Semiconductor Etching Solution

Abstract

A semiconductor etching solution is provided which, when treating a workpiece containing Si and SiGe, has a large etching ratio of SiGe to Si and is excellent in storage stability. [Solution] A semiconductor etching solution containing a fluoride ion source, a carboxylic acid, a percarboxylic acid, hydrogen peroxide, and bromide ions, wherein the content of bromide ions is less than 500 ppm by mass with respect to the total mass of the semiconductor etching solution.

Description

[Technical field]

[0001] The present invention relates to a semiconductor etching solution. [Background technology]

[0002] 2. Description of the Related Art As semiconductor devices become increasingly miniaturized, there is an increasing demand for highly efficient and accurate etching, cleaning, and other processes using processing liquids during the semiconductor device manufacturing process. For example, Patent Document 1 discloses a method for selectively removing silicon germanium relative to silicon using an aqueous etching composition containing hydrogen fluoride, dissolved hydrogen peroxide, dissolved acetic acid, dissolved formic acid, and dissolved sulfuric acid. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2020-517108 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have studied a semiconductor etching solution (aqueous etching composition) based on Patent Document 1 and found that although it is possible to selectively etch a silicon germanium-containing material (hereinafter also simply referred to as "SiGe") relative to a silicon-containing material (hereinafter also simply referred to as "Si"), there is room for improvement in the storage stability of the semiconductor etching solution.

[0005] In view of the above circumstances, an object of the present invention is to provide a semiconductor etching liquid that has a large etching ratio of SiGe to Si and excellent storage stability when treating a workpiece containing Si and SiGe. [Means for solving the problem]

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

[0007] [1] A fluoride ion source; Carboxylic acid, Peroxycarboxylic acid, Hydrogen peroxide, bromide ions, A semiconductor etching solution having a bromide ion content of less than 500 ppm by mass based on the total mass of the semiconductor etching solution. [2] A fluoride ion source; Carboxylic acid, Peroxycarboxylic acid, Hydrogen peroxide, At least one compound selected from the group consisting of N-(3-aminopropyl)diethanolamine, 3-morpholino-1,2 propanediol, and diisopropanolamine; Naphthalenesulfonic acid formalin condensate, methanesulfonic acid, C 12 ~C 14 At least one compound selected from the group consisting of alkyldiphenyletherdisulfonic acid and triisopropylnaphthalenesulfonic acid; bromide ions, A semiconductor etching solution having a bromide ion content of less than 500 ppm by mass based on the total mass of the semiconductor etching solution. [3] The semiconductor etching solution according to [1] or [2], wherein the bromide ion content is 5 ppt by mass or more based on the total mass of the semiconductor etching solution. [4] The mass ratio of the carboxylic acid content to the bromide ion content is 1.0 x 10 10 The semiconductor etching solution according to any one of [1] to [3] above. [5] A fluoride ion source; Carboxylic acid, Peroxycarboxylic acid, and hydrogen peroxide. Relative to the total mass of the carboxylic acid, the percarboxylic acid, and hydrogen peroxide, The content of the carboxylic acid is 55.0 to 94.0% by mass, The content of the percarboxylic acid is 5.0 to 25.0% by mass, A semiconductor etching solution having a hydrogen peroxide content of 1.0 to 20.0 mass %. [6] A fluoride ion source; Carboxylic acid, Peroxycarboxylic acid, Hydrogen peroxide, At least one compound selected from the group consisting of N-(3-aminopropyl)diethanolamine, 3-morpholino-1,2 propanediol, and diisopropanolamine; Naphthalenesulfonic acid formalin condensate, methanesulfonic acid, C 12 ~C 14 and at least one compound selected from the group consisting of alkyldiphenyletherdisulfonic acid and triisopropylnaphthalenesulfonic acid, Relative to the total mass of the carboxylic acid, the percarboxylic acid, and hydrogen peroxide, The content of the carboxylic acid is 55.0 to 94.0% by mass, The content of the percarboxylic acid is 5.0 to 25.0% by mass, A semiconductor etching solution having a hydrogen peroxide content of 1.0 to 20.0 mass %. [7] The semiconductor etching solution according to any one of [1] to [6], wherein the carboxylic acid is acetic acid and the percarboxylic acid is peracetic acid. [8] The semiconductor etching solution according to any one of [1] to [7], wherein the fluoride ion source is hydrogen fluoride. [9] Further containing bromate ions, The semiconductor etching solution according to any one of [1] to [8], wherein the content of the bromate ions is 1 to 100 ppm by mass with respect to the total mass of the semiconductor etching solution.

[10] The semiconductor etching solution according to any one of [1] to [9], which does not contain an alcohol-based solvent.

[11] The semiconductor etching solution according to any one of [1] to

[10] , further comprising sulfuric acid.

[12] The semiconductor etching solution according to any one of [1] to

[11] , further comprising an organic compound having a sulfonic acid group.

[13] The semiconductor etching solution according to

[12] , wherein the organic compound having a sulfonic acid group is a polymer containing a repeating unit having a sulfonic acid group.

[14] The semiconductor etching solution according to any one of [1] to

[13] , further comprising an amine.

[15] Further comprising a metal impurity component containing one or more elements selected from the group consisting of Mn, Ni, V, Co, Fe, and Cr; The semiconductor etching solution according to any one of [1] to

[14] , wherein the content of any element contained in the metal impurity components is less than 1.0 ppb by mass with respect to the total mass of the semiconductor etching solution.

[16] The mass ratio of the content of peroxycarboxylic acid to the total content of elements contained in the metal impurity components is 2.0 × 10 9 The semiconductor etching solution according to any one of [1] to

[15] above.

[17] The mass ratio of the content of the fluoride ion source to the total content of elements contained in the metal impurity components is 2.0 × 10 7 The semiconductor etching solution according to any one of [1] to

[16] above.

[18] A method for producing a semiconductor device, comprising using the semiconductor etching solution according to any one of [1] to

[17] .

[19] A semiconductor device manufactured by the method for manufacturing a semiconductor device according to

[18] . Effect of the Invention

[0008] According to the present invention, it is possible to provide a semiconductor etching liquid that has a large etching ratio of SiGe to Si and has excellent storage stability when treating a workpiece containing Si and SiGe. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0010] The following describes the meaning of each description in this specification. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, "ppm" is an abbreviation for "parts per million" and is expressed as 10 -6 "ppb" is an abbreviation for "parts per billion" and is 10 -9 "ppt" is an abbreviation for "parts per trillion" and stands for 10 -12 means...

[0011] In this specification, the term "silicon-containing material" refers to a material that is substantially composed of only Si element. The term "substantially" means that the content of Si element is 90 atomic % or more with respect to the total atoms of the material. Therefore, as long as the content of Si element is within the above range, other elements (excluding Ge element) may be contained. In addition, in this specification, the term "silicon germanium-containing material" refers to a material substantially composed of only Si and Ge elements. The above "substantially" means that the total content of Si and Ge elements is 90 atomic % or more with respect to the total atoms of the material. Therefore, other elements may be contained as long as the total content of Si and Ge elements is within the above range. In addition, in silicon germanium, the content ratio of Si and Ge elements is not particularly limited, and the content of Ge elements with respect to the total amount of Si and Ge elements is preferably 10 to 70 atomic %.

[0012] {Semiconductor etching solution} A first embodiment and a second embodiment of the semiconductor etching solution of the present invention (hereinafter, simply referred to as "etching solution") will be described. Specifically, each component and optional component in the first embodiment and the second embodiment of the etching solution, a method for producing the etching solution, a container for the etching solution, and a method for providing the etching solution will be described below. A first embodiment of the etching solution is an etching solution that contains a fluoride ion source, a carboxylic acid, a percarboxylic acid, hydrogen peroxide, and bromide ions, and the bromide ion content is less than 500 ppm by mass with respect to the total mass of the etching solution. A second embodiment of the etching solution is an etching solution containing a fluoride ion source, a carboxylic acid, a percarboxylic acid, and hydrogen peroxide, in which the carboxylic acid content is 55.0 to 94.0 mass%, the percarboxylic acid content is 5.0 to 25.0 mass%, and the hydrogen peroxide content is 1.0 to 15.0 mass%, relative to the total mass of the percarboxylic acid, the carboxylic acid, and the hydrogen peroxide. In the following description, when at least one of the following is satisfied: the etching ratio of SiGe to Si is larger, and the storage stability of the etching solution is superior, it is also said that "the effect of the present invention is superior."

[0013] [Component: First embodiment] The components contained in the etching solution according to the first embodiment will be described below. A first embodiment of the etching solution of the present invention comprises a fluoride ion source, a carboxylic acid, a percarboxylic acid, hydrogen peroxide, and bromide ions, and the content of bromide ions is less than 500 ppm by mass relative to the total mass of the etching solution.

[0014] (Fluoride Ion Source: First Embodiment) A first embodiment of the etching solution of the present invention includes a source of fluoride ions. The fluoride ion source is a component in the etching solution that releases fluoride ions. Examples of fluoride ions include F - and H.F. 2 -Examples of ions include those containing fluorine atoms. Although the mechanism is unclear, the inventors speculate that the etching solution contains fluoride ions, and thus exhibits the etching ability for SiGe.

[0015] Examples of fluoride ion sources include hydrogen fluoride (HF; hydrogen fluoride may be used as hydrofluoric acid (HF aqueous solution), hexafluorophosphoric acid (HPF 6 ), hexafluorosilicic acid (H 2 SiF 6 ), and tetrafluoroboric acid (HBF 4 ), and salts thereof. Also, examples of fluoride ion sources include bifluoride ion (HF 2 - ), and fluoride-containing ions (e.g., MF 6 n- , M: any atom, n: 1 to 3). Examples of counter cations constituting the salt include alkali metal ions, ammonium cations, quaternary ammonium cations, sulfonium cations, and iodonium cations.

[0016] Specific examples of hydrogen fluoride salts include lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), and ammonium fluoride (NH 4 F) and tetra-n-butylammonium fluoride (N(C 4 H 9 ) 4 F), tetramethylammonium fluoride (N(CH 3 ) 4 F) can be mentioned. Specific examples of salts of hexafluorophosphate include lithium hexafluorophosphate (LiPF 6 ), sodium hexafluorophosphate (NaPF 6 ), potassium hexafluorophosphate (KPF 6 ), ammonium hexafluorophosphate (NH 4 PF 6), and tetra-n-butylammonium hexafluorophosphate (N(C 4 H 9 ) 4 PF 6 ) are mentioned. Specific examples of salts of hexafluorosilicic acid include sodium hexafluorosilicate (Na 2 SiF 6 ), potassium hexafluorosilicate (K 2 SiF 6 ), and ammonium hexafluorosilicate ((NH 4 ) 2 SiF 6 ) are mentioned. Specific examples of salts of tetrafluoroboric acid include lithium tetrafluoroborate (LiBF 4 ), sodium tetrafluoroborate (NaBF 4 ), potassium tetrafluoroborate (KBF 4 ), and ammonium tetrafluoroborate (NH 4 BF 4 ) are mentioned. A specific example of a component that releases bifluoride ions is sodium hydrogen fluoride (NaHF 2 ), potassium hydrogen fluoride (KHF 2 ), and ammonium hydrogen fluoride (NH 4 -HF) are examples. Specific examples of components that release fluoride-containing ions include sodium hexafluoroaluminate (Na 3 AlF 6 ), 2-ammonium hexafluorotitanate ((NH 4 ) 2 TiF 6 ), potassium hexafluoroniobate (KNbF 6 ), and sodium hexafluoroantimonate (NaSbF 6 ) are mentioned. Among the above, the fluoride ion source is preferably hydrogen fluoride, hexafluorophosphoric acid, or hexafluorosilicic acid, and hydrogen fluoride is more preferable in terms of providing better effects of the present invention.

[0017] The content of the fluoride ion source in the first embodiment of the etching liquid is not particularly limited, but is preferably 0.05 to 1.0 mass %, more preferably 0.1 to 0.5 mass %, and even more preferably 0.1 to 0.4 mass %, relative to the total mass of the etching liquid, in that the etching rate for SiGe is appropriately excellent.

[0018] The fluoride ion source may be used alone or in combination of two or more. When two or more fluoride ion sources are used, the total amount thereof is preferably within the above range.

[0019] (Carboxylic Acid: First Embodiment) A first embodiment of the etching solution of the present invention comprises a carboxylic acid. The etching solution contains both carboxylic acid and hydrogen peroxide, which will be described later, and generates percarboxylic acid, which will be described later.

[0020] As used herein, a carboxylic acid is an organic compound having a carboxy group. The number of carboxy groups contained in the carboxylic acid is not particularly limited as long as it is 1 or more, preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. Carboxylic acids include, for example, carboxylic acids having an aliphatic group and carboxylic acids having an aromatic group.

[0021] The aliphatic group in the carboxylic acid having an aliphatic group includes an alkyl group, an alkenyl group, and an alkynyl group. The aliphatic group may be linear, branched, or cyclic. The aliphatic group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms. The aliphatic group may have a substituent other than the carboxy group. The substituent that the aliphatic group may have is not particularly limited, and examples thereof include, in addition to a carboxy group, a hydroxy group, a thiol group, a fluoro group, a chloro group, a bromo group, an iodo group, an amino group, a nitro group, and a cyano group. -CH which constitutes an aliphatic group 2 A part of - may be replaced by a divalent substituent. -CH 2 Examples of the divalent substituent replacing a part of - include -O-, -S-, -CO-, -COO-, -OCO-, -NH-, and -NR T - and -SO 2 - is one of them. T represents an alkyl group. The aliphatic group is preferably an alkyl group, more preferably a linear alkyl group.

[0022] The aromatic group in the carboxylic acid having an aromatic group may have a structure exhibiting aromaticity, and may be an aryl group, a heteroaryl group, or a group obtained by combining these with a non-aromatic group. The aromatic group may have a substituent other than the carboxy group. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. The substituents which the aromatic group may have are the same as the substituents which the alkyl group may have. The number of carboxy groups in the aryl group is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0023] Examples of carboxylic acids include formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, valeric acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, aconitic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, cyclohexanediaminetetraacetic acid, triethylenetetramine hexaacetic acid, taurine diacetic acid, methylglycine diacetic acid, glutamic acid diacetic acid, trifluoroacetic acid, chloroacetic acid, benzoic acid, p-chlorobenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, mellitic acid, and salicylic acid. Among these, in terms of superior effects of the present invention, formic acid, acetic acid, trifluoroacetic acid, benzoic acid, m-chlorobenzoic acid, or phthalic acid is preferred, acetic acid or m-chlorobenzoic acid is more preferred, and acetic acid is even more preferred.

[0024] The content of the carboxylic acid in the first embodiment of the etching solution is not particularly limited, but in terms of better effects of the present invention, the content is preferably 30.0 to 80.0 mass%, more preferably 40.0 to 70.0 mass%, and even more preferably 50.0 to 65.0 mass%, relative to the total mass of the etching solution.

[0025] The carboxylic acid may be used alone or in combination of two or more. When two or more carboxylic acids are used, the total amount thereof is preferably within the above range.

[0026] (Hydrogen Peroxide: First Embodiment) A first embodiment of the etching solution of the present invention contains hydrogen peroxide. The etching solution contains the above-mentioned carboxylic acid and hydrogen peroxide at the same time, and generates a percarboxylic acid, which will be described later. Hydrogen peroxide may be used in the form of aqueous hydrogen peroxide in terms of safety and availability. The content of hydrogen peroxide in the first embodiment of the etching solution is not particularly limited, but in terms of better effects of the present invention, the content is preferably 1.0 to 10.0 mass%, more preferably 2.0 to 6.0 mass%, and even more preferably 2.5 to 5.0 mass%, relative to the total mass of the etching solution.

[0027] (Percarboxylic acid: first embodiment) A first embodiment of the etching solution of the present invention comprises a percarboxylic acid. Although the mechanism is unclear, the inventors speculate that the etching solution contains both the above-mentioned carboxylic acid and hydrogen peroxide, generating percarboxylic acid, and that the generated percarboxylic acid acts in concert with the above-mentioned fluoride ions, thereby increasing the etching ratio of SiGe to Si.

[0028] Percarboxylic acid is thought to be produced by the equilibrium reaction of the following formula (1) when carboxylic acid and hydrogen peroxide are simultaneously contained in the etching solution. In formula (1), R represents a residue. The percarboxylic acid may be added separately to the etching solution, if necessary.

[0029] [ka]

[0030] In the etching solution, percarboxylic acid corresponding to the carboxylic acid contained in the etching solution is generated. Examples of percarboxylic acids include performic acid, peracetic acid, perpropionic acid, peracrylic acid, perbutyric acid, perlactic acid, percitric acid, peroxalic acid, permalonic acid, persuccinic acid, perglutaric acid, peradipic acid, perfumaric acid, permaleic acid, trifluoroperacetic acid, chloroperacetic acid, perbenzoic acid, p-chloroperbenzoic acid, o-chloroperbenzoic acid, m-chloroperbenzoic acid, perphthalic acid, perisophthalic acid, perterephthalic acid, pertrimesic acid, permellitic acid, and persalicylic acid, as well as the percarboxylic acids corresponding to valeric acid, malic acid, aconitic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, cyclohexanediaminetetraacetic acid, triethylenetetraminehexaacetic acid, taurinediacetic acid, methylglycinediacetic acid, and glutamic aciddiacetic acid. The preferred percarboxylic acid is the percarboxylic acid generated from the above-mentioned preferred carboxylic acid.Preferred percarboxylic acid includes, for example, performic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, and perphthalic acid.Among them, peracetic acid or m-chlorobenzoic acid is more preferred, and peracetic acid is even more preferred, in terms of the effect of the present invention being more excellent. When the percarboxylic acid is added separately, the preferred percarboxylic acid is the same as the above-mentioned preferred percarboxylic acid.

[0031] The content of percarboxylic acid can be quantified by known methods, such as titration using manganese peroxide, potassium iodide, and sodium thiosulfate. Specific procedures are described below. The etching solution to be measured is acidified with sulfuric acid, and the hydrogen peroxide contained in the etching solution is titrated with potassium permanganate. Potassium iodide is then added to the etching solution to produce an amount of free iodine equivalent to the amount of percarboxylic acid. The free iodine is titrated with sodium thiosulfate to determine the amount of percarboxylic acid. The end point of each titration can be monitored by the change in the solution's redox potential. The percarboxylic acid content herein is measured using the titration method described above.

[0032] The content of the percarboxylic acid in the first embodiment of the etching solution is preferably 5.0 to 20.0 mass%, more preferably 8.0 to 15.0 mass%, and further preferably 10.0 to 13.0 mass%, relative to the total mass of the etching solution, in that the effects of the present invention are more excellent.

[0033] The mass ratios of the carboxylic acid, percarboxylic acid, and hydrogen peroxide contained in the first embodiment of the etching solution are not particularly limited, but in terms of better effects of the present invention, the carboxylic acid content is preferably 55.0 to 94.0 mass%, the percarboxylic acid content is 5.0 to 25.0 mass%, and the hydrogen peroxide content is 1.0 to 20.0 mass%, relative to the total mass of the carboxylic acid, percarboxylic acid, and hydrogen peroxide, and more preferably the carboxylic acid content is 70.0 to 89.0 mass%, the percarboxylic acid content is 10.0 to 20.0 mass%, and the hydrogen peroxide content is 1.0 to 10.0 mass%, relative to the total mass of the carboxylic acid, percarboxylic acid, and hydrogen peroxide.

[0034] The percarboxylic acid may be used alone or in combination of two or more. When two or more percarboxylic acids are used, the total amount thereof is preferably within the above range.

[0035] (Bromide ion: first embodiment) A first embodiment of the etching solution of the present invention contains bromide ions, and the content of bromide ions is less than 500 ppm by mass relative to the total mass of the etching solution. Although the mechanism is unclear, the inventors speculate that the etching solution has excellent storage stability by containing less than 500 ppm by mass of bromide ions relative to the total mass of the etching solution.Furthermore, they speculate that the surface roughness of SiGe after etching is reduced due to the affinity of bromide ions to Ge.

[0036] The bromide ion content in the first embodiment of the etching solution is preferably 10 mass ppm or less, more preferably 10 mass ppb or less, and preferably 100 mass ppt or less, relative to the total mass of the etching solution, in terms of better effects of the present invention. The lower limit of the bromide ion content is preferably 1 ppt by mass or more, and more preferably 5 ppt by mass or more, relative to the total mass of the etching solution, in that the surface roughness of SiGe is reduced.

[0037] An example of a method for supplying bromide ions to the etching solution is to add a compound containing bromide ions (bromide ion source) to the etching solution. The bromide ion source includes bromide and a salt of a bromide ion and a cation. The bromide includes hydrobromic acid (HBr aqueous solution). The bromide ion and a salt of a cation include a salt of an alkali metal ion and a bromide ion, a salt of an alkaline earth metal ion and a bromide ion, and a salt of a basic compound ion and a bromide ion. Examples of salts consisting of an alkali metal ion and a bromide ion include lithium bromide, sodium bromide, and potassium bromide. Examples of salts consisting of alkaline earth metal ions and bromide ions include magnesium bromide, calcium bromide, and strontium bromide. Examples of salts consisting of a basic compound ion and a bromide ion include ammonium bromide, methylammonium bromide, ethylammonium bromide, diethylammonium bromide, triethylammonium bromide, tetraethylammonium bromide, and tetrabutylammonium bromide.

[0038] The bromide ion content can be measured by a known method, for example, ion chromatography. The bromide ion content in this specification refers to a method measured using ion chromatography. More specifically, the analysis is carried out using an ion chromatograph (Dionex ICS-6000). If bromide ions are not detected using the above device, the etching solution is concentrated using a Dionex® IonPac® AC15 concentration column to detect bromide ions. If bromide ions are not detected by this concentration operation, the bromide ion content is set to 0.

[0039] The mass ratio of the carboxylic acid content to the bromide ion content is not particularly limited, but is preferably 1.0×10 8 In most cases, the effect of the present invention is more excellent, so it is 1.0×10 10 The upper limit of the mass ratio of the carboxylic acid content to the bromide ion content is not particularly limited, but it is preferably 1.0×10 11 The following is preferred:

[0040] (Optional components, etc.: First embodiment) Optional components that may be contained in the first embodiment of the etching solution will be described below. Optional components that may be included in the first embodiment of the etching solution of the present invention include a solvent, bromate ions, sulfuric acid, a compound having sulfonic acid, an amine, and metal impurities.

[0041] <Solvent: First embodiment> The first embodiment of the etching solution of the present invention may contain a solvent. The solvent is not particularly limited as long as it can dissolve the above components and optional components, and examples of the solvent include water and organic solvents. Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, sulfone-based solvents, sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents. The first embodiment of the etching solution preferably does not contain an alcohol-based solvent. Examples of the alcohol-based solvent include methanol, ethanol, propanol, and propylene glycol. As described later, amines are not included in the alcohol-based solvent. More specifically, alkanolamines are not included in the alcohol-based solvent. Although the mechanism is unclear, the inventors speculate that the absence of an alcohol-based solvent in the etching solution inhibits the reduction of hydrogen peroxide and / or percarboxylic acid, thereby improving storage stability. The solvent is preferably water, and more preferably ultrapure water.

[0042] The content of the solvent in the first embodiment of the etching solution is not particularly limited, but is preferably 15.0 to 70.0 mass %, more preferably 18.0 to 60.0 mass %, further preferably 20.0 to 50.0 mass %, and particularly preferably 20.0 to 30.0 mass %, based on the total mass of the etching solution.

[0043] <Bromate ion: first embodiment> The first embodiment of the etching solution of the present invention may contain bromate ions. The inventors speculate that by including bromate ions in the etching solution, decomposition of hydrogen peroxide and / or percarboxylic acid is suppressed, and storage stability is improved.

[0044] When bromate ions are added to the etching solution, a compound containing bromate ions may be added to the etching solution, or an aqueous solution of a compound containing bromate ions may be added to the etching solution. Compounds containing bromate ions include salts of alkali metal ions and bromate ions, salts of alkaline earth metals and bromate ions, salts of basic compound ions and bromate ions, and bromic acid (HBrO 3 ) are mentioned. Examples of salts consisting of an alkali metal ion and a bromate ion include sodium bromate and potassium bromate. Examples of salts consisting of alkaline earth metals and bromate ions include calcium bromate and strontium bromate. An example of a salt formed from a basic compound ion and a bromate ion is ammonium bromate. The compounds containing bromate ions may be used in combination of two or more kinds.

[0045] The content of bromate ions in the first embodiment of the etching solution is not particularly limited, but is often 100 ppb by mass to 500 ppm by mass. In terms of better effects of the present invention, the content is more preferably 1 to 100 ppm by mass, and more preferably 50 to 100 ppm by mass, relative to the total mass of the etching solution.

[0046] <Sulfuric acid: first embodiment> The first embodiment of the etching solution of the present invention may contain sulfuric acid. Although the mechanism is unclear, the inventors speculate that the etching solution contains sulfuric acid, which acts in concert with carboxylic acid, hydrogen peroxide, and / or percarboxylic acid to increase the etching ratio of SiGe to Si.

[0047] The content of sulfuric acid in the first embodiment of the etching solution is not particularly limited, but is preferably 0.01 to 2.0 mass %, more preferably 0.1 to 1.0 mass %, based on the total mass of the etching solution.

[0048] <Organic Compound Having Sulfonic Acid Group: First Embodiment> The first embodiment of the etching liquid of the present invention may contain an organic compound having a sulfonic acid group. Although the mechanism is unclear, the inventors speculate that the etching solution contains an organic compound having a sulfonic acid group, which acts in concert with the carboxylic acid, hydrogen peroxide, and / or percarboxylic acid to increase the etching ratio of SiGe to Si.

[0049] The organic compound having a sulfonic acid group in the first embodiment of the etching solution is not particularly limited, and may be, for example, alkylsulfonic acid, arylsulfonic acid, or a salt thereof. The organic compound having a sulfonic acid group may be a polymer containing a repeating unit having the above-mentioned sulfonic acid group, or may be a salt thereof. Examples of cations that form salts with sulfonic acids include lithium ions, sodium ions, potassium ions, and ammonium cations.

[0050] The alkyl group in the alkylsulfonic acid may be linear or branched, and may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, an amino group, and a hydroxyl group. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, and further preferably 1. Examples of alkylsulfonic acids include methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, and dodecylsulfonic acid. Among these, methanesulfonic acid is preferred.

[0051] The aryl group in the arylsulfonic acid may have a group exhibiting aromaticity, and may be a combination of an alkyl group and a group exhibiting aromaticity. Aryl groups include, for example, phenyl, naphthyl, and biphenyl groups. Examples of arylsulfonic acids include benzenesulfonic acid, 2-naphthalenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dipropylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, dodecyldiphenyletherdisulfonic acid, and tetradecyldiphenyletherdisulfonic acid. Among these, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, triisopropylnaphthalenesulfonic acid, dodecyldiphenyletherdisulfonic acid, and tetradecyldiphenyletherdisulfonic acid are preferred.

[0052] Examples of the polymer containing a repeating unit having a sulfonic acid group include polymers containing a repeating unit having the above-mentioned group derived from an alkylsulfonic acid and / or the above-mentioned group derived from an arylsulfonic acid. The polymer may contain repeat units that do not have a sulfonic acid group. The weight average molecular weight of the polymer is preferably 400 to 50,000. Examples of polymers containing a repeating unit having a sulfonic acid group include formaldehyde condensates of benzenesulfonic acid and formaldehyde condensates of naphthalenesulfonic acid.

[0053] As the organic compound having a sulfonic acid group, a sulfonic acid surfactant is also preferred. Examples of sulfonic acid surfactants include formalin condensates of arylsulfonic acids such as alkylbenzenesulfonic acids, alkylnaphthalenesulfonic acids, alkyldiphenyletherdisulfonic acids, polyoxyalkylenealkylethersulfonic acids, styrenesulfonic acids, and phenolsulfonic acids, and salts thereof (lithium salts, sodium salts, potassium salts, or ammonium salts).

[0054] The content of the organic compound having a sulfonic acid group in the first embodiment of the etching solution is not particularly limited, but is preferably 0.001 to 1.0 mass %, more preferably 0.01 to 0.5 mass %, based on the total mass of the etching solution.

[0055] The organic compound having a sulfonic acid group may be used alone or in combination of two or more. When two or more organic compounds having a sulfonic acid group are used, the total amount thereof is preferably within the above range.

[0056] <Amine: First embodiment> The first embodiment of the etching solution of the present invention may contain an amine. Although the mechanism is unclear, the inventors speculate that the etching solution contains an amine-containing compound, which acts in concert with the fluoride ion source, carboxylic acid, hydrogen peroxide, and / or percarboxylic acid to increase the etching ratio of SiGe to Si. In this specification, an amine refers to a compound in which one or more of the hydrogen atoms of ammonia are substituted with a hydrocarbon group that may have a substituent. However, even if the hydrocarbon group has a hydroxyl group as a substituent, the compound is not included in the alcohol-based solvent. In other words, the etching solution may contain an amine having a hydroxyl group.

[0057] Examples of the hydrocarbon group which may have a substituent include an alkyl group which may have a substituent, and an aryl group which may have a substituent. The alkyl group, which may have a substituent, may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 3. Examples of the substituent that the alkyl group may have include a halogen atom, a cyano group, an amino group (-NH 2 ), and a hydroxy group. Among these, an amino group and a hydroxy group are preferred. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 2,3-hydroxypropyl group, a 2-aminoethyl group, and a 3-aminopropyl group. When there are two or more alkyl groups in the amine, the two may be bonded together to form a ring to form a cyclic amine. The cyclic amine may or may not exhibit aromaticity. Examples of the cyclic amine formed include a pyrrolidine ring, a piperidine ring, a morpholine ring, a pyrrole ring, and a pyridine ring. Among them, a morpholine ring is preferred. Examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group, a furyl group, a pyrrolyl group, a p-hydroxyphenyl group, and a p-chlorophenyl group.

[0058] Examples of amines include methylamine, dimethylamine, trimethylamine, ethylamine, ethanolamine, diethylamine, diethanolamine, propylamine, diisopropanolamine, N-(3-aminopropyl)diethanolamine, morpholine, and 3-morpholino-1,2-propanediol. Among them, diisopropanolamine, N-(3-aminopropyl)diethanolamine, and 3-morpholino-1,2-propanediol are preferred.

[0059] The content of the amine in the first embodiment of the etching solution is not particularly limited, but is preferably 0.01 to 1 mass %, more preferably 0.02 to 0.1 mass %, based on the total mass of the etching solution.

[0060] The amine may be used alone or in combination of two or more kinds. When two or more kinds of amines are used, the total amount thereof is preferably within the above range.

[0061] <Metal Impurities: First Embodiment> The first embodiment of the etching solution of the present invention may further contain a metal impurity component including one or more elements (hereinafter also referred to as "specific elements") selected from the group consisting of Mn, Ni, V, Co, Fe, and Cr. The content of each element contained in the metal impurity component is preferably less than 1.0 ppb by mass relative to the total mass of the etching solution. In other words, the content of each specific element is preferably less than 1.0 ppb by mass. There is no particular lower limit for the content of any of the elements, but it may be 1 ppt by mass or more, and may not be detectable. Although the mechanism is unclear, the inventors speculate that by making the mass of any element of the metal impurity components less than 1.0 ppb by mass relative to the total mass of the etching solution, the decomposition of hydrogen peroxide and / or percarboxylic acid is suppressed, and storage stability is improved.

[0062] The metal impurity components may be in the form of metal particles and metal ions. The metal impurity component may contain one type of specific element or may contain two or more types of specific elements. The metal particles may be a simple substance or an alloy, or the metal may be present in a form associated with an organic substance.

[0063] The content of specific elements in the metal impurity components in the etching solution can be measured using the SP-ICP-MS method (Single Nano Particle-Inductively Coupled Plasma-Mass Spectrometry). Here, the SP-ICP-MS method uses the same equipment as the normal ICP-MS method (inductively coupled plasma mass spectrometry), and only the data analysis is different. Data analysis of the SP-ICP-MS method can be performed using commercially available software.

[0064] The measurement method by the SP-ICP-MS method can be performed, for example, by using an Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma-mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, Inc., according to the method described in the Examples. As other devices, NexION350S manufactured by PerkinElmer, Inc. and Agilent 8900 manufactured by Agilent Technologies, Inc. can also be used. If the content of the specific element cannot be detected in the above measurement, the etching solution is concentrated and the above measurement is performed. If the specific element is not detected after concentration, the content is recorded as 0. The above concentration operation is carried out by first adding ammonia water to the etching solution to adjust the pH to 6 to 8, and then leaving it at room temperature for one week, and then heating the obtained etching solution to 100° C. and concentrating it 100 times.

[0065] The mass ratio of the content of the fluoride ion source to the total content of the specific elements contained in the metal impurity components is not particularly limited, but is preferably 1.0×10 6 In most cases, the effect of the present invention is more excellent, so 2.0×10 7The upper limit is not particularly limited, but is preferably 1.0×10 10 Less than or equal to 1.0×10 is preferred. 9 The following is more preferred:

[0066] The mass ratio of the content of percarboxylic acid to the total content of specific elements contained in the metal impurity components is not particularly limited, but is preferably 1.0×10 8 In most cases, the effect of the present invention is more excellent, so 2.0×10 9 The upper limit is not particularly limited, but is preferably 1.0×10 10 The following is preferred:

[0067] <Other components: First embodiment> The first embodiment of the etching solution may contain components other than those described above. Other components that may be contained in the first embodiment of the etching solution include, for example, an oxidizing agent and a surfactant. Examples of oxidizing agents include nitric acid, peroxides, persulfides (such as monopersulfides and dipersulfides), percarbonates, oxide halides (such as iodic acid and periodic acid), perboric acid, permanganates, molybdic acid compounds, cerium compounds, and ferricyanides, as well as acids or salts thereof, although peroxides do not include percarboxylic acids. Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. The surfactants do not include the above-mentioned organic compounds having a sulfonic acid group.

[0068] A preferred embodiment of the first embodiment of the etching solution is as follows: a source of fluoride ions; Carboxylic acid, Peroxycarboxylic acid, Hydrogen peroxide, At least one compound selected from the group consisting of N-(3-aminopropyl)diethanolamine, 3-morpholino-1,2 propanediol, and diisopropanolamine; Naphthalenesulfonic acid formalin condensate, methanesulfonic acid, C 12 ~C 14 At least one compound selected from the group consisting of alkyldiphenyletherdisulfonic acid and triisopropylnaphthalenesulfonic acid; bromide ions, The semiconductor etching solution may have a bromide ion content of less than 500 ppm by mass relative to the total mass of the semiconductor etching solution.

[0069] [Component: Second embodiment] The components contained in the etching solution according to the second embodiment will be described below. A second embodiment of the etching solution of the present invention contains a fluoride ion source, a carboxylic acid, a percarboxylic acid, and hydrogen peroxide, and the content of the carboxylic acid is 55.0 to 94.0 mass%, the content of the percarboxylic acid is 5.0 to 25.0 mass%, and the content of the hydrogen peroxide is 1.0 to 20.0 mass%, based on the total mass of the carboxylic acid, the percarboxylic acid, and the hydrogen peroxide. The second embodiment of the etching solution of the present invention has the same configuration as the first embodiment of the etching solution of the present invention, except that bromide ions are not an essential component and that the carboxylic acid, the percarboxylic acid, and the hydrogen peroxide satisfy a predetermined mass relationship.

[0070] (Fluoride Ion Source: Second Embodiment) A second embodiment of the etching solution of the present invention includes a source of fluoride ions. The fluoride ion source is the same as that explained in the first embodiment, and the preferred embodiments (eg, the type of fluoride ion source, the content of the fluoride ion source in the etching solution, etc.) are also the same.

[0071] (Carboxylic Acid: Second Embodiment) A second embodiment of the etching solution of the present invention comprises a carboxylic acid. The carboxylic acid is the same as that explained in the first embodiment, and the preferred embodiments (eg, the type of carboxylic acid and the content of the carboxylic acid in the etching solution) are also the same.

[0072] (Hydrogen Peroxide: Second Embodiment) A second embodiment of the etching solution of the present invention comprises hydrogen peroxide. The hydrogen peroxide is the same as that described in the first embodiment, and the preferred embodiments (eg, the content of hydrogen peroxide in the etching solution) are also the same.

[0073] (Percarboxylic acid: second embodiment) A second embodiment of the etching solution of the present invention comprises a percarboxylic acid. The percarboxylic acid is the same as that explained in the first embodiment, and the preferred embodiments (eg, the type of percarboxylic acid and the content of percarboxylic acid in the etching solution) are also the same.

[0074] (Mass ratio of carboxylic acid, percarboxylic acid and hydrogen peroxide: second embodiment) The mass ratios of the carboxylic acid, percarboxylic acid, and hydrogen peroxide in the second embodiment of the etching solution are such that the carboxylic acid content is 55.0 to 94.0 mass%, the percarboxylic acid content is 5.0 to 25.0 mass%, and the hydrogen peroxide content is 1.0 to 20.0 mass%, relative to the total mass of the carboxylic acid, percarboxylic acid, and hydrogen peroxide. In particular, in terms of better effects of the present invention, the carboxylic acid content is preferably 70.0 to 89.0 mass%, the percarboxylic acid content is 10.0 to 20.0 mass%, and the hydrogen peroxide content is 1.0 to 10.0 mass%, relative to the total mass of the carboxylic acid, percarboxylic acid, and hydrogen peroxide, and it is more preferable that the carboxylic acid content is 75.0 to 85.0 mass%, the percarboxylic acid content is 12.0 to 17.5 mass%, and the hydrogen peroxide content is 3.0 to 7.5 mass%.

[0075] (Optional components, etc.: Second embodiment) Hereinafter, optional components that may be contained in the second embodiment of the etching solution will be described. Optional components that may be included in the second embodiment of the etching solution of the present invention include a solvent, bromide ions, bromate ions, sulfuric acid, a compound having sulfonic acid, an amine, and metal impurities. Each component is the same as that explained in the first embodiment, and the preferred embodiments (type, content, etc.) are also the same. In the second embodiment of the etching solution, similarly to the first embodiment, bromide ions may be contained, and the content of bromide ions is preferably less than 500 ppm by mass with respect to the total mass of the etching solution. The preferred range of the bromide ion content is the same as the preferred range described in the first embodiment.

[0076] A preferred embodiment of the second embodiment of the etching solution is as follows: a source of fluoride ions; Carboxylic acid, Peroxycarboxylic acid, Hydrogen peroxide, At least one compound selected from the group consisting of N-(3-aminopropyl)diethanolamine, 3-morpholino-1,2 propanediol, and diisopropanolamine; Naphthalenesulfonic acid formalin condensate, methanesulfonic acid, C 12 ~C 14 and at least one compound selected from the group consisting of alkyldiphenyletherdisulfonic acid and triisopropylnaphthalenesulfonic acid, Relative to the total mass of the carboxylic acid, the percarboxylic acid, and hydrogen peroxide, The content of the carboxylic acid is 55.0 to 94.0% by mass, The content of the percarboxylic acid is 5.0 to 25.0% by mass, The semiconductor etching solution may have a hydrogen peroxide content of 1.0 to 20.0% by mass.

[0077] [Method of manufacturing semiconductor etching solution] The method for producing the etching solution (first embodiment and second embodiment) is not particularly limited, and a known production method can be used. For example, when producing the etching solution of the first embodiment, a method of mixing a fluoride ion source, a carboxylic acid, hydrogen peroxide, and a bromide ion source in a predetermined amount can be mentioned. When mixing the above components, an optional component such as water may be mixed together as necessary. In addition, when producing the etching solution, a filtration treatment using a filter may be performed as necessary. The filtration treatment may be performed on the raw materials or on the etching solution after mixing.

[0078] [Container for semiconductor etching liquid and method for providing semiconductor etching liquid] The etching solution (first embodiment and second embodiment) may be stored in a container until use. Such a container and the etching solution contained in the container are collectively referred to as an etching solution container. The etching solution is taken out from the stored etching solution container and used. The etching solution may also be transported as an etching solution container and provided between a manufacturer and a user, or between a storage location and a usage location, etc.

[0079] The container preferably has a degassing mechanism for adjusting the pressure (internal pressure) in the container. The degassing mechanism is a mechanism that, for example, when the temperature of the etching solution in the container rises during storage of the etching solution container and / or gas is generated from the etching solution due to decomposition of some components of the etching solution, releases the generated gas from inside the container to the outside, thereby keeping the internal pressure within a certain range without excessively increasing it. Examples of venting mechanisms include check valves and venting caps that include a venting mechanism. Furthermore, from the standpoint of ease of handling the etching liquid, it is preferable that the etching liquid be provided from the manufacturer to the user, or between the storage location and the usage location, by a method using such an etching liquid container.

[0080] The container (particularly the container body) is preferably one that has a high degree of cleanliness inside the container and has little elution of impurities for semiconductor applications. Examples of containers that can be used include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd. The inner wall of the container (particularly the container body) is preferably formed from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin and polyethylene-polypropylene resin, or from a resin different from these.

[0081] The different resin is preferably a fluororesin (perfluororesin). By using a container whose inner wall is made of a fluororesin, the occurrence of the problem of elution of ethylene or propylene oligomers can be suppressed compared to a container whose inner wall is made of a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin. An example of a container whose inner wall is a fluororesin is FluoroPure PFA composite drum manufactured by Entegris, Inc. In addition, containers described on page 4 or the like of JP-A-3-502677, on page 3 or the like of WO 2004 / 016526, and on pages 9 and 16 or the like of WO 99 / 046309 can also be used.

[0082] The inside of these containers (container body, cap, etc.) is preferably washed before filling with the etching liquid. The liquid used for washing is preferably one that has a reduced amount of metal impurities. After production, the etching solution may be bottled in containers such as gallon bottles or coated bottles for transport or storage.

[0083] In order to prevent the etching solution from changing during storage, the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) with a purity of 99.99995% by volume or more. In particular, a gas with a low moisture content is preferable. In addition, the etching solution may be transported and stored at room temperature, but the temperature may be controlled to a range of -20 to 20°C to prevent deterioration.

[0084] The etching solution may be prepared as a kit in which the raw materials are divided into a plurality of parts.

[0085] {Use} The etching solution (first and second embodiments) is used in semiconductor processing. More specifically, it is preferably used for semiconductor devices. "For use in semiconductor devices" means for use in the manufacture of semiconductor devices. The etching solution can also be used in processes for manufacturing semiconductor devices, for example, to treat materials composed of silicon germanium present on a substrate, insulating films, resist films, anti-reflective films, etching residues, and ashing residues (hereinafter simply referred to as "residues"). The etching solution may also be used to treat a substrate after chemical mechanical polishing. In particular, the etching solution is preferably used to treat a workpiece containing Si and SiGe (hereinafter simply referred to as "workpiece").

[0086] {Item to be processed} The workpiece includes Si and SiGe. In the case of SiGe, the content of Ge element relative to the total amount of Si element and Ge element is preferably 10 to 70 atomic %. For example, the content of Ge element relative to the total amount of Si element and Ge element is typically 15 atomic %, 30 atomic %, and 50 atomic %. The workpiece is not particularly limited as long as it contains Si and SiGe, but typically, Si and SiGe are disposed on a substrate. Here, "on the substrate" includes any of the front and back surfaces, side surfaces, and inside grooves of the substrate. In addition, "Si and SiGe are disposed on a substrate" includes cases where Si and SiGe are directly on the surface of the substrate, and cases where Si and SiGe are on the substrate via another layer. In addition, "Si and SiGe are disposed on a substrate" refers to any form of existence as long as Si and SiGe are present simultaneously on the substrate. For example, Si and SiGe may be in contact with each other, or may be in contact with each other via another layer or member. In addition, Si and SiGe may be present on the same substrate but not in contact with each other.

[0087] The substrate is not particularly limited, and examples thereof include metal substrates, semiconductor substrates, conductive substrates other than metal, metal oxide substrates, glass substrates, and resin substrates. Among these, semiconductor substrates are preferred. Examples of semiconductor substrates include semiconductor wafers, glass substrates for photomasks, glass substrates for liquid crystal displays, glass substrates for plasma displays, substrates for FEDs (Field Emission Displays), substrates for optical disks, substrates for magnetic disks, and substrates for magneto-optical disks. Examples of materials that may be used for the semiconductor substrate include silicon, Group III-V compounds such as GaAs, and combinations thereof. The size, thickness, shape, layer structure, etc. of the substrate are not particularly limited and can be appropriately selected as desired.

[0088] The form of the Si or SiGe on the substrate may be any of a film, wiring, plate, column, and particle arrangement.

[0089] The workpiece may include layers and / or structures other than Si and SiGe as desired. For example, one or more members selected from the group consisting of metal wiring, a gate electrode, a source electrode, a drain electrode, an insulating layer, a ferromagnetic layer, and a non-magnetic layer may be disposed on the substrate. The substrate may include an exposed integrated circuit structure. The integrated circuit structure includes, for example, interconnect features such as metal wiring and dielectric materials. Metals and alloys used in the interconnect features include, for example, aluminum, copper aluminum alloys, copper, nickel, nickel silicide, cobalt, cobalt silicide, ruthenium, platinum, gold, titanium, tantalum, tungsten, silicon, titanium nitride, and tantalum nitride. The substrate may include one or more layers of a material selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

[0090] The method for manufacturing the object to be processed is not particularly limited. For example, the object to be processed may be manufactured by forming an insulating film on a substrate, disposing SiGe and Si on the insulating film by a method such as sputtering, chemical vapor deposition (CVD), or molecular beam epitaxy (MBE), and then carrying out a planarization process such as CMP.

[0091] Examples of applications of the processed object include Dynamic Random Access Memory (DRAM), Ferroelectric Random Access Memory (FRAM (registered trademark)), Magnetoresistive Random Access Memory (MRAM), Phase change Random Access Memory (PRAM), logic circuits, and processors.

[0092] {Method of treating object} The method for processing a workpiece of the present invention (hereinafter also referred to as "the present processing method") has a step A of contacting a workpiece containing Si and SiGe with an etching solution (first embodiment and second embodiment). By carrying out the present processing method, SiGe in the workpiece is selectively etched. The object to be treated used in this treatment method is as described above.

[0093] [Process A] Step A of bringing the etching solution into contact with the workpiece will be described. Examples of the contact method include a method of immersing the workpiece in the etching solution contained in a tank, a method of spraying the etching solution onto the workpiece, a method of flowing the etching solution onto the workpiece, and a combination of these methods. Of these, the method of immersing the workpiece in the etching solution is preferred. Additionally, mechanical agitation methods may be used to further enhance the cleaning ability of the etching solution. Examples of mechanical stirring methods include a method of circulating the etching solution above the workpiece, a method of passing or spraying the etching solution above the workpiece, and a method of stirring the etching solution by ultrasonic or megasonic means.

[0094] The treatment time of step A can be adjusted as appropriate. The treatment time (contact time between the etching solution and the object to be treated) is preferably 0.25 to 10 minutes, and more preferably 0.5 to 2 minutes. The temperature of the etching solution during the treatment is preferably 20 to 100°C, and more preferably 40 to 80°C. The etching process using the etching solution of the present invention has a large etching ratio of SiGe to Si, that is, the process can satisfactorily etch SiGe while suppressing etching of Si in the workpiece. In this process, when the content of Ge element relative to the total amount of Si element and Ge element in SiGe is 30 atomic %, the etching ratio of SiGe to Si is preferably 10 or more, more preferably 30 or more, and further preferably 40 or more. There is no particular upper limit, but it is preferably 1000 or less. Furthermore, the etching rate of SiGe in this process is preferably 100 Å / min or more, more preferably 200 to 500 Å / min, and even more preferably 300 to 500 Å / min, when the content of Ge element relative to the total amount of Si element and Ge element in SiGe is 30 atomic %. The etching rate of Si in this treatment is preferably less than 25 Å / min, and more preferably 0.01 to 15 Å / min.

[0095] (Rinse process) The present processing method may include a rinsing step of performing a rinsing process on the processing object using a rinsing liquid, if necessary. For example, after the workpiece is brought into contact with the etching solution, a rinsing step may be further carried out.

[0096] Examples of the rinse liquid include water, hydrofluoric acid (preferably 0.001 to 1 mass% hydrofluoric acid), hydrochloric acid (preferably 0.001 to 1 mass% hydrochloric acid), hydrogen peroxide solution (preferably 0.5 to 31 mass% hydrogen peroxide solution, more preferably 3 to 15 mass% hydrogen peroxide solution), a mixture of hydrofluoric acid and hydrogen peroxide solution (FPM), a mixture of sulfuric acid and hydrogen peroxide solution (SPM), a mixture of ammonia water and hydrogen peroxide solution (APM), a mixture of hydrochloric acid and hydrogen peroxide solution (HPM), carbon dioxide water (preferably 10 to 60 mass ppm carbon dioxide water), ozone water (preferably 10 to 60 mass ppm ozone water), hydrogen water (preferably 10 to 20 mass ppm hydrogen water), a citric acid solution (preferably a 0.01 to 10 mass% citric acid solution), sulfuric acid (preferably a 1 to 10 mass% sulfuric acid solution), ammonia, Aqueous ammonia (preferably 0.01 to 10% by mass ammonia water), isopropyl alcohol (IPA), an aqueous hypochlorous acid solution (preferably 1 to 10% by mass hypochlorous acid solution), aqua regia (preferably aqua regia corresponding to a volume ratio of "37% by mass hydrochloric acid:60% by mass nitric acid" of "2.6:1.4" to "3.4:0.6"), ultrapure water, nitric acid (preferably 0.001 to 1% by mass nitric acid), perchloric acid (preferably 0.001 to 1% by mass perchloric acid), an aqueous oxalic acid solution (preferably a 0.01 to 10% by mass oxalic acid solution), acetic acid (preferably a 0.01 to 10% by mass acetic acid solution or acetic acid undiluted solution), or an aqueous periodic acid solution (preferably a 0.5 to 10% by mass periodic acid solution. Examples of periodic acid include orthoperiodic acid and metaperiodic acid).

[0097] The composition of the APM is preferably within the range of "ammonia water: hydrogen peroxide water: water = 1:1:1" to "ammonia water: hydrogen peroxide water: water = 1:3:45" (mass ratio), for example. The composition of the FPM is preferably within the range of "hydrofluoric acid:hydrogen peroxide:water=1:1:1" to "hydrofluoric acid:hydrogen peroxide:water=1:1:200" (mass ratio), for example. The composition of the SPM is preferably within the range of "sulfuric acid:hydrogen peroxide:water=3:1:0" to "sulfuric acid:hydrogen peroxide:water=1:1:10" (mass ratio), for example. The composition of HPM is preferably within the range of "hydrochloric acid:hydrogen peroxide:water=1:1:1" to "hydrochloric acid:hydrogen peroxide:water=1:1:30" (mass ratio), for example. Note that these preferred composition ratios are intended to mean composition ratios in which ammonia water is 28 mass% ammonia water, hydrofluoric acid is 49 mass% hydrofluoric acid, sulfuric acid is 98 mass% sulfuric acid, hydrochloric acid is 37 mass% hydrochloric acid, and hydrogen peroxide solution is 30 mass% hydrogen peroxide solution. The volume ratio is based on the volume at room temperature. The description of a preferred range of ["A:B:C=x:y:z" to "A:B:C=X:Y:Z"] indicates that it is preferable to satisfy at least one (preferably two, and more preferably all) of the ranges of ["A:B=x:y" to "A:B=X:Y"], ["B:C=y:z" to "B:C=Y:Z"], and ["A:C=x:z" to "A:C=X:Z"]. Hydrofluoric acid, nitric acid, perchloric acid, and hydrochloric acid are abbreviated as HF, HNO 3 , HClO 4 and HCl dissolved in water. Ozone water, carbon dioxide water, and hydrogen water are respectively 3 , CO 2 , and H 2 In the present invention, an aqueous solution of These rinsing liquids may be mixed and used as long as the purpose of the rinsing step is not impaired. The rinse liquid may also contain an organic solvent.

[0098] A specific example of the rinsing step is a method in which a rinsing liquid is brought into contact with the object to be treated. The contact may be performed by immersing the substrate in the rinse liquid contained in a tank, spraying the rinse liquid onto the substrate, flowing the rinse liquid onto the substrate, or any combination of these methods.

[0099] The treatment time (contact time between the rinse liquid and the object to be treated) is not particularly limited, but is, for example, 5 seconds to 5 minutes. The temperature of the rinse liquid during the treatment is not particularly limited, but is generally preferably 16 to 60° C., more preferably 18 to 40° C. When SPM is used as the rinse liquid, the temperature is preferably 90 to 250° C.

[0100] (drying process) In addition, the present processing method may include a drying step in which a drying process is performed after the rinsing step, if necessary. The drying method is not particularly limited, but examples thereof include spin drying, flow of a dry gas over the substrate, heating the substrate with a heating means such as a hot plate or an infrared lamp, IPA (isopropyl alcohol) vapor drying, Marangoni drying, Rotagoni drying, or a combination thereof. Drying times vary depending on the particular method used, but are typically on the order of 30 seconds to several minutes.

[0101] [Other processes] In addition to the above step A, the present processing method may include other steps. Other processes include, for example, a process for forming one or more structures selected from the group consisting of metal wiring, a gate structure, a source structure, a drain structure, an insulating layer, a ferromagnetic layer, and a non-magnetic layer (e.g., layer formation, etching, chemical mechanical polishing, and modification), a resist formation process, an exposure process and a removal process, a heat treatment process, a cleaning process, a drying process, and an inspection process. This processing method may be performed at any stage of the back end process (BEOL: Back end of the line), middle process (MOL: Middle of the line), or front end process (FEOL: Front end of the line), and is preferably performed in the front end process or middle process. EXAMPLES

[0102] The present invention will be described in further detail below with reference to examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0103] {Preparation of etching solution} For Example 1-1, hydrogen fluoride as a fluoride ion source, acetic acid as a carboxylic acid, hydrogen peroxide, sulfuric acid, naphthalenesulfonic acid formalin condensate ("Takesurf A45-Q" manufactured by Takemoto Oil Co., Ltd.) as an organic compound having a sulfonic acid group, and bromide ions were added to ultrapure water in amounts shown in Table 1 to prepare a mixed liquid, and the mixed liquid was thoroughly stirred with a stirrer to obtain the etching liquid of Example 1. The content of each component in Table 1 is expressed as mass % with respect to the total mass of the etching solution. However, the content of ultrapure water corresponds to the remaining mass (remainder) after subtracting the total mass of the components other than ultrapure water listed in Table 1 from the etching solution. Regarding the content of bromide ions in the etching solution, each component and ultrapure water to be added to the etching solution were filtered to remove bromide ions, and then hydrobromic acid was added to adjust the bromide ion content to that listed in Table 1. Except for changing the type and amount of each component according to Table 1, the etching solutions of Examples 1-2 to 1-18 and Comparative Examples 1-1 and 1-2 were obtained in the same manner as in Example 1-1. Examples 2-1 to 2-8 were obtained in the same manner as Example 1-1, except that the types and amounts of each component were changed according to Table 2 (part 1) and Table 2 (part 2). The concentrations of the metal elements Mn, Ni, V, Co, Fe, and Cr in the etching solution were appropriately adjusted by adding these components to the composition or filtering the composition so as to obtain the values ​​in the tables. In addition, blank spaces in the compound columns in Tables 1 and 2 indicate that the corresponding component was not added. Each of the components shown in Tables 1 and 2 was classified as semiconductor grade or a high purity grade equivalent thereto.

[0104] [component] The components listed in each table are described below. (Fluoride ion source) HF: Hydrogen fluoride (Note that in each example, hydrofluoric acid was used. As shown in the table below, the hydrogen fluoride (HF) content was used within a specified range.)

[0105] (Carboxylic Acid) Acetic acid

[0106] (hydrogen peroxide) ·hydrogen peroxide

[0107] (solvent) ·Ultra pure water ·PG: Propylene glycol

[0108] (Bromate ion) Bromate ion source: Bromate

[0109] (sulfuric acid) S-1: Sulfuric acid

[0110] (Organic compounds having sulfonic acid groups) S-2: Naphthalenesulfonic acid formalin condensate (Takemoto Oil Co., Ltd. "Takesurf A45-Q") S-3: Methanesulfonic acid S-4:C 12 ~C 14 Alkyl diphenyl ether disulfonic acid ("Takesurf A43-NQ" manufactured by Takemoto Oil Co., Ltd.) S-5: Triisopropylnaphthalenesulfonic acid (Takemoto Oil Co., Ltd. "Takesurf A47-Q") S-6: p-Toluenesulfonic acid S-7: Dodecylbenzenesulfonic acid

[0111] (Amine) A-1: N-(3-aminopropyl)diethanolamine A-2: 3-morpholino-1,2-propanediol A-3: Diisopropanolamine

[0112] (Metal impurities) The Mn, Ni, V, Co, Fe, and Cr contents in Table 2 (part 2) were measured using an Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200).

[0113] <Measurement conditions> The sample introduction system used a quartz torch, a coaxial PFA (perfluoroalkoxyalkane) nebulizer (for self-absorption), and a platinum interface cone. The measurement parameters under cool plasma conditions were as follows: RF (Radio Frequency) Output (W): 600 Carrier gas flow rate (L / min): 0.7 Makeup gas flow rate (L / min): 1 Sampling depth (mm): 18 In the measurement of the content of each elemental component, the etching solution itself to be determined was used as the measurement object. When the content of each elemental component present in the etching solution was below the detection limit in the case where the etching solution itself was used as the measurement object, the measurement was performed again in a state where the etching solution to be measured was appropriately concentrated, and the obtained measurement value was converted to the concentration of the etching solution before concentration, and the content of each elemental component was calculated.

[0114] {Testing and Evaluation} The following tests were carried out using the prepared etching solutions of the Examples and Comparative Examples.

[0115] [Evaluation of etching rate] A substrate on which silicon germanium (Si:Ge=70:30 (element ratio); also referred to as SiGe30 later) was laminated to a thickness of 100 nm, and a substrate on which silicon was laminated to a thickness of 100 nm were fabricated, and each of these substrates was cut into a 2 x 2 cm square to prepare test pieces. Hereinafter, each laminated film is also referred to as "SiGe film" and "Si film." The test piece was immersed in the etching solution (25° C.) of the example or comparative example for 10 minutes. Before and after the immersion test, the thicknesses of the SiGe film and the Si film stacked on the substrate were measured using an optical film thickness meter, Ellipsometer M-2000 (manufactured by JA Woollam Co., Ltd.) The etching rate (Å / min) of each film when using each etching solution was calculated from the measured film thicknesses before and after immersion. The results of the etching rate evaluation for the SiGe film and the Si film using each etching solution are shown in Tables 1 and 2.

[0116] [Evaluation of surface smoothness] When etching is performed using an etching solution, it is preferable that the surface smoothness of the SiGe after the etching is high, as this contributes greatly to the processing precision of the device and leads to an improvement in yield. In the film thickness evaluation in the etching ratio evaluation test, the surface roughness (Ra) was measured at the same time as the film thickness using an optical film thickness meter Ellipsometer M-2000 (manufactured by JA Woollam Co., Ltd.). The surface roughness (Ra) obtained when the surface smoothness was evaluated using each etching solution is shown in Tables 1 and 2. It is preferable that Ra is small.

[0117] [Evaluation of storage stability] Next, a storage test was carried out using the etching solutions of each of the Examples and Comparative Examples, and the storage stability of each etching solution was evaluated. Specifically, 200 mL of each etching solution was first filled into a 250 mL high-density polyethylene container and sealed. The container filled with the etching solution was stored in an environment of 25° C. for 7 days (storage test). Except for using the etching solution after the storage test, the etching rate of the SiGe film was evaluated according to the above-mentioned method for evaluating the etching rate of the SiGe film. The maintenance rate of the etching rate of the SiGe film (Å / min) obtained using the etching solution after the storage test was calculated (=[SiGe film etching rate (Å / min) obtained using the etching solution after the storage test] / [SiGe film etching rate (Å / min) obtained using the etching solution immediately after preparation]×100) when the etching rate of the SiGe film (Å / min) obtained using the etching solution before the storage test (etching solution immediately after preparation) was set to 100%. Hereinafter, the maintenance rate is also simply referred to as "maintenance rate". Tables 1 and 2 show the retention rates when storage stability evaluation tests were conducted using each etching solution.

[0118] The "balance" in the "ultrapure water" column in Tables 1 and 2 means that the remaining portion other than the components listed in Tables 1 and 2 (fluoride ion source, carboxylic acid, hydrogen peroxide, percarboxylic acid, bromide ion, bromate ion, sulfuric acid, organic compounds having sulfonic acid groups, amines, and PG) corresponds to "ultrapure water." In Tables 1 and 2, "ppt," "ppm," and "ppb" all mean "ppt by mass," "ppm by mass," and "ppb by mass." In Tables 1 and 2, content ratio A represents the content (mass%) of carboxylic acid relative to the total mass of carboxylic acid, percarboxylic acid, and hydrogen peroxide, content ratio B represents the content (mass%) of hydrogen peroxide relative to the total mass of carboxylic acid, percarboxylic acid, and hydrogen peroxide, and content ratio C represents the content (mass%) of percarboxylic acid relative to the total mass of carboxylic acid, percarboxylic acid, and hydrogen peroxide. For Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-2, the components of the etching solutions and the evaluation results are shown in Table 1 (Part 1) and Table 1 (Part 2). For example, in Example 1-1, the content of the fluoride ion source was 0.2 mass%, the content ratio A was 79.9%, and the SiGe30 (Å / min) was 338. For Examples 2-1 to 2-8, the components of the etching solution and the evaluation results are shown in Table 2 (part 1) and Table 2 (part 2). For example, in Example 2-1, the content of the fluoride ion source was 0.2 mass%, the content of Mn was 0.5 mass ppb, and SiGe30 (Å / min) was 345. In addition, in Tables 1 and 2, "SeGe30 / Si" represents the ratio of the etching rate of SiGe shown in the "SiGe30 (Å / min)" column to the etching rate of Si shown in the "Si (Å / min)" column. Table 2 (part 2) also shows the ratio of carboxylic acid to bromide ion, the ratio of percarboxylic acid to metal impurities, and the ratio of fluoride ion source to metal impurities. In each table, "En" stands for "x10 -n " and the notation "E+n" is "×10 n " n represents an integer. In Table 1, the notation "< X" indicates that the value is less than X. Additionally, the notation "-" indicates that either the evaluation was not performed or the value could not be calculated.

[0119] [Table 1]

[0120] [Table 2]

[0121] [Table 3]

[0122] [Table 4]

[0123] Comparison of Examples 1-1 to 1-18 and 2-1 to 2-8 with Comparative Examples 1-1 and 1-2 confirmed that the etching solution of the present invention has a large etching ratio of SiGe to Si and is excellent in storage stability. From a comparison of Examples 1-12 and 1-14 to 1-16 with other Examples, it was confirmed that when the etching solution contains bromate ions and the content of the bromate ions is 1 to 100 ppm by mass with respect to the total mass of the etching solution, the etching rate of SiGe is high and the storage stability is excellent. From a comparison between Examples 1-11 and other Examples, it was confirmed that the effect of the present invention is more excellent when the etching solution does not contain an alcohol-based solvent. From a comparison of Examples 1-7 to 1-9 with Examples 1-1, 1-3 to 1-5, 1-10, 1-17, and 1-18, it was confirmed that the effect of the present invention was more excellent when the etching solution contained sulfuric acid. From a comparison of Examples 1-7 to 1-9 with Examples 1-2 to 1-6, 1-13, and 1-17, it was confirmed that the effect of the present invention was more excellent when the etching solution contained an organic compound having a sulfonic acid group. From a comparison of Example 2-5 with Examples 2-1 to 2-4, it was confirmed that the effect of the present invention is better when the etching solution further contains metal impurity components including one or more elements selected from the group consisting of Mn, Ni, V, Co, Fe, and Cr, and the content of any element component contained in the metal impurity components is less than 1.0 mass ppb with respect to the total mass of the etching solution. From a comparison of Example 2-6 with Examples 2-1 to 2-4, it was found that the mass ratio of the content of percarboxylic acid to the total content of specific elements contained in the metal impurity components was 2.0 × 10 9 It was confirmed that the effect of the present invention is more excellent in the above cases. From a comparison of Example 2-7 with Examples 2-1 to 2-4, it was found that the mass ratio of the content of the fluoride ion source to the total content of the specific elements contained in the metal impurity components was 2.0 × 10 7 It was confirmed that the effect of the present invention is more excellent in the above cases. From a comparison of Example 2-8 with Examples 2-1 to 2-4, it was found that the mass ratio of the carboxylic acid content to the bromide ion content was 1.0 × 10 10 It was confirmed that the effect of the present invention is more excellent in the above cases.

[0124] Also, as Example 1-19, an etching solution containing hydrofluoric acid (used so that the hydrogen fluoride content was 0.2 mass%), acetic acid (content: 60.5 mass%), hydrogen peroxide (content: 10 mass%), peracetic acid (content: 11.8 mass%), bromide ion (content: 1 ppt by mass), S-1 (content: 1 mass%), and water (balance) was obtained. The above contents represent the content of each component relative to the total mass of the etching solution, with water making up the remainder. When the etching solution prepared in Example 1-19 is evaluated, the etching ratio of SiGe to Si is large and the storage stability is excellent, similar to Examples 1-1 to 1-18. However, in Example 1-19, the surface roughness of the SiGe after treatment is large compared to Example 1-18.

[0125] Also, using the etching solutions prepared in Examples 1-1, 1-7, and 1-10, an [Etching Rate Evaluation] was performed using silicon germanium (Si:Ge=50:50 (element ratio)) instead of the silicon germanium (Si:Ge=70:30 (element ratio)) used in the above [Etching Rate Evaluation], and the etching rates for the SiGe film were obtained. The results using the etching solutions of Examples 1-1, 1-7, and 1-10 were 540 Å / min, 501 Å / min, and 536 Å / min, respectively. In addition, the etching solutions prepared in Examples 1-1 to 1-6, Example 1-10, and Example 1-17 were used to perform an [Etching Rate Evaluation] in which silicon germanium (Si:Ge=85:15 (mass ratio)) was used instead of the silicon germanium (Si:Ge=70:30 (mass ratio)) used in the above [Evaluation of Etching Rate], and the etching rates for the SiGe film were obtained. The results using the etching solutions of Examples 1-1 to 1-6, Example 1-10, and Example 1-17 were 30 Å / min, 40 Å / min, 39 Å / min, 13 Å / min, 42 Å / min, 37 Å / min, 29 Å / min, and 44 Å / min, respectively.

[0126] In addition, the etching solutions prepared in Examples 2-1, 2-5, and 2-6 were used to perform an [Etching Rate Evaluation] in which silicon germanium (Si:Ge=50:50 (mass ratio)) was used instead of the silicon germanium (Si:Ge=70:30 (mass ratio)) used in the above [Etching Rate Evaluation], and the etching rates for the SiGe film were obtained. The results using the etching solutions of Examples 2-1, 2-5, and 2-6 were 512 Å / min, 501 Å / min, and 499 Å / min, respectively. Also, using the etching solutions prepared in Examples 2-1 to 2-4 and Examples 2-6 to 2-7, an [Etching Rate Evaluation] was performed using silicon germanium (Si:Ge=85:15 (mass ratio)) instead of the silicon germanium (Si:Ge=70:30 (mass ratio)) used in the above [Evaluation of Etching Rate], and the etching rates for the SiGe film were obtained. The results using the etching solutions of Examples 2-1 to 2-4 and Examples 2-6 to 2-7 were 41 Å / min, 13 Å / min, 42 Å / min, 37 Å / min, 45 Å / min, and 12 Å / min, respectively.

Claims

1. a source of fluoride ions; Carboxylic acid, Peroxycarboxylic acid, Hydrogen peroxide, bromide ions, The semiconductor etching solution has a bromide ion content of less than 500 ppm by mass based on the total mass of the semiconductor etching solution.

2. a source of fluoride ions; Carboxylic acid, Peroxycarboxylic acid, Hydrogen peroxide, At least one compound selected from the group consisting of N-(3-aminopropyl)diethanolamine, 3-morpholino-1,2 propanediol, and diisopropanolamine; Naphthalenesulfonic acid formalin condensate, methanesulfonic acid, C １２ ~C １４ At least one compound selected from the group consisting of alkyldiphenyletherdisulfonic acid and triisopropylnaphthalenesulfonic acid; bromide ions, The semiconductor etching solution has a bromide ion content of less than 500 ppm by mass based on the total mass of the semiconductor etching solution.

3. 2. The semiconductor etching solution according to claim 1, wherein the bromide ion content is 5 ppt by mass or more based on the total mass of the semiconductor etching solution.

4. The mass ratio of the content of the carboxylic acid to the content of the bromide ion is 1.0×10 １０ The semiconductor etching solution according to claim 1 or 2.

5. a source of fluoride ions; Carboxylic acid, Peroxycarboxylic acid, and hydrogen peroxide. Relative to the total mass of the carboxylic acid, the percarboxylic acid, and the hydrogen peroxide, The content of the carboxylic acid is 55.0 to 94.0% by mass, The content of the percarboxylic acid is 5.0 to 25.0% by mass, The semiconductor etching solution has a hydrogen peroxide content of 1.0 to 20.0 mass %.

6. a source of fluoride ions; Carboxylic acid, Peroxycarboxylic acid, Hydrogen peroxide, At least one compound selected from the group consisting of N-(3-aminopropyl)diethanolamine, 3-morpholino-1,2 propanediol, and diisopropanolamine; Naphthalenesulfonic acid formalin condensate, methanesulfonic acid, C １２ ~C １４ and at least one compound selected from the group consisting of alkyldiphenyletherdisulfonic acid and triisopropylnaphthalenesulfonic acid, Relative to the total mass of the carboxylic acid, the percarboxylic acid, and the hydrogen peroxide, The content of the carboxylic acid is 55.0 to 94.0% by mass, The content of the percarboxylic acid is 5.0 to 25.0% by mass, The semiconductor etching solution has a hydrogen peroxide content of 1.0 to 20.0 mass %.

7. 7. The semiconductor etching solution according to claim 1, wherein the carboxylic acid is acetic acid and the percarboxylic acid is peracetic acid.

8. 7. The semiconductor etching solution according to claim 1, wherein the fluoride ion source is hydrogen fluoride.

9. further comprising bromate ions, 7. The semiconductor etching solution according to claim 1, wherein the content of the bromate ions is 1 to 100 ppm by mass with respect to the total mass of the semiconductor etching solution.

10. The semiconductor etching solution according to any one of claims 1, 2, 5 and 6, which does not contain an alcohol-based solvent.

11. The semiconductor etching solution according to claim 1 , further comprising sulfuric acid.

12. The semiconductor etching solution according to claim 1 , further comprising an organic compound having a sulfonic acid group.

13. The semiconductor etching solution according to claim 12 , wherein the organic compound having a sulfonic acid group is a polymer containing a repeating unit having a sulfonic acid group.

14. The semiconductor etching solution according to claim 1 , further comprising an amine.

15. Further containing a metal impurity component containing one or more elements selected from the group consisting of Mn, Ni, V, Co, Fe, and Cr; 7. The semiconductor etching solution according to claim 1, wherein the content of any of the elements contained in the metal impurity components is less than 1.0 ppb by mass with respect to the total mass of the semiconductor etching solution.

16. The composition further comprises a metal impurity component containing one or more elements selected from the group consisting of Mn, Ni, V, Co, Fe, and Cr; The mass ratio of the content of the percarboxylic acid to the total content of the elements contained in the metal impurity components is 2.0 × 10 ９ The semiconductor etching solution according to any one of claims 1, 2, 5 and 6.

17. The composition further comprises a metal impurity component containing one or more elements selected from the group consisting of Mn, Ni, V, Co, Fe, and Cr; The mass ratio of the content of the fluoride ion source to the total content of the elements contained in the metal impurity component is 2.0 × 10 ７ The semiconductor etching solution according to any one of claims 1, 2, 5 and 6.

18. A method for manufacturing a semiconductor device, using the semiconductor etching solution according to any one of claims 1, 2, 5 and 6.

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