (registered trademark)" series, manufactured by Nissin Chemical Industry Co., Ltd.), the "Olfine (registered trademark)" series (manufactured by Nissin Chemical Industry Co., Ltd.); the "Acetylenol (registered trademark)" series (manufactured by Kawaken Fine Chemicals Co., Ltd.), Dynol 604, and Dynol 607.

[0041] 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 0.001 to 5% by mass, and even more preferably 0.01 to 3.5% by mass, based on the total mass of the chemical solution, in terms of more excellent effects of the present invention.

[0042] [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 ６２－ , 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. Preferred cations contained in the fluoride ion source include H ＋ , Li ＋ , Na ＋ , K. ＋ , and NH ４ ＋ are mentioned, and H ＋ is preferred.

[0043] 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 and its salts (KBF ４ , N.H. ４ BF ４ etc.), fluoroboric acid, hexafluorotitanic acid (H ２ TiF ６ ), hexafluorozirconate (H ２ ZrF ６ ), hexafluorophosphate (HPF ６ ), and hexafluoroboric acid (HBF ４ ) are exemplified, hydrofluoric acid or ammonium fluoride is preferred, and hydrofluoric acid is more preferred.

[0044] The fluoride ion source may be used alone or in combination of two or more. The content of the fluoride ion source is preferably less than 25.0 mass%, more preferably 15.0 mass% or less, and even more preferably 10.0 mass% or less, relative to the total mass of the chemical solution. 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.

[0045] [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 more excellent 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 a value based on a standard hydrogen electrode, and a value described in any literature can be adopted.

[0046] 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.

[0047] In terms of achieving superior effects of the present invention, 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, more preferably hydrogen peroxide or periodic acid, and even more preferably hydrogen peroxide. 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 produce peracetic acid, and the peracetic acid may function as the oxidizing agent.

[0048] 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 10 mass %, and even more preferably 0.05 to 5 mass %, relative to the total mass of the chemical solution, in terms of more excellent effects of the present invention.

[0049] [Water] The chemical solution of the present invention contains water. The water content is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 80% by mass or more, and most preferably 85% by mass or more, relative to the total mass of the chemical solution, in order to obtain a more excellent effect of the present invention. The upper limit is less than 100% by mass, preferably 99.5% by mass or less, more preferably 98% by mass or less, and even more preferably less than 95% by mass. In particular, when the specific unsaturated compound is a compound containing a triple bond, the water content is preferably 70.0% by mass or less, relative to the total mass of the chemical solution. Furthermore, in order to obtain a more excellent effect of the present invention, the water content is preferably 95.0% by mass or more, relative to the total mass of the solvent contained in the chemical solution.

[0050] [Specific Compound] In order to obtain more excellent effects of the present invention, the chemical solution of the present invention preferably further contains a specific compound selected from a silane compound, an amide compound, and a nitrogen-containing polymer. The specific compound is a compound different from the specific unsaturated compound.

[0051] <Silane Compound> 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 is preferred. The molecular weight of the silane compound (when the silane compound has a molecular weight distribution, the weight average molecular weight) is preferably 50 to 1,000, more preferably 100 to 800, and even more preferably 150 to 500. Examples of the silane compound include alkoxysilanes and chlorosilanes. In terms of achieving better effects of the present invention, alkoxysilanes are preferred, dialkoxysilanes or trialkoxysilanes are more preferred, and trialkoxysilanes are even more preferred.

[0052] Furthermore, the silane compound is particularly advantageous in that it contains an amino group (—NR Ｎ ２ It is also preferable that the compound has R Ｎ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent. Ｎ At least one of the groups is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably both are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.

[0053] Among them, the silane compound is preferably a compound represented by the following formula (S): (R Ｓ ) ｄ Si(H) ｅ (X) ４－ｄ－ｅ (S)

[0054] 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. In formula (S), R Ｓ represents a monovalent organic group. Ｓ If there are multiple R Ｓ The groups represented by R may be the same or different. Ｓ If there are multiple R Ｓ The total number of carbon atoms in the group represented by the formula (I) is preferably 3 to 35, and more preferably 3 to 25.

[0055] The number of carbon atoms in the monovalent organic group is preferably 1 to 25, more preferably 1 to 10, and even more preferably 1 to 6. The monovalent organic group is not particularly limited, but may be an amino group (—NR Ｎ１ ２ ), a cyclic ether group, an ether bond (—O—), and —NR Ｎ２ - is preferably a hydrocarbon group which may contain a group or structure selected from the group consisting of -, and more preferably a hydrocarbon group which may contain one or two of the above groups or structures. Ｎ１ and R Ｎ２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and preferably an epoxy group.

[0056] Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group. The alkyl group may be linear, branched, or cyclic, but is preferably linear. The linear or branched alkyl group preferably has 1 to 18 carbon atoms, and more preferably 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a sec-butyl group, a t-butyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. The cyclic alkyl group (cycloalkyl group) preferably has 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 6 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group and a cyclohexyl group. The alkenyl group preferably has 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms. Examples of the alkenyl group include a vinyl group and an allyl group. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 10. Examples of the aryl group include a phenyl group.

[0057] In the above formula (S), X represents a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group and a halogen atom. When a plurality of Xs are present, the groups represented by the plurality of Xs may be the same or different, but are preferably the same. 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, with a chlorine atom being preferred. X is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms.

[0058] Examples of alkoxysilanes include CH ３ Si(OCH ３ ) ３ , C ２ H ５ Si(OCH ３ ) ３ , C ３ H ７ Si(OCH ３ ) ３ , C ４ H ９ Si(OCH ３ ) ３ , C ５ H １１ Si(OCH ３ ) ３ , C ６ H １３ Si(OCH ３ ) ３ , C ７ H １５ Si(OCH ３ ) ３ , C ８ H １７ Si(OCH ３ ) ３ , C ９ H １９ Si(OCH ３ ) ３ , C １０ H ２１ Si(OCH ３ ) ３ , C １１ H ２３ Si(OCH ３ ) ３ , C １２ H ２５Si(OCH ３ ) ３ 、C １３ H ２７ Si(OCH ３ ) ３ 、C １４ H ２９ Si(OCH ３ ) ３ 、C １５ H ３１ Si(OCH ３ ) ３ 、C １６ H ３３ Si(OCH ３ ) ３ 、C １７ H ３５ Si(OCH ３ ) ３ 、C １８ H ３７ Si(OCH ３ ) ３ 、C ２０ H ４１ Si(OCH ３ ) ３ 、C ２４ H ４９ Si(OCH ３ ) ３ ,(H ３ ) ２ Si(OCH ３ ) ２ 、C ２ H ５ Si(H) ３ )(OCH ３ ) ２ 、(C ２ H ５ ) ２ Si(OCH ３ ) ２ 、C ３ H ７ Si(H) ３ )(OCH ３ ) ２ 、(C ３ H ７ ) ２ Si(OCH ３ ) ２ 、C ４ H ９ Si(H) ３ )(OCH ３ ) ２ 、(C ４ H９ ) ２ Si(OCH ３ ) ２ 、C ５ H １１ Si(H) ３ )(OCH ３ ) ２ 、C ６ H １３ Si(H) ３ )(OCH ３ ) ２ 、C ７ H １５ Si(H) ３ )(OCH ３ ) ２ 、C ８ H １７ Si(H) ３ )(OCH ３ ) ２ 、C ９ H １９ Si(H) ３ )(OCH ３ ) ２ 、C １０ H ２１ Si(H) ３ )(OCH ３ ) ２ 、C １１ H ２３ Si(H) ３ )(OCH ３ ) ２ 、C １２ H ２５ Si(H) ３ )(OCH ３ ) ２ 、C １３ H ２７ Si(H) ３ )(OCH ３ ) ２ 、C １４ H ２９ Si(H) ３ )(OCH ３ ) ２ 、C １５ H ３１ Si(H) ３ )(OCH ３ ) ２ 、C １６ H ３３ Si(H) ３ )(OCH ３ )２ 、C １７ H ３５ Si(H) ３ )(OCH ３ ) ２ 、C １８ H ３７ Si(H) ３ )(OCH ３ ) ２ ,(H ３ ) ３ SiOCH ３ 、C ２ H ５ Si(H) ３ ) ２ OCH ３ 、(C ２ H ５ ) ２ Si(H) ３ )OCH ３ 、(C ２ H ５ ) ３ SiOCH ３ 、C ３ H ７ Si(H) ３ ) ２ OCH ３ 、(C ３ H ７ ) ２ Si(H) ３ )OCH ３ 、(C ３ H ７ ) ３ SiOCH ３ 、C ４ H ９ Si(H) ３ ) ２ OCH ３ 、(C ４ H ９ ) ３ SiOCH ３ 、C ５ H １１ Si(H) ３ ) ２ OCH ３ 、C ６ H １３ Si(H) ３ ) ２ OCH ３ 、C ７ H １５ Si(H) ３ )２ OCH ３ 、C ８ H １７ Si(H) ３ ) ２ OCH ３ 、C ９ H １９ Si(H) ３ ) ２ OCH ３ 、C １０ H ２１ Si(H) ３ ) ２ OCH ３ 、C １１ H ２３ Si(H) ３ ) ２ OCH ３ 、C １２ H ２５ Si(H) ３ ) ２ OCH ３ 、C １３ H ２７ Si(H) ３ ) ２ OCH ３ 、C １４ H ２９ Si(H) ３ ) ２ OCH ３ 、C １５ H ３１ Si(H) ３ ) ２ OCH ３ 、C １６ H ３３ Si(H) ３ ) ２ OCH ３ 、C １７ H ３５ Si(H) ３ ) ２ OCH ３ 、C １８ H ３７ Si(H) ３ ) ２ OCH ３ ,(H ３ ) ２ Si (H)OCH ３ ,H ３ Si (H) ２ OCH ３ 、(C ２ H５ ) ２ Si(H)OCH ３ , C ２ H ５ Si(H) ２ OCH ３ , C ２ H ５ Si(CH ３ ) (H) OCH ３ , and (C ３ H ７ ) ２ Si(H)OCH ３ and alkylalkoxysilanes in which the methoxy group in the alkylmethoxysilane is replaced with an alkoxy group having 2 to 10 carbon atoms. Specific examples of the alkoxysilane compound include the compounds described in paragraphs

[0056] to

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

[0059] Examples of chlorosilanes include trimethylchlorosilane (TMCS), triethylchlorosilane, tributylchlorosilane, triphenylchlorosilane, dimethyldichlorosilane (DMCS), t-butyldimethylchlorosilane, dimethylphenylchlorosilane, and di-tert-butyldichlorosilane.

[0060] <Amide Compound> The amide compound is not particularly limited as long as it is a compound having an amide bond, but a low molecular weight compound is preferred. Note that a polymer compound refers to a compound having multiple repeating units. The molecular weight of the amide compound is preferably 50 to 1,000, more preferably 100 to 800, and even more preferably 150 to 500.

[0061] In terms of achieving better effects of the present invention, the amide compound is preferably a compound represented by formula (A).

[0062]

[0063] In formula (A), R １ ~R ３ R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １ ~R ３is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom. The alkyl group is preferably linear or branched. In formula (A), X represents a divalent linking group selected from the group consisting of an alkylene group having 1 to 5 carbon atoms, a polyoxyalkylene group having 1 to 10 repeating units, and a group formed by combining these. Among these, X is preferably an alkylene group having 1 to 5 carbon atoms. The number of repeating units of the polyoxyalkylene group is preferably 1 to 6. Furthermore, the polyoxyalkylene group is preferably a polyoxyethylene group or a polyoxypropylene group. In formula (A), R Ｎ１ ~R Ｎ３ R each independently represents an alkyl group having 1 to 6 carbon atoms. Ｎ１ ~R Ｎ３ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. － represents an anion. The anion is not particularly limited, and examples thereof include a halide ion (e.g., a chloride ion), a sulfate ion, a nitrate ion, an acetate ion, a methyl sulfate ion, an ethyl sulfate ion, a sulfamate ion, and a hydroxide ion.

[0064] <Nitrogen-Containing Polymer> The nitrogen-containing polymer has a repeating unit containing a nitrogen-containing group and is a compound different from the above-mentioned amide compound. The number of nitrogen-containing groups in the repeating unit containing a nitrogen-containing group is preferably 1 to 6, more preferably 1 or 2, and even more preferably 1. The content of the repeating unit containing a nitrogen-containing group is preferably 50 to 100 mol %, more preferably 80 to 100 mol %, based on the total repeating units of the nitrogen-containing polymer. The nitrogen-containing polymer may contain repeating units other than the repeating unit containing a nitrogen-containing group.

[0065] The upper limit of the weight average molecular weight of the nitrogen-containing polymer is not particularly limited, but is preferably not more than 100,000, more preferably not more than 80,000, and even more preferably not more than 50,000. The lower limit of the weight average molecular weight of the nitrogen-containing polymer is not particularly limited, but is preferably not less than 500, more preferably not less than 800, and even more preferably not less than 1,500. Here, the weight-average molecular weight is the manufacturer's nominal value listed in the product catalog or the like. However, when the manufacturer's nominal value is unknown, a polystyrene-equivalent value obtained by GPC measurement using a Gel Permeation Chromatography (GPC) device (Shimadzu Corporation, Prominence UFLC) [eluent: tetrahydrofuran, flow rate (sample injection amount): 50 μL, column: Tosoh Corporation, TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL, column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector (Refractive Index Detector)] is used.

[0066] Examples of the nitrogen-containing group include an amino group (—NR Ｎ ２ ), quaternary ammonium base (-N ＋ R Ｎ ３ ), an amide group, a hydrazine group, a guanidine group, and a nitrogen-containing heterocyclic group. Ｎ R each independently represents a hydrogen atom or an organic group (a group containing at least one carbon atom). Ｎ The number of carbon atoms in the organic group represented by the formula (I) is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The amide group is preferably —NR Ｎ -CO- and a group obtained by removing a hydrogen atom from a lactam compound. ＮThe definition and preferred embodiments of are as described above. The amide group is preferably a group obtained by removing a hydrogen atom on a nitrogen atom in a lactam compound selected from β-lactam, γ-lactam, and δ-lactam. Examples of the nitrogen-containing heterocyclic group include nitrogen-containing aromatic heterocyclic groups such as pyrrole group, imidazole group, pyrazole group, oxazolyl group, triazole group, benzimidazole group, benztriazole group, pyridyl group, and triazine group, and nitrogen-containing aliphatic heterocyclic groups such as pyrrolidinyl group, piperidinyl group, and piperazinyl group.

[0067] In order to obtain a more excellent effect of the present invention, the nitrogen-containing polymer is preferably a polymer having a repeating unit containing a group selected from the group consisting of a primary amino group or a salt thereof, a secondary amino group or a salt thereof, a tertiary amino group or a salt thereof, a quaternary ammonium salt, and an amide group. Specific examples and preferred embodiments of each group are as described above.

[0068] The repeating unit containing a nitrogen-containing group is preferably a repeating unit represented by general formula (1-a) or a repeating unit represented by general formula (1-b).

[0069]

[0070] In general formula (1-a), L １ａ and L ２ａ each independently represents a single bond or a methylene group. １ａ is a single bond, L ２ａ is a methylene group, and L １ａ is a methylene group, L ２ａ is a single bond. １ａ is preferably a single bond, and L ２ａ is preferably a methylene group.

[0071] In the general formula (1-a), X represents a group represented by the formula (X1) or a group represented by the formula (X2). * represents a bonding position. In the formulas (X1) and (X2), R １ａrepresents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group may be linear, branched, or cyclic, and examples thereof include alkyl groups having 1 to 4 carbon atoms which may have a hydroxyl group, of which methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, or cyclohexyl groups are preferred. Examples of aralkyl groups having 7 to 10 carbon atoms include benzyl, methylbenzyl, naphthylmethyl, and phenethyl groups. R １ａ Among these, a hydrogen atom, a methyl group, an ethyl group, or a benzyl group is preferable as the aryl group.

[0072] D － represents a monovalent anion. － Examples of the monovalent anion represented by the formula (I) include a halide ion (e.g., a chloride ion), a sulfate ion, a nitrate ion, an acetate ion, a methyl sulfate ion, an ethyl sulfate ion, a sulfamate ion, and a hydroxide ion.

[0073] In general formula (1-b), L １ｂ and L ２ｂ each independently represents a single bond or a methylene group. １ｂ is a single bond, L ２ｂ is a methylene group, and L １ｂ is a methylene group, L ２ｂ is a single bond. １ｂ is preferably a single bond, and L ２ｂ is preferably a methylene group.

[0074] In general formula (1-b), R １ｂ and R ２ｂ each independently represents an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms. Specific examples and preferred embodiments of the alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group and the aralkyl group having 7 to 10 carbon atoms are１ａ These are the same as the specific examples and preferred embodiments of the alkyl group having 1 to 10 carbon atoms and the aralkyl group having 7 to 10 carbon atoms which may have a hydroxyl group, represented by the following formula:

[0075] In general formula (1-b), D － represents a monovalent anion. － Examples of the monovalent anion represented by the formula (1-a) include D － Examples of the monovalent anion include the ions exemplified above.

[0076] In general formula (1-b), R １ｂ , R ２ｂ and D － Examples of the combination of D include Examples 1 to 5. － The chloride ion represented by the formula (I) may be replaced by an anion selected from bromide ion, iodide ion, methyl sulfate ion and ethyl sulfate ion.

[0077] Example 1: R １ｂ =R ２ｂ = methyl group, D － = Chloride ion Example 2: R １ｂ =R ２ｂ = ethyl group, D － = chloride ion Example 3: R １ｂ =R ２ｂ = propyl group, D － = chloride ion Example 4: R １ｂ =R ２ｂ = butyl group, D － = chloride ion Example 5: R １ｂ = ethyl group, R ２ｂ = benzyl group, D － = chloride ion Example 6: R １ｂ = methyl group, R ２ｂ = ethyl group, D － = Ethyl sulfate ion

[0078] Specific examples of nitrogen-containing polymers include quaternized dialkylaminoalkyl (meth)acrylate polymers such as polyvinylpyrrolidone, vinylpyrrolidone / N,N-dimethylaminoethyl methacrylate diethyl sulfate copolymer, and N,N-dimethylaminoethyl methacrylate diethyl sulfate / N,N-dimethylacrylamide / polyethylene glycol dimethacrylate copolymer; polydiallyldimethylammonium chloride, diallyldimethylammonium chloride / acrylic acid copolymer, diallyldimethylammonium chloride / acrylamide copolymer, diallyldimethylammonium chloride / acrylic acid / acrylamide copolymer, diallyldimethylammonium chloride polymer, diallyldimethylammonium chloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-acrylamide copolymer, diallylamine amide sulfate-maleic acid copolymer, methyldiallylamine-maleic acid copolymer, diallyldimethylammonium chloride-maleic acid copolymer, diallylmethylethylammonium ethyl sulfate-sulfur dioxide copolymer, maleic acid-diallyldimethylammonium Diallyl quaternary ammonium salt polymers such as ammonium ethyl sulfate-sulfur dioxide copolymer; vinylimidazolium trichloride / vinylpyrrolidone copolymer; vinylpyrrolidone / alkylaminoalkyl (meth)acrylate copolymer; vinylpyrrolidone / alkylaminoalkyl (meth)acrylate / vinyl caprolactam copolymer; vinylpyrrolidone / (meth)acrylamidopropyl trimethylammonium chloride copolymer; alkylacrylamide / (meth)acrylate / alkylaminoalkylacrylamide / polyethylene glycol (meth)acrylate copolymer; adipic acid / dimethylaminohydroxypropyl ethylenetriamine copolymer; acrylic acid / methyl acrylate / methacrylamidopropyl trimethylammonium chloride copolymer (Polyquaternium-47); acrylic acid / acrylamide / methacrylamidopropyl trimethylammonium chloride (Polyquaternium-53); methacryloylethyl dimethylbetaine / methacryloylethyltrimethylammonium chloride / methoxypolyethylene glycol methacrylate copolymer (Polyquaternium-49);Examples of such copolymers include methacryloylethyldimethylbetaine, methacryloylethyltrimethylammonium chloride, and 2-hydroxyethyl methacrylate (Polyquaternium-48); diallyldimethylammonium chloride and acrylamide copolymer (Polyquaternium-7); acrylamide, acrylic acid, and dimethyldiallylammonium chloride copolymer (Polyquaternium-39); N,N-dimethylaminoethyl diethyl methacrylate sulfate / N,N-dimethylacrylamide / polyethylene glycol dimethacrylate copolymer (Polyquaternium-52); and polymers described in JP-A Nos. 53-139734 and 60-36407.

[0079] The specific compound may be used alone or in combination of two or more. The content of the specific compound is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.01 to 3.5% by mass, based on the total mass of the chemical solution, in terms of more excellent effects of the present invention.

[0080] [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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] [Other Additives] The chemical solution of the present invention may contain other additives in addition to those described above. Examples of other additives include basic compounds, acidic compounds, surfactants, antifoaming agents, and organic solvents. Note that all of these components are different from the components described above.

[0087] <Basic Compound> The chemical solution of the present invention may contain a basic compound. Examples of the basic compound include organic basic compounds and inorganic basic compounds. Examples of the organic basic compound include amine compounds, 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 compound is a compound different from the heterocyclic compounds described above. Examples of the inorganic basic compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, and ammonia or salts thereof.

[0088] The content of the basic compound is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total mass of the chemical solution.

[0089] <Acidic Compound> The chemical solution of the present invention may contain an acidic compound. Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and phosphonic acid, with sulfuric acid being preferred.

[0090] The content of the acidic compound is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the chemical solution.

[0091] <Surfactant> The chemical solution of the present invention may contain a surfactant. The surfactant is not particularly limited as long as it is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule, and examples thereof include nonionic surfactants, cationic surfactants, and anionic 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.

[0092] Examples of the nonionic surfactant include ester-type nonionic surfactants, ether-type nonionic surfactants, and ester-ether-type nonionic surfactants, and ether-type nonionic surfactants are preferred. Examples of the nonionic surfactant include the compounds exemplified in paragraph

[0126] of WO 2022 / 044893, the contents of which are incorporated herein by reference.

[0093] Examples of cationic surfactants include primary to tertiary alkylamine salts (e.g., monostearyl ammonium chloride, distearyl ammonium chloride, and tristearyl ammonium chloride), and modified aliphatic polyamines (e.g., polyethylene polyamine).

[0094] Examples of anionic surfactants include sulfonic acid surfactants having a sulfonic acid group, sulfate ester surfactants having a sulfate ester group, and carboxylic acid surfactants having a carboxylic acid 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.

[0095] <Antifoaming Agent> The chemical solution of the present invention 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, acetylene diol-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.

[0096] The chemical solution of the present invention may further contain an organic solvent, but in order to achieve better effects of the present invention, the content of the organic solvent is preferably less than 20.0 mass %, more preferably less than 5.0 mass %, and even more preferably less than 1.0 mass %, relative to the total mass of the solvents contained in the chemical solution. The lower limit may be 0.0 mass % or more.

[0097] When the chemical solution contains 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 of 20 g / 100 g or more in water (100 g) at 25° C. Examples of the organic solvent include ether solvents, alcohol solvents, carboxylic acid solvents, sulfoxide solvents, ester solvents, ketone solvents, sulfone solvents, amide solvents, and nitrile solvents.

[0098] 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.

[0099] 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.

[0100] Examples of carboxylic acid solvents include formic acid, acetic acid, and propionic acid.

[0101] An example of a sulfoxide solvent is dimethyl sulfoxide (DMSO).

[0102] 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.

[0103] Among these, the water-soluble organic solvent preferably contains at least one selected from the group consisting of ethylene glycol monobutyl ether (EGBE), formic acid, acetic acid, and propionic acid.

[0104] [Physical properties of chemical solution] <pH> The pH of the chemical solution is preferably 0.5 to 9, more preferably 1 to 7, and even more preferably 3 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.

[0105] <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.

[0106] <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.

[0107] <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.

[0108] 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.

[0109] [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.

[0110] <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 containing a double bond or a triple bond, and, if necessary, any optional components to a container containing water, followed by stirring to mix. Alternatively, the solution may be prepared by adjusting the pH of the mixed solution by adding a pH adjuster. Furthermore, when adding the components to a container, they may be added all at once, or may be added in multiple divided portions.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] (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.

[0115] 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 any 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).

[0116] The purification treatment may be carried out by combining two or more of the above purification methods, or may be carried out multiple times.

[0117] (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.

[0118] 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.

[0119] In order to prevent changes in the components of the chemical 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 more. Furthermore, during transportation and storage, the chemical solution may be stored at room temperature, or the temperature may be controlled within a range of −20° C. to 20° C. to prevent deterioration. The method for producing the chemical solution may further include a static elimination step of eliminating static electricity from the chemical solution.

[0120] [Uses] The chemical solution of the present invention is used in the processing of semiconductor substrates, on a workpiece having two silicon-germanium-containing materials with different germanium concentrations, to remove at least a portion of the silicon-germanium-containing material with a high germanium concentration. 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 treat, for example, SiGe (silicon-germanium)-containing materials, SiOx-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 is more preferably applied to a workpiece having two silicon-germanium-containing materials with different germanium concentrations and a silicon-containing material. The workpiece preferably includes a silicon-containing material that does not contain oxygen atoms or germanium atoms. The chemical solution of the present invention can be suitably used as a solution (etching solution) for removing at least a portion of a SiGe-containing material from a processing object having two silicon-germanium-containing materials with different germanium concentrations.

[0121] [Workpiece] The workpiece to be treated with the chemical solution of the present invention preferably has two SiGe-containing materials with different Ge concentrations. The elemental ratio of Si and Ge in the SiGe-containing material with a high Ge concentration in the workpiece, i.e., the Ge content relative to the total content of Si and Ge in the SiGe-containing material (Ge / (Si+Ge)), is preferably 25 to 60 atomic %, more preferably 35 to 50 atomic %. The Ge content relative to the total content of Si and Ge in the SiGe-containing material with a low Ge concentration in the workpiece (Ge / (Si+Ge)), is preferably 5 to 35 atomic %, more preferably 10 to 30 atomic %. Furthermore, the difference between the Ge content in the SiGe-containing material with a high Ge concentration and the Ge content in the SiGe-containing material with a low Ge concentration in the workpiece is preferably 5 atomic % or more, more preferably 10 atomic % or more.

[0122] The workpiece often has two SiGe-containing materials with different Ge concentrations arranged on a substrate. Examples of substrates include metal substrates, semiconductor substrates, non-metallic conductive substrates, metal oxide substrates, glass substrates, and resin substrates, with semiconductor substrates being preferred. The substrate may also have three or more SiGe-containing materials with different Ge concentrations. In this specification, "on the substrate" includes the front and back surfaces, side surfaces, and grooves of the substrate. The term "a predetermined material is arranged on the substrate" also includes cases where a predetermined material is directly on the surface of the substrate, and cases where a predetermined material is on the substrate via another layer. The SiGe-containing materials may be arranged on only one major surface of the substrate, or on both major surfaces. They may also be arranged on the entire major surface of the substrate, or on a portion of the major surface of the substrate.

[0123] [Method for Treating a Workpiece] A method for treating a workpiece using the chemical solution of the present invention includes contacting a workpiece having two silicon-germanium-containing materials with different germanium concentrations with the chemical solution of the present invention, and removing at least a portion of the silicon-germanium-containing material with a high germanium concentration. By this treatment method, SiGe-containing materials with a high Ge concentration in the workpiece are selectively removed (etched).

[0124] 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.

[0125] 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 1 second to 60 minutes, more preferably 1 second to 20 minutes. The temperature of the chemical solution during treatment is preferably 10 to 100°C, more preferably 15 to 60°C.

[0126] The present processing method may, if necessary, include processing steps other than the treatment of contacting the substrate with a chemical solution. For example, it may include a rinsing step in which the substrate is rinsed using a rinsing liquid. For example, after the substrate is contacted with the chemical solution, a rinsing step may be further performed. An example of a rinsing method is a method in which the substrate is contacted with a rinsing liquid. The above-mentioned method of contacting the substrate with a rinsing liquid can also be applied as a method of contacting the substrate with a chemical solution. If necessary, the rinsing step may be followed by a drying step in which a drying process is performed. The drying method is not particularly limited, but examples 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.

[0127] [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.

[0128] 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.

[0129] 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.

[0130] [Preparation of Chemical Solutions] The chemical solutions of each Example and Comparative Example were prepared by mixing the components (fluoride ion source, oxidizing agent, solvent, specific unsaturated compound, and other optional components) shown in the table below so that the content of each component was the value shown in the table below. The pH of the chemical solutions of each Example and Comparative Example was 3 to 7. The components used in preparing the chemical solutions are as follows:

[0131] [Fluoride ion source] HF (hydrogen fluoride) NH ４ F (ammonium fluoride)

[0132] [Oxidizing agent] Periodic acid (standard oxidation-reduction potential 1.6 V) Hydrogen peroxide (H ２ O ２ , standard redox potential 1.8 V)

[0133] [Specific unsaturated compounds] Ethylene glycol monoallyl ether (compound corresponding to formula (3)) Sanicol M-0700 (manufactured by Sanyo Chemical Industries, Ltd., compound corresponding to formula (3)) Sanicol DMT-4715 (manufactured by Sanyo Chemical Industries, Ltd.) Emulgen 409PV (manufactured by Kao Corporation) (compound corresponding to formula (3)) Emulgen 430 (manufactured by Kao Corporation) (compound corresponding to formula (3)) Glycerol diallyl ether (compound corresponding to formula (4)) 2-allylphenol (compound corresponding to formula (2)) 3-phenyl-2-propen-1-ol (compound corresponding to formula (2)) Surfynol 104E (manufactured by Nissin Chemical Industry Co., Ltd.) (compound corresponding to formula (5))

[0134] [Specific Compounds] The compound name or chemical formula of each specific compound is shown in Table 1. In Table 1, the weight average molecular weight (Mw) of PVP K30 was 40,000, and the Mw of PAS-H-1L was 8,500.

[0135]

[0136] [Other ingredients] 1,2,4-triazole (corrosion inhibitor) Acetic acid, ammonia, deionized water (DIW, solvent) EGBE (ethylene glycol monobutyl ether, solvent)

[0137] [Evaluation] According to the procedure shown below, the etching (removal) selectivity of each chemical solution was evaluated by measuring the dissolution rate of low-concentration silicon germanium (SiGe) and high-concentration silicon germanium in each chemical solution prepared by the above procedure.

[0138] [Etching (removal) selectivity] A substrate on which low-concentration SiGe (SiGe25, Si:Ge=75:25 (element ratio)) was laminated to a thickness of 30 nm, and a substrate on which high-concentration SiGe (SiGe40, Si:Ge=60:40 (element ratio)) was laminated to a thickness of 20 nm were prepared, and these substrates were each cut into 2×2 cm squares to prepare test specimens. Each test specimen was immersed in the chemical solution of each Example or Comparative Example at 25° C. for the following times: Low-concentration SiGe test specimen: 1 minute High-concentration SiGe test specimen: 5 seconds

[0139] The film thickness of the SiGe film was measured before and after the immersion using an optical film thickness meter, Ellipsometer M-2000 (manufactured by JA Woollam). The dissolution rate (Å / min) of each film when using each chemical solution was calculated from the measured change in film thickness before and after immersion. 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.

[0140] (Evaluation criteria: etching ability 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

[0141] (Evaluation criteria: etching property of SiGe 40) H: Dissolution rate is 1300 Å / min or more M: Dissolution rate is 500 Å / min or more but less than 1300 Å / min L: Dissolution rate is less than 500 Å / min

[0142] (Evaluation criteria: etching selectivity of SiGe40 relative to SiGe25) H: The ratio of the dissolution rate of SiGe40 to the dissolution rate of SiGe25 (SiGe40 / SiGe25) is 18 or more M: SiGe40 / SiGe25 is 7 or more and less than 18 L: SiGe40 / 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 high-concentration SiGe can be selectively removed relative to low-concentration SiGe.

[0143] [Residue Removability] After the evaluation of [Etching (Removal) Selectivity] above was performed, the treated substrate surface was observed for each substrate. If a uniform metallic luster was observed, the residue removability was evaluated as good, and if not, the evaluation result was evaluated as poor.

[0144] [Results] The composition of each chemical solution and the evaluation results are shown in the table below. The evaluation results of the [etching (removal) selectivity] are shown in Table 2, and the evaluation results of [residue removability] are shown in Table 3. In the table below, the column "SiGe40 / SiGe25" shows the evaluation results of the etching selectivity of SiGe40 relative to SiGe25.

[0145]

[0146]

[0147]

[0148] From the above table, it can be seen that the chemical solution not containing the specific unsaturated compound (the chemical solution of the comparative example) was unable to selectively remove SiGe-containing materials with a high Ge concentration from a workpiece having two SiGe-containing materials with different compositions. On the other hand, it was confirmed that the chemical solution of the present invention (the chemical solution of the example) was able to selectively remove SiGe-containing materials with a high Ge concentration from a workpiece having two SiGe-containing materials with different compositions. Furthermore, comparisons of Examples 2, 19, and 20 with other examples confirmed that the effects of the present invention were more excellent when the specific unsaturated compound had an aromatic ring structure. Comparisons of Examples 35 and 36 confirmed that residue removal was more excellent when the specific unsaturated compound was a compound containing a triple bond and the water content was 70.0 mass% or less relative to the total mass of the chemical solution.

Claims

1. A chemical solution used on a workpiece having two silicon-germanium-containing materials with different germanium concentrations to remove 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 that contains a double bond or a triple bond and does not have an amide group; and water.

2. The chemical solution according to claim 1, wherein the specific unsaturated compound is a compound having a group represented by formula (1a). Ｘ ２ C=C(R Ｙ )-* Formula (1a) In formula (1a), R Ｘ R each independently represents a hydrogen atom, a carboxylic acid group, or a hydrocarbon group which may have a substituent. Ｙ represents a hydrogen atom or a substituent. * represents a bonding position.

3. The chemical solution according to claim 1, wherein the specific unsaturated compound is a compound containing a triple bond, and the content of water is 70.0 mass % or less relative to the total mass of the chemical solution.

4. 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 amino group, and a hydroxy group.

5. The chemical solution according to claim 1, wherein the specific unsaturated compound is a compound that does not have a hydrocarbon group having 18 or more carbon atoms.

6. The chemical solution according to claim 2, wherein the specific unsaturated compound contains an aromatic ring structure having a substituent, and the substituent is at least one of a group represented by formula (1a) and a group represented by formula (1b). Ｘ ２ C=C(R Ｙ )-CH ２ -* Formula (1b) In formula (1b), R Ｘ R each independently represents a hydrogen atom, a carboxylic acid group, or a hydrocarbon group which may have a substituent. Ｙ represents a hydrogen atom or a substituent. * represents a bonding position.

7. In the formula (1a), R Ｘ The drug solution according to claim 2, wherein is a hydrogen atom.

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

9. The chemical solution according to claim 1, wherein the content of the water is 95.0 mass % or more based on the total mass of the solvent contained in the chemical solution.

10. The chemical solution according to claim 1, wherein the standard oxidation-reduction potential of the oxidizing agent is 1.3 V or more.

11. The chemical solution of claim 1, wherein the oxidizing agent is hydrogen peroxide.

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

13. 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 any one of claims 1 to 12, and removing at least a portion of the silicon-germanium-containing material with the higher germanium concentration.

14. A method for manufacturing a semiconductor device, comprising the method for processing an object according to claim 13.

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