TW201838970A - Cleaning liquid anticorrosion agent and method for manufacturing the same - Google Patents

Abstract

An object of the present invention is to provide a cleaning liquid, an anticorrosive agent, and a method for producing the same, which are excellent in corrosion inhibition performance. The cleaning solution of the present invention is a cleaning liquid of the present invention, which comprises an alkanol hydroxylamine represented by the following general formula (1), an alkanolamine represented by the following general formula (2), a solvent, and Any of a basic compound or an acidic compound other than the aforementioned alkanol hydroxylamine and the aforementioned alkanolamine. In the general formula (1), R ^a1 and R ^a2 each independently represent an alkyl group having 1 to 10 carbon atoms and a hydrogen atom. However, R ^a1 and R ^a2 do not simultaneously become hydrogen atoms. In the general formula (2), R ^b1 and R ^b2 each independently represent an alkyl group having 1 to 10 carbon atoms and a hydrogen atom. However, R ^b1 and R ^b2 are not simultaneously be a hydrogen atom.

Description

Cleaning solution, anticorrosive agent, and method of manufacturing the same

[0001] The present invention relates to a cleaning solution, an anticorrosive agent, and a method of manufacturing the same.

[0002] A semiconductor device is formed by laminating a metal wiring layer, a low dielectric material layer, an insulating layer, or the like on a substrate, and such a semiconductor device performs etching processing by using a resist pattern as a mask. It is produced by processing each of the above layers. [0003] A resist film, a temporary laminated film (also referred to as a sacrificial film) used in the above photolithography method, and a residue derived from a metal wiring layer or a low dielectric material layer which are generated in an etching step, The method of the next step is not hindered, and the cleaning liquid is removed using a method that does not become an obstacle to the semiconductor device. [0004] Conventionally, a cleaning liquid containing a hydroxylamine derivative has been proposed as a cleaning liquid used in the semiconductor device manufacturing step (see, for example, Patent Document 1). The cleaning liquid containing such a hydroxylamine derivative has improved removal performance for various residues as compared with the conventional cleaning liquid. [Prior Art Document] [Patent Document] [0005] [Patent Document 1] International Publication No. 2011/027772

[Problems to be Solved by the Invention] In recent years, with the increase in density and integration of semiconductor devices, for example, a wiring forming method using a damascene method has been employed. In such a wiring forming method, as a metal wiring material constituting a metal wiring layer of a semiconductor device, a corrosive metal is, for example, a form of a single substance or an alloy of cobalt, copper or tungsten, or a germanium compound such as SiGe, as a semiconductor device. Metal wiring materials are used. The other corrosive metals such as cobalt, copper, tungsten, and SiGe used as the metal wiring material have a problem of being easily corroded by the cleaning liquid. Therefore, in the case of cleaning the substrate, a cleaning liquid which is less likely to corrode even other corrosive metals such as cobalt, copper, tungsten, SiGe or the like is being sought. [0007] The present invention has been made in view of such a conventional fact, and provides a cleaning liquid, an anticorrosive agent, and the like, which are excellent in corrosion inhibiting function, at least for other corrosive metals such as cobalt, copper, tungsten, SiGe, and the like. The method of making such is for the purpose. [Means for Solving the Problem] [0008] The present inventors have repeated efforts to solve the above problems. As a result, it has been found that the above problems can be solved by using a mixture of a specific alkanol hydroxylamine and an alkanolamine as the cleaning liquid, and the present invention is completed. Specifically, the present invention provides the following. [0009] The first aspect of the present invention is a cleaning liquid comprising the alkanol hydroxylamine represented by the following general formula (1), an alkanolamine represented by the following general formula (2), a solvent, and the alkane. Any one of a basic compound or an acidic compound other than the hydroxylamine and the alkanolamine, (wherein R ^a1 and R ^a2 each independently represent an alkyl group having 1 to 10 carbon atoms and a hydrogen atom of 1 to 10; respectively, R ^a1 and R ^a2 do not simultaneously become a hydrogen atom) (wherein R ^b1 and R ^b2 each independently represent an alkyl group having 1 to 10 carbon atoms and a hydrogen atom; but R ^b1 and R ^b2 do not simultaneously become a hydrogen atom). [0010] A second aspect of the present invention is an anticorrosive agent comprising the alkanol hydroxylamine represented by the above general formula (1) and the alkanolamine represented by the above general formula (2). [0011] A third aspect of the present invention is a method for producing a cleaning liquid or an anticorrosive agent containing the alkanol hydroxylamine represented by the above general formula (1), characterized in that the method comprises the step of oxidizing the above The alkanolamine represented by the general formula (2) is used to synthesize the alkanol hydroxylamine. [Effects of the Invention] According to the present invention, it is possible to provide a cleaning liquid, an anticorrosive agent, and the like which are excellent in corrosion inhibiting function for at least other corrosive metals such as cobalt, copper, tungsten, SiGe, and the like. method.

<<Cleaning liquid>> The cleaning liquid of the present invention is an alkanol hydroxylamine represented by the above general formula (1) (in the present specification, may be simply referred to as "alkanol hydroxylamine"), and the above general formula (2) an alkanolamine (in the present specification, sometimes simply referred to as "alkanolamine"), a solvent, and a basic compound other than the alkanol hydroxylamine and the alkanolamine (in the present specification, sometimes abbreviated as abbreviations The composition (any of the "basic compound") or the acidic compound is preferably used as a cleaning liquid or an anticorrosive agent. Further, the cleaning liquid of the present embodiment is preferably R in the above general formula (1). ^A1 With R in the above general formula (2) ^B1 For the same base, in the above general formula (1) R ^A2 With R in the above general formula (2) ^B2 For the same base. Further, the cleaning liquid of the present embodiment is preferably R in the above general formula (1). ^A1 With R ^A2 For the same base, in the above general formula (2) R ^B1 With R ^B2 For the same base, better for R ^A1 , R ^A2 , R ^B1 And R ^B2 For the same base. [0015] The cleaning liquid is suitable as a cleaning liquid for electronic parts such as a semiconductor device or a liquid crystal display (LCD). For example, it is suitable as a BEOL (Back End of Line) step of a FEOL (Front End of Line) step or a wiring forming step of a photolithography step, an etching step, a chemical mechanical polishing (CMP), or the like in a semiconductor manufacturing step, or The cleaning liquid used in the subsequent steps such as the through electrode (TSV) or the C4 method (Controlled Collapse Chip Connection) is preferably used for washing with a substrate having a metal on the surface. The substrate having a metal on the surface refers to a substrate in which at least a part of the surface of the substrate exposes metal. The metal is, for example, a metal formed of a metal wiring layer, a plug, and other metal structures forming a substrate of a semiconductor device. The substrate is formed by laminating a metal wiring layer, a low dielectric material layer, an insulating layer, or the like on a substrate such as a germanium wafer, and forming a substrate of a semiconductor device or the like. Further, the substrate may be a substrate including a vaporized layer containing germanium or the like. The cleaning solution of the present embodiment is suitable for cleaning by photolithography and cleaning for photolithography, and can be used as a cleaning solution for lithography. [0016] Examples of the metal include cobalt of a corrosive metal or an alloy thereof. Examples of the alloy of cobalt include an alloy of at least one of other transition elements and typical elements (for example, phosphorus, boron, ruthenium, etc.), and specific examples thereof include phosphorus and/or boron alloys such as CoWPB, CoSi, and the like.矽 矽. Further, the metal may be copper, tungsten, tantalum or an alloy of any of the other corrosive metals, and examples of the alloy include at least one of copper and tungsten, and other transition elements and typical elements ( For example, an alloy containing at least one of phosphorus, boron, ruthenium, and the like is exemplified by a phosphorus or a boron alloy such as CuPB or a telluride such as WSi or SiGe. When the dialkanol hydroxylamine and the dialkanolamine described later are used, not only cobalt can easily obtain a corrosion inhibiting effect even for copper, tungsten or SiGe. Hereinafter, in the present specification, "cobalt or its alloy", "copper or its alloy", and "tungsten or its alloy" may be simply referred to as "cobalt", "copper" and "tungsten", respectively. [0017] The cleaning solution of the present embodiment has an excellent corrosion inhibiting function by containing an alkanol hydroxylamine and an alkanolamine, at least for a chelate compound of cobalt, copper, tungsten, SiGe or the like. Therefore, when the substrate is cleaned, the cleaning solution satisfies the vaporization of cobalt, copper, tungsten, SiGe, etc., even if it is in contact with other corrosive metals such as cobalt, copper, tungsten, or SiGe on the surface of the substrate. Corrosion of other corrosive metals. Although the mechanism of action is not clear, it is presumed that the reduction of other corrosive metals such as cobalt, copper, tungsten, SiGe, etc. by cobalt, copper, tungsten, SiGe, etc. is inhibited by the reduction of the alkanol hydroxylamine and the alkanolamine. Moreover, it is very clear that the mixture of the alkanol hydroxylamine and the alkanolamine has a large anticorrosive effect as compared with the case of the alkanolamine alone. Further, the alkanol hydroxylamine has a lower vapor pressure than the alkanolamine, and even if the cleaning liquid is heated to a specific temperature and washed, the composition change can be suppressed, and it is useful as a cleaning liquid. For example, an alkanol hydroxylamine having a vapor pressure of preferably 0.3 mmHg or less, more preferably 0.1 mmHg, still more preferably 0.05 mmHg or less is suitably used. By using an alkanol hydroxylamine and an alkanolamine having such a property in combination, it is possible to obtain a washing liquid which is more resistant to corrosion than the alkanolamine alone. Further, the alkanol hydroxylamine has a higher water solubility than the alkanolamine, and it is possible to use a low-cost water for the solvent and the solvent, and to prevent the residue from being washed by the aqueous solution, as a washing. Liquid is useful. For example, an alkanol hydroxylamine having a LogP of preferably 0.5 or less is suitably used. By using an alkanol hydroxylamine and an alkanolamine having such a property in combination, it is possible to obtain a washing liquid which is more resistant to corrosion than the alkanolamine alone. [0020] The LogP value means an octanol/water partition coefficient, which can be calculated by calculation using parameters of Ghose, Pritchett, Crippen, etc. (refer to J. Comp. Chem., 9, 80 (1998)). This calculation can be performed using software such as CAChe 6.1 (made by Fujitsu Co., Ltd.). [0021] Hereinafter, each component of the cleaning liquid of the present embodiment will be described in detail. <Alkanol Hydroxylamine> As the alkanol hydroxylamine, the alkanol hydroxylamine represented by the above general formula (1) is used. Where, R ^A1 And R ^A2 Each of the alkyl groups having 1 to 10 carbon atoms having 1 to 3 hydroxyl groups or a hydrogen atom is independently represented. Only, R ^A1 And R ^A2 Will not become a hydrogen atom at the same time. [0023] As the alkanol hydroxylamine, preferably R ^A1 And R ^A2 It is a dialkanol hydroxylamine having an alkyl group having 1 to 3 carbon atoms and having 1 to 10 carbon atoms. The use of such an alkanol hydroxylamine is preferred not only for cobalt but also for the corrosion inhibiting effect of other corrosive metals such as copper, tungsten or SiGe. [0024] at R ^A1 And R ^A2 The number of the hydroxyl groups may be one or two, and the effect of the present invention can be sufficiently exerted even by one. In R ^A1 And R ^A2 Hydroxyl group, in R ^A1 And R ^A2 When the number of carbon atoms of each alkyl group is 3, it may constitute either a first-order alcohol or a second-order alcohol, and further, in R ^A1 And R ^A2 When the number of carbon atoms of each alkyl group is 4 to 10, it may constitute any of the first-stage alcohol, the second-stage alcohol or the third-stage alcohol, but it is preferably a second-stage alcohol. [0025] as in R ^A1 And R ^A2 The alkyl group having 1 to 10 carbon atoms may be a linear, branched or cyclic alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Base, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, cyclopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl, 2-methylpentyl, 1,2- Dimethyl butyl, 2,3-dimethylbutyl, 1-ethylbutyl, cyclohexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, etc., preferably A linear or branched alkyl group having 1 to 4 carbon atoms is particularly preferably an ethyl group, an n-propyl group or an isopropyl group. As in R ^A1 And R ^A2 Specific examples of the linear or branched alkyl group having 1 to 3 carbon atoms and having 1 to 3 hydroxyl groups include, for example, 1-hydroxyethyl group, 2-hydroxyethyl group, and 1,2-dihydroxy group. Ethyl, 2,2-dihydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1,2-dihydroxy-n-propyl , 1,3-dihydroxy-n-propyl, 2,2-dihydroxy-n-propyl, 2,3-dihydroxy-n-propyl, 3,3-dihydroxy-n-propyl, 1 , 2,3-trihydroxy-n-propyl, 2,2,3-trihydroxy-n-propyl, 2,3,3-trihydroxy-n-propyl, 1-hydroxyisopropyl, 2- Hydroxyisopropyl, 1,1-dihydroxyisopropyl, 1,2-dihydroxyisopropyl, 1,3-dihydroxyisopropyl, 1,2,3-trihydroxyisopropyl, 1-hydroxyl -n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl, 1,2-dihydroxy-n-butyl, 1,3-di Hydroxy-n-butyl, 1,4-dihydroxy-n-butyl, 2,2-dihydroxy-n-butyl, 2,3-dihydroxy-n-butyl, 2,4-dihydroxy- N-butyl, 3,3-dihydroxy-n-butyl, 3,4-dihydroxy-n-butyl, 4,4-dihydroxy-n-butyl, 1,2,3-trihydroxy- N-butyl, 1,2,4-trihydroxy-n-butyl, 1,3,4-trihydroxy-n-butyl, 2,2,3-trihydroxy-n-butyl , 2,2,4-trihydroxy-n-butyl, 2,3,3-trihydroxy-n-butyl, 3,3,4-trihydroxy-n-butyl, 2,4,4-tri Hydroxy-n-butyl, 3,4,4-trihydroxy-n-butyl, 2,3,4-trihydroxy-n-butyl, 1-hydroxy-sec-butyl, 2-hydroxy-sec- Butyl, 3-hydroxy-sec-butyl, 4-hydroxy-sec-butyl, 1,1-dihydroxy-sec-butyl, 1,2-dihydroxy-sec-butyl, 1,3-di Hydroxy-sec-butyl, 1,4-dihydroxy-sec-butyl, 2,3-dihydroxy-sec-butyl, 2,4-dihydroxy-sec-butyl, 3,3-dihydroxy- Sec-butyl, 3,4-dihydroxy-sec-butyl, 4,4-dihydroxy-sec-butyl, 1-hydroxy-2-methyl-n-propyl, 2-hydroxy-2-methyl Base-n-propyl, 3-hydroxy-2-methyl-n-propyl, 1,2-dihydroxy-2-methyl-n-propyl, 1,3-dihydroxy-2-methyl- N-propyl, 2,3-dihydroxy-2-methyl-n-propyl, 3,3-dihydroxy-2-methyl-n-propyl, 3-hydroxy-2-hydroxymethyl-n -propyl, 1,2,3-trihydroxy-2-methyl-n-propyl, 1,3,3-trihydroxy-2-methyl-n-propyl, 2,3,3-trihydroxy -2-methyl-n-propyl, 1,3-dihydroxy-2-hydroxymethyl-n-propyl, 2,3-dihydroxy-2-hydroxymethyl-n-propyl, 1-hydroxyl -2-methylisopropyl, 1,3-dihydroxy-2-methyliso Yl, 2-hydroxymethyl-1,3-dihydroxy-isopropyl group, particularly preferably 2-hydroxyethyl, 2-hydroxy -n- propyl, 2-hydroxy isopropyl. The content of the alkanol hydroxylamine relative to the total of the alkanol hydroxylamine and the alkanolamine is preferably 0.01 to 99.9% by mass, more preferably 1 to 90% by mass, still more preferably 10 to 70% by mass. By such a content, it is possible to suppress the corrosion of the corrosive metal, particularly the antimony of cobalt, copper, tungsten, SiGe or the like, and to effectively remove the object to be washed. Further, the content of the alkanol hydroxylamine is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, still more preferably 0.01 to 0.5% by mass, based on the total amount of the cleaning liquid. By such a content, it is possible to suppress the corrosion of the corrosive metal, particularly the antimony of cobalt, copper, tungsten, SiGe or the like, and to effectively remove the object to be washed. <Alkanolamine> As the alkanolamine, the alkanolamine represented by the above general formula (2) is used. In formula (2), R ^B1 And R ^B2 Each of the alkyl groups having 1 to 10 carbon atoms having 1 to 3 hydroxyl groups or a hydrogen atom is independently represented. Only, R ^B1 And R ^B2 Will not become a hydrogen atom at the same time. [0030] As the alkanolamine, preferably R ^B1 And R ^B2 It is a dialkanol hydroxylamine having an alkyl group having 1 to 3 carbon atoms and having 1 to 10 carbon atoms. The use of such an alkanolamine is preferred not only for cobalt but also for the corrosion inhibiting effect of other corrosive metals such as copper, tungsten or SiGe. [0031] as in R ^B1 And R ^B2 The hydroxyl group, which is related to R in the general formula (1) ^A1 And R ^A2 The hydroxyl group is explained by the same, in R ^B1 And R ^B2 When the number of carbon atoms of each alkyl group is 3, and again, in R ^B1 And R ^B2 When the number of carbon atoms of each alkyl group is 4 to 10, it is preferred to constitute a second-stage alcohol. [0032] as in R ^B1 And R ^B2 The alkyl group having 1 to 10 carbon atoms is the same as those described in the general formula (1), and is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, particularly preferably an ethyl group. , n-propyl, isopropyl. [0033] as in R ^B1 And R ^B2 Specific examples of the linear or branched alkyl group having 1 to 3 carbon atoms and having 1 to 4 carbon atoms are the same as those described in the general formula (1), and particularly preferably 2-hydroxyethyl group. , 2-hydroxy-n-propyl. Further, the content of the alkanolamine is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, still more preferably 0.01 to 0.5% by mass, based on the total amount of the cleaning liquid. By such a content, it is possible to remove the object to be washed while suppressing corrosion of other corrosive metals such as cobalt, copper, tungsten, SiGe, or the like. <Solvent> The solvent preferably contains water, and as the water, pure water, deionized water, ion-exchanged water or the like can be used. The solvent, in addition to water, may be a water-soluble organic solvent in order to enhance the solubility of the alkanol hydroxylamine and the alkanolamine. As the water-soluble organic solvent, a compound conventionally used in the art can be used. The water-soluble organic solvent may be used singly or in combination of two or more. The solvent is preferably water and a water-soluble organic solvent. When the solvent and the water-soluble organic solvent are used together, the total content of water with respect to water and the water-soluble organic solvent is preferably from 1 to 99% by mass, more preferably from 10 to 40% by mass, still more preferably from 15 to 30%. quality%. [0036] Examples of the water-soluble organic solvent include an anthracene such as dimethyl hydrazine; dimethyl hydrazine, diethyl hydrazine, bis(2-hydroxyethyl) fluorene, tetramethylene hydrazine or the like. Terpenes; N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamidine Amidoxime such as amine; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, etc. ; lactones such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone; 1,3-dimethyl- Tetrahydroimidazolidones such as 2-tetrahydroimidazolidone, 1,3-diethyl-2-tetrahydroimidazolidone, 1,3-diisopropyl-2-tetrahydroimidazolidone, etc.; ethylene glycol, propylene glycol , 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, glycerol, diethylene glycol and other polyols; ethylene glycol monomethyl ether, ethylene glycol single B Ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoallyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether 3-methoxy-3-methyl-1-butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl Ether, diethylene glycol monobenzyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethyl ether Glycol monoalkyl ethers such as diol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, ethylene glycol dimethyl ether, two Glycol dioxane such as ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether Glycol ether solvent such as ether; ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, etc. Glycol ester solvent. [0037] wherein, selected as a preferred water-soluble organic solvent, selected from the group consisting of dipropylene glycol monomethyl ether (DPM), propylene glycol (PG), 3-methoxy-3-methyl-1-butanol, dimethyl a group consisting of hydrazine, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol monoethyl ether (ethyl diethylene glycol) and diethylene glycol monobutyl ether At least one of the groups. When the water-soluble organic solvent is contained, the content thereof is preferably from 1 to 99% by mass, more preferably from 10 to 85% by mass, still more preferably from 30 to 80% by mass, based on the total amount of the cleaning liquid. By such a content, it is possible to suppress the corrosion of the corrosive metal, particularly the antimony of cobalt, copper, tungsten, SiGe or the like, and to effectively remove the object to be washed. <Basic Compound> The basic compound is not particularly limited as long as it has a washing function other than the alkanol hydroxylamine and the alkanolamine. For example, as the basic compound, at least one selected from the group consisting of a hydroxylamine compound other than the alkanol hydroxylamine represented by the fourth-order ammonium hydroxide and the above-described general formula (1), an alkylamine, and ammonia is preferably used. The basic compounds may be used singly or in combination of two or more. [Level 4 Ammonium Hydroxide] As the basic compound, for example, a fourth-order ammonium hydroxide can be used. The fourth-order ammonium hydroxide is preferably a compound represented by the following general formula (3). [0041] [0042] In the above general formula (3), R ^C1 ~R ^C4 Each independently represents an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or a hydroxyalkyl group having 1 to 16 carbon atoms. [0043] Among the compounds represented by the above general formula (3), selected from tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltri Propyl ammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide, cetyltrimethyl At least one of the group consisting of ammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide is particularly preferable from the viewpoint of easy availability. Further, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferred from the viewpoints of high solubility to the object to be washed and high cleaning performance. [Inorganic Base] Further, as the basic compound, for example, an inorganic base and a fourth-grade ammonium hydroxide can be used in combination. The inorganic base is preferably a hydroxide of an alkali metal such as potassium hydroxide, sodium hydroxide or barium hydroxide, more preferably potassium hydroxide. [Hydroxyamine compound] Further, as the basic compound, for example, a hydroxylamine compound other than the alkanol hydroxylamine represented by the general formula (1) can be used. As the hydroxylamine compound, hydroxylamine (HO-NH) can be cited. ₂ N-methylhydroxylamine, N,N-diethylhydroxylamine, N-ethylhydroxylamine, N,N-dimethylhydroxylamine, N-(tert-butyl)hydroxylamine, N-propylhydroxylamine, and the like. [Alkylamine] Further, as the basic compound, for example, an alkylamine can be used. As the alkylamine compound, N-methylamine, N,N-diethylamine, N-ethylamine, N,N-dimethylamine, N-(tert-butyl)amine, N- Propylamine and the like. [Other Basic Compounds] Further, as the basic compound, ammonia can also be used. The content of the basic compound varies depending on the strength of the basicity of the compound, but is preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass based on the total amount of the cleaning solution. By such a content, it is possible to suppress the corrosion of the corrosive metal, particularly the antimony of cobalt, copper, tungsten, SiGe or the like, and to effectively remove the object to be washed. When the inorganic base is used in combination with the fourth-stage ammonium hydroxide, the content of the inorganic base is preferably 0.1 ppm by mass to 1% by mass, and more preferably 1 ppm by mass to 1000% by mass based on the total amount of the washing liquid. By such a content, it is possible to suppress the corrosion of the corrosive metal, particularly the antimony of cobalt, copper, tungsten, SiGe or the like, and to effectively remove the object to be washed. <Acid Compound> When the cleaning solution is acidic, the acidic compound blended in the cleaning liquid can be appropriately selected from protic acids insofar as it does not inhibit the object of the present invention. Specific examples of suitable acidic compounds include hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, lactic acid, oxalic acid, malonic acid, Protonic acids such as succinic acid, glutaric acid, adipic acid, citric acid, glycolic acid, diglycolic acid, phosphoric acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid and the like. Two or more types of acidic compounds can be used in combination. The blending amount of the acidic compound washing liquid varies depending on the acidity of the compound, but it is usually 0.1 to 20% by mass, more preferably 0.5, based on the total amount of the cleaning liquid. ～15% by mass. More preferably, it is 1.0 to 10% by mass. By such a content, it is possible to suppress the corrosion of the corrosive metal, particularly the antimony of cobalt, copper, tungsten, SiGe or the like, and to effectively remove the object to be washed. <Other components> In the cleaning liquid of the present embodiment, other components such as a surfactant may be added in a range that does not impair the effects of the present invention. The surfactant is not particularly limited, and examples thereof include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. Further, in the case where the cleaning liquid of the present embodiment contains the alkanol hydroxylamine represented by the above general formula (1) and the alkanolamine represented by the general formula (2), it is not necessary to contain other anticorrosive agent, but Can also be used to contain other anti-corrosion agents. The other anticorrosive agent is not particularly limited, but is, for example, benzotriazole, aminotetrazole, 5-amino-1-phenyltetrazole, 5-amino-1-(1-naphthyl). Nitrogen containing tetrazole, 1-methyl-5-aminotetrazole, 1,5-diaminotetrazole, imidazole, indole, indole, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, etc. Examples of the heterocyclic compound include a secondary amine compound and an amino acid compound. <<Anticorrosive agent>> The anticorrosive agent of the present invention is a composition containing the alkanol hydroxylamine represented by the above general formula (1) and the alkanolamine represented by the above general formula (2), which is typically The liquid composition) is suitable as an anticorrosive agent. Further, the anticorrosive agent of the present embodiment is preferably R in the above general formula (1). ^A1 With R in the above general formula (2) ^B1 For the same base, in the above general formula (1) R ^A2 With R in the above general formula (2) ^B2 For the same base. Further, the anticorrosive agent of the present embodiment is preferably R in the above general formula (1) ^A1 With R ^A2 For the same base, in the above general formula (2) R ^B1 With R ^B2 For the same base, better for R ^A1 , R ^A2 , R ^B1 And R ^B2 For the same base. [0055] The anticorrosive agent of the present embodiment can effectively inhibit the metal, especially cobalt, copper, tungsten, SiGe, etc., from other corrosive properties by using a mixture of an alkanol hydroxylamine and an alkanolamine as described above. Corrosion of metal. <<Method for Producing Cleaning Liquid or Corrosion Preventing Agent>> A method for producing the cleaning liquid or the corrosion preventing agent of the present invention is a method for producing a washing containing the alkanol hydroxylamine represented by the above general formula (1) A method of purifying liquid or an anticorrosive agent comprising synthesizing the alkanol hydroxylamine by oxidizing the alkanolamine represented by the above general formula (2). The method for producing the cleaning liquid or the anticorrosive agent of the present invention is suitable as a method for producing the cleaning liquid of the first aspect of the present invention or the corrosion preventing agent of the second aspect of the present invention. [0057] Examples of the oxidizing agent for the oxidized alkanolamine include hydrogen peroxide and the like. The amount of the oxidizing agent added to the alkanolamine is preferably from 30 to 100 mol%, more preferably from 60 to 80 mol%, based on the molar amount of the alkanolamine. By forming such a content, an alkanol hydroxylamine is formed from an alkanolamine, and a mixed liquid having a high anticorrosive effect can be obtained. The reaction temperature of the oxidized alkanolamine is, for example, preferably 40 to 80 ° C, more preferably 50 to 70 ° C. Further, the reaction time is preferably from 20 to 120 minutes, more preferably from 30 to 90 minutes. By carrying out an oxidation reaction under such conditions, an alkanol hydroxylamine is formed from an alkanolamine, and a mixed liquid having a high anticorrosive effect can be obtained. According to this method, a mixture of an alkanolamine of a starting material and an alkanol hydroxylamine of a reaction product is easily obtained, and the mixture obtained after the oxidation reaction is not directly used, that is, the isolated alkanolamine or alkanol is isolated. As the hydroxylamine, a cleaning liquid or an anticorrosive agent of the present embodiment can be used, and the production efficiency is good. Further, as compared with the case where the alkanolamine or the alkanol hydroxylamine is used alone in the cleaning liquid or the anticorrosive agent, a cleaning liquid or an anticorrosive agent having a high anticorrosive effect can be obtained. [0061] For example, as shown in the following reaction formula, hydrogen peroxide water (H) is added by the diethanolamine of the alkanolamine ₂ O ₂ The oxidation reaction is carried out to obtain a reaction product represented by the following structural formula (alkanol hydroxylamine, 2,2'-(hydroxyimino)bisethanol). However, in the following reaction, it is difficult to oxidize the entire amount of diethanolamine, and the obtained reaction liquid becomes a mixture of diethanolamine and 2,2'-(hydroxyimino)diethanol. The yield of the alkanol hydroxylamine, ie, 2,2'-(hydroxyimino)bisethanol, varies depending on the reaction conditions, but is about 25% to 70%. [0062] <<Washing Method>> The washing method using the washing liquid of the present invention is also one of the inventions. The cleaning method of the present invention is a method of washing a substrate by using the above-mentioned cleaning solution, an anticorrosive agent, or a cleaning liquid or an anticorrosive agent produced by the above method to wash the substrate. [0064] The cleaning of the substrate is suitable for cleaning as a substrate for photolithography. For example, the cleaning method of the present embodiment is an etching mask layer forming step of forming an etching mask layer of a specific pattern on the surface of the substrate, and etching is performed after the etching step of etching the substrate exposed from the etching mask layer. A method of cleaning the etched substrate. The cleaning method of the present embodiment is suitable for a case where at least a part of the surface of the substrate is made of a non-corrosive metal such as cobalt, copper, tungsten or SiGe. At this time, at least a part of the other corrosive metal such as cobalt, copper, tungsten, or SiGe is exposed on the surface of the substrate, and is in contact with the cleaning liquid, but other compounds such as cobalt, copper, tungsten, and SiGe are formed. Corrosion of corrosive metals is well suppressed. Therefore, by washing with the above-described cleaning liquid, it is possible to effectively remove the object to be washed while suppressing corrosion of other corrosive metals such as cobalt, copper, tungsten, SiGe, or the like. As will be described later, the cleaning method of the present embodiment is as small as 0.2 nm/min or less, preferably 0.1 nm/min or less, more preferably 0.09 nm/min or less, based on the evaluation of the etching rate. The corrosion inhibition effect is large. Further, similarly, the corrosion rate can be expected to be as small as 0.4 nm/min or less, preferably 0.2 nm/min or less, more preferably 0.04 nm/min or less, depending on the evaluation of the etching rate. Further, similarly, the corrosion rate can be expected to be as small as 0.2 nm/min or less, preferably 0.1 nm/min or less, more preferably 0.01 nm/min or less, depending on the evaluation of the etching rate. Further, similarly, the evaluation of the etching rate can be as small as 0.05 nm/min or less, preferably 0.01 nm/min or less with respect to SiGe, and a corrosion suppression effect can be expected. When the above-described dialkanol hydroxylamine and dialkanolamine are used, not only cobalt but also other corrosive metals such as copper, tungsten, SiGe or the like are easily corroded. [0066] The specific washing method is not particularly limited as long as it is a usual method. For example, a dipping method, a paddle method, a shower method, or the like is used, and the substrate is treated by contacting the substrate with the above-mentioned cleaning solution for 1 to 40 minutes. Although washing is usually carried out at room temperature, in order to improve the washing effect, the washing liquid may be heated to about 85 ° C. <<Anti-corrosion method>> Thus, the method for preventing corrosion of corrosive metals by using the above-mentioned cleaning liquid, anticorrosive agent or the cleaning liquid or anticorrosive agent produced by the above method is also one of the inventions . The anti-corrosion method includes, for example, contacting a chelate compound of cobalt, copper, tungsten, SiGe or the like with another corrosive metal (for example, a substrate having a surface exposed to the corrosive metal) with the cleaning liquid or the anticorrosive agent, specifically This can be carried out in the same manner as the above-described washing method. [0068] Moreover, the method for preventing corrosion of the corrosive metal by using the above-mentioned anticorrosive agent or the anticorrosive agent produced by the above method comprises adding the anticorrosive agent to the cleaning solution, the developer, and the eluent by using the anticorrosive agent a lithographic chemical solution or the like, such as a stripping solution, is contained in a lithographic chemical solution, for example, a chelate compound such as cobalt, copper, tungsten or SiGe, or other corrosive metal (for example, a substrate having a surface exposed to the corrosive metal) The lithography is contacted with a chemical solution. In the anticorrosion method, for example, a cleaning method generally used in photolithography can be used in accordance with the type and use of the lithographic chemical solution including the cleaning solution, the developing solution, the eluent, and the stripping liquid of the anticorrosive agent. For example, the above washing method), a developing method, a rinsing method, and a peeling method. The photographic liquid for lithography containing the anticorrosive agent of the present embodiment is preferably a cleaning solution or a developer. As the developer, for example, an alkali developer such as a tetramethylammonium hydroxide (TMAH) 2.38% aqueous solution can be used. [0069] The lithographic solution containing the anticorrosive agent of the present invention is also one of the inventions. The chemical solution for lithography includes, for example, a cleaning liquid, a developing solution, an eluent, a peeling liquid, and the like, and is preferably a cleaning liquid. <<Method of Manufacturing Semiconductor>> A method of manufacturing a semiconductor using the cleaning method of the present invention is also one of the inventions. The method of producing the semiconductor of the present invention includes a method of manufacturing a semiconductor including a substrate by washing the substrate using the above-described cleaning method. [0071] According to the method of the present embodiment, as described above, at least a part of the surface of the substrate is made of other corrosive metals such as cobalt, copper, tungsten, SiGe, or the like, and cobalt, copper, and the like are also inhibited. The etching of tungsten, SiGe, etc., other corrosive metals to produce semiconductors. <<Photolithography Method>> A photolithography method including the cleaning method of the present invention or the anticorrosion method of the present invention is also one of the inventions. As the anti-corrosion method of the present invention, the cleaning solution, the anticorrosive agent or the cleaning liquid or the anticorrosive agent produced by the above method may be used as a method for preventing corrosion of the corrosive metal, or the anticorrosive agent may be included. The lithographic chemical solution contained in the cleaning solution, the developing solution, the eluent, and the stripping liquid, and the above-mentioned prevention of the corrosive metal (for example, a substrate on which the corrosive metal is exposed) is brought into contact with the lithography liquid. Corrosion method. [Examples] Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited to the examples. [Comparative Example] As a comparative example, a solution composed of 75.0% by mass of ethyl diglycol, 2.0% by mass of tetramethylammonium hydroxide TMAH, and 23.0% by mass of water (remaining portion) was prepared. [Examples 1 to 4] In the examples, in the amounts shown in Table 1, alkanolamine (monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine) dissolved in water, respectively. Hydrogen peroxide water (H ₂ O ₂ It took 60 minutes to drip at 60 ° C with stirring. Furthermore, after further reacting at 60 ° C for 1 hour, the obtained reaction liquid was added in an amount of 0.5 parts by mass based on 99.5 parts by mass of the solution of the comparative example to prepare a washing liquid. [0076] For example, the composition of the cleaning solution of Example 1 is 75.0 parts by mass of ethyl diethylene glycol, 2.0 parts by mass of tetramethylammonium hydroxide (TMAH), 0.5 parts by mass of the above reaction liquid, and water (remaining portion). 22.5 parts by mass. The reaction liquid obtained by adding hydrogen peroxide water to the alkanolamine in Examples 1 to 4 is a mixture of the alkanolamine of the starting material and the alkanol hydroxylamine which is a product of the oxidation reaction, as shown in Table 3. The matter was confirmed by liquid chromatography mass spectrometry (LC-MS). [0078] An example of the analysis result is shown. The reaction liquid obtained in Example 4 was evaluated by liquid chromatography mass spectrometry (LC-MS), and a peak was observed at a position where the m/z value became 134.1172 and 150.1122. As a result, it was found that the reaction liquid obtained in Example 4 was a mixture of diisopropanolamine as a starting material and diisopropanol hydroxylamine in which a hydroxyl group was bonded to a nitrogen atom as a product of an oxidation reaction. Further, the reaction liquid of the reaction liquid of Example 4 was evaluated by a nuclear magnetic resonance apparatus (NMR) to confirm the molar ratio of the starting material: reaction product = 59:41, and the yield of diisopropanol hydroxylamine was 32.2%. [Example 5] As a cleaning liquid, 1.0 mass% was added to 100% by mass of an aqueous solution (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) of 2.38% of tetramethylammonium hydroxide (TMAH). The reaction liquid obtained in Example 4 was used to prepare a washing liquid. [Example 6] As a cleaning liquid, 100 parts of an aqueous solution (trade name: NMD-W, manufactured by Tokyo Ohka Kogyo Co., Ltd.) containing 2.38% of tetramethylammonium hydroxide (TMAH) and a surfactant %, 1.0% by mass of the reaction liquid obtained in Example 4 was added to prepare a washing liquid. [Example 7] As a cleaning liquid, it was 65 mass% of dipropylene glycol monomethyl ether (DPM), propylene glycol (PG) 5 mass%, tetramethyl ammonium hydroxide (TMAH) 2.0 mass%, and water. (Remaining part) A mixed solution of 28% by mass was added to 1.0% by mass of the reaction liquid obtained in Example 4 to prepare a washing liquid. [Comparative Examples 1 to 6] In Comparative Examples 1 to 6, as shown in Table 2, as a comparative control compound for an anticorrosive agent, monoethanolamine, diethanolamine, diethylamine, monoisopropanolamine, and the like were mixed. 0.5 parts by mass of a mixture of diisopropanolamine, dipropylamine and water was added to 99.5 parts by mass of a solution of the comparative example to prepare a washing liquid. [Comparative Example 7] In Comparative Example 7, as a comparative control compound as an anticorrosive agent in an amount shown in Table 1, hydrogen peroxide water (H) was dissolved with respect to dipropylamine dissolved in water. ₂ O ₂ It took 60 minutes to drip at 60 ° C with stirring. Furthermore, after further reacting at 60 ° C for 1 hour, the obtained reaction liquid was added in an amount of 0.5 parts by mass based on 99.5 parts by mass of the solution of the comparative example to prepare a washing liquid. The reaction liquid obtained in Comparative Example 7 is a mixture of dipropylamine and dipropylhydroxylamine as shown in Table 4. [Comparative Example 8] A cleaning liquid was prepared in the same manner as in Example 5 except that the reaction liquid obtained in Example 4 was not added. [Comparative Example 9] A cleaning liquid was prepared in the same manner as in Example 6 except that the reaction liquid obtained in Example 4 was not added. [Comparative Example 10] A cleaning liquid was prepared in the same manner as in Example 7 except that the reaction liquid obtained in Example 4 was not added. [0087] [0088] [Evaluation of Etching Rate with Copper Layer, Tungsten Layer or Cobalt Layer] Copper, tungsten or cobalt was formed on a tantalum substrate to obtain a tantalum substrate having a copper layer, a tungsten layer or a cobalt layer having a thickness of 100 nm. This ruthenium substrate was immersed in a washing liquid heated to 60 ° C for 60 minutes. After the completion of the immersion, the ruthenium substrate was rinsed with pure water, and the thickness of the copper layer, the tungsten layer or the cobalt layer was measured, and the etching rate of the copper layer, the tungsten layer or the cobalt layer was determined from the difference in film thickness before and after immersion. The results are shown in Tables 3 and 4. [0090] The evaluation of the etching rates in Tables 3 and 4 is based on the following criteria. Further, the etching rate obtained by the solution of the comparative example was 2.21 for the copper layer, 0.14 for the tungsten layer, and 0.35 for the cobalt layer. The unit of evaluation of the etching rate is [nm/min]. ‧ copper (Cu) ◎: 0.2 or less, 〇: more than 0.2 and 0.4 or less, ×: more than 0.4 ‧ tungsten (W) ◎: 0.1 or less, 〇: more than 0.1 and 0.2 or less, ×: more than 0.2 ‧ cobalt (Co ◎: 0.1 or less, 〇: more than 0.1 and 0.2 or less, ×: more than 0.2 [0091] [0092] From the results of Tables 3 and 4, the cleaning solutions of Examples 1 to 4 containing a mixed solution of an alkanol hydroxylamine and an alkanolamine, and the cleaning solutions of Comparative Examples 1 to 7 which did not contain an alkanol hydroxylamine. In contrast, cobalt has a small etching rate and excellent corrosion inhibition performance. Among them, in the cleaning liquids of Examples 2 and 4 containing a mixed liquid of a dialkylol hydroxylamine and a dialkanolamine, the etching rate of copper or tungsten was also smaller than that of the cleaning liquids of Comparative Examples 1 to 7, and corrosion was performed. The suppression function is also excellent. Further, the alkanol hydroxylamine obtained in the examples was found to have a larger LogP value and superior water solubility than the amine used in the comparative example, and the vapor pressure was low, and the composition stability was excellent. [Evaluation of Etching Rate of SiGe Layer] A ruthenium substrate having a SiGe layer having a thickness of 100 nm was immersed in the cleaning liquids (25 ° C) of Examples 5 to 7 and Comparative Examples 8 to 10 for 10 minutes. After the completion of the immersion, the ruthenium substrate was rinsed with pure water, the film thickness of the SiGe layer was measured, and the etching rate of the SiGe layer was determined from the difference in film thickness before and after immersion. The results are shown in Table 5. [0095] The evaluation of the etching rate in Table 5 is based on the following criteria. The unit of evaluation of the etching rate is [nm/min]. ‧SiGe ◎: 0.01 or less, 〇: more than 0.01 and 0.05 or less, ×: more than 0.05 [0096] From the results of Table 5, the cleaning liquids of Examples 5 to 7 used in the reaction liquid obtained in Example 4 containing a mixed liquid of an alkanol hydroxylamine and an alkanolamine, and the alkanol hydroxylamine (1) were not contained. In comparison with the cleaning liquids of Comparative Examples 8 to 10 of 1' (hydroxyimino) bis(2-propanol), it was confirmed that the etching rate was small even for the SiGe layer, and the corrosion inhibiting function was excellent.

Claims (9)

A cleaning solution containing an alkanol hydroxylamine represented by the following general formula (1), an alkanolamine represented by the following general formula (2), a solvent, and an alkalinity other than the above alkanol hydroxylamine and the aforementioned alkanolamine Any of a compound or an acidic compound, (wherein R ^a1 and R ^a2 each independently represent an alkyl group having 1 to 10 carbon atoms and a hydrogen atom of 1 to 10; respectively, R ^a1 and R ^a2 do not simultaneously become a hydrogen atom) (wherein R ^b1 and R ^b2 each independently represent an alkyl group having 1 to 10 carbon atoms and a hydrogen atom; but R ^b1 and R ^b2 do not simultaneously become a hydrogen atom). The cleaning solution according to claim 1, wherein R ^a1 in the above general formula (1) is the same as R ^b1 in the above general formula (2), and R ^a2 in the above general formula (1) is in the foregoing general R ^b2 of the formula (2) is the same group. The cleaning solution according to claim 1, wherein R ^a1 and R ^a2 in the above general formula (1) are the same group, and R ^b1 and R ^b2 in the above general formula (2) are the same group. An application for cleaning a lithographic cleaning solution according to any one of claims 1 to 3. An anticorrosive agent comprising an alkanol hydroxylamine represented by the following general formula (1) and an alkanolamine represented by the following general formula (2), (wherein R ^a1 and R ^a2 each independently represent an alkyl group having 1 to 10 carbon atoms and a hydrogen atom of 1 to 10; respectively, R ^a1 and R ^a2 do not simultaneously become a hydrogen atom) (wherein R ^b1 and R ^b2 each independently represent an alkyl group having 1 to 10 carbon atoms and a hydrogen atom; but R ^b1 and R ^b2 do not simultaneously become a hydrogen atom). A method for producing a cleaning liquid or an anticorrosive agent containing an alkanol hydroxylamine represented by the following general formula (1), characterized in that the method comprises an alkanol represented by the general formula (2): An amine to synthesize the aforementioned alkanol hydroxylamine, (wherein R ^a1 and R ^a2 each independently represent an alkyl group having 1 to 10 carbon atoms and a hydrogen atom of 1 to 10; respectively, R ^a1 and R ^a2 do not simultaneously become a hydrogen atom) (wherein R ^b1 and R ^b2 each independently represent an alkyl group having 1 to 10 carbon atoms and a hydrogen atom; but R ^b1 and R ^b2 do not simultaneously become a hydrogen atom). A cleaning solution according to any one of claims 1 to 3, an anticorrosive agent according to claim 5, or a cleaning solution or an anticorrosive agent produced by the method according to claim 6, To clean the substrate. A method of manufacturing a semiconductor comprising the substrate, comprising washing the substrate using the method of claim 7. A method of preventing corrosion of a corrosive metal, characterized by comprising the corrosive metal described above and the cleaning solution according to claim 1, the anticorrosive agent as recited in claim 5, or by claim 6 The cleaning solution or the anticorrosive agent produced by the method described is contacted.