Cleaning methods for components and substrates of semiconductor devices

Abstract

This invention provides a composition for semiconductor devices with excellent residue removal properties. Furthermore, this invention provides a method for cleaning a substrate using the above-described composition. The composition is for semiconductor devices and contains an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, and water.

Description

Technical field

[0001] The present invention relates to a method for cleaning a composition and a substrate.

Prior technology

[0002] Use photolithography technology to form fine electronic circuit patterns on the substrate to manufacture semiconductor components such as CCD (Charge-Coupled Device, charge-coupled device) and memory. For example, a semiconductor element is formed by arranging a laminate of a metal layer as a wiring material and an etching stopper film and an interlayer insulating film on a substrate, forming a photoresist film on the laminate, and performing photolithography and drying. conventional etching steps (for example, plasma etching process) to manufacture. Specifically, in the photolithography step, the obtained photoresist film is used as a mask, and the metal layer and / or the interlayer insulating film on the substrate are etched by dry etching. At this time, residues from the metal layer and / or the interlayer insulating film may adhere to the substrate, the metal layer, and / or the interlayer insulating film. In order to remove the attached residue, cleaning using a treatment liquid is usually performed in many cases. Moreover, the photoresist film used as a mask at the time of etching is removed from the laminated body by a dry method (dry ashing) by ashing (ashing), a wet method, or the like thereafter. Residues from the photoresist film etc. may adhere to the laminate where the resist is removed by dry ashing. In order to remove the attached residue, cleaning using a treatment liquid is usually performed in many cases. On the other hand, as a wet method for removing a photoresist film, an aspect in which a photoresist film is removed using a processing liquid is mentioned. As described above, the treatment liquid is used to remove residues (etching residues and ashing residues) and / or photoresist films and the like in the semiconductor element manufacturing steps.

[0003] For example, Patent Document 1 discloses a stripping liquid composition containing a combination of alkanolamines, aromatic alcohols, and preservatives.

[0004] [Patent Document 1] International Publication No. 2009 / 051237

[0005] As a result of investigations on the composition described in Patent Document 1, the present inventors have clarified that the above composition has further improved residue removal properties (especially, residue removal properties after dry etching). space.

Content of invention

[0006] Accordingly, an object of the present invention is to provide a composition for semiconductor elements that is excellent in residue removal properties (in particular, residue removal properties after dry etching). Moreover, the subject of this invention is providing the cleaning method of the board|substrate using the said composition.

[0007] In order to solve the above-mentioned problems, the inventors of the present invention conducted painstaking studies and found that the above-mentioned problems can be solved by the following configuration.

[0008] [1] A composition for a semiconductor element, comprising an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, and water. [2] The composition as described in [1], wherein the pH is 9-11. [3] The composition as described in [1] or [2], wherein the alcohol includes a monoalcohol. [4] The composition as described in [1] or [2], wherein the alcohol includes a monoalcohol having a main chain skeleton containing an aliphatic hydrocarbon group and an alcoholic hydroxyl group, or a monoalcohol having a main chain skeleton containing an aliphatic hydrocarbon group and an alcoholic hydroxyl group. Hydroxyl polyols. [5] The composition according to any one of [1] to [4], wherein the aprotic polar solvent contains at least one selected from the group consisting of dimethylsulfoxide and cyclobutane . [6] The composition according to any one of [1] to [5], wherein the aprotic polar solvent contains cyclobutane. [7] The composition according to any one of [1] to [6], further comprising component A selected from the group consisting of cyclobutene and dipropylene. [8] The composition according to [7], wherein the content of the component A is 100 ppt by mass or more and 100 ppm by mass or less relative to the total mass of the composition. [9] The composition according to [7] or [8], wherein the mass ratio of the content of the azole compound to the content of the component A is 1.0×103 to 1.0×1010.

[10] The composition according to any one of [7] to [9], wherein the mass ratio of the content of the aprotic polar solvent to the content of the component A is 1.0×104 to 1.0×1010.

[11] The composition as described in any one of [1] to

[10] , wherein the alcohol is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol At least one selected from the group of alcohol, tertiary butanol, 1-pentanol, 3-pentanol and cyclopentanol.

[12] The composition according to any one of [1] to

[11] , wherein the content of the alcohol is 50 to 80% by mass relative to the total mass of the composition.

[13] The composition according to any one of [1] to

[12] , wherein the content of the aprotic polar solvent is 1 to 20% by mass relative to the total mass of the composition.

[14] The composition as described in any one of [1] to

[13] , wherein the azole compound is selected from the group consisting of 1,2,4-triazole, 1,2,3-triazole, 1H-tetra Azole, 5-aminotetrazole, 1H-benzotriazole, tolyltriazole, 5-methyltriazole, carboxybenzotriazole and 2,2'-[{(methyl-1H-benzotriazole At least one of the group of azol-1-yl)methyl}imino]bisethanol.

[15] The composition according to any one of [1] to

[14] , wherein the content of the azole compound is 0.1 to 5% by mass relative to the total mass of the composition.

[16] The composition according to any one of [1] to

[15] , wherein the content of the water is 10 to 40% by mass relative to the total mass of the composition.

[17] The composition according to any one of [1] to

[16] , wherein the alkanolamine is selected from the group consisting of diethanolamine, 2-(2-aminoethylamino)ethanol, 2-( 2-aminoethoxy)ethanol, triethanolamine, 2-aminoethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine and at least one of the group consisting of N-methylethanolamine.

[18] The composition according to any one of [1] to

[17] , wherein the content of the alkanolamine is 0.3 to 10% by mass relative to the total mass of the composition.

[19] The composition according to any one of [1] to

[18] , which further contains a chelating agent.

[20] The composition according to

[19] , wherein the chelating agent has two or more ligands selected from the group consisting of carboxyl groups, phosphonic acid groups, phosphoric acid groups, and amine groups.

[21] The composition according to

[19] or

[20] , wherein the chelating agent contains at least one selected from the group consisting of amino polycarboxylic acids and polycarboxylic acids.

[22] A method for cleaning a substrate, comprising a cleaning step of cleaning a substrate having a metal layer using the composition described in any one of [1] to

[21] . [Invention effect]

[0009] According to the present invention, it is possible to provide a composition for semiconductor elements excellent in residue removal properties (especially, residue removal properties after dry etching). Also, according to the present invention, a method of cleaning a substrate using the above composition can be provided.

Implementation

[0011] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. In this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. When referred to as "preparation" in this specification, in addition to synthesis and preparation of specific materials and the like, those obtained by purchasing and the like are also included. In this specification, when a certain component exists 2 or more types, the "content" of the said component means the total content of these 2 or more types of components.

[0012] In this specification, "ppm" refers to "parts-per-million: one millionth (10-6)", "ppb" refers to "parts-per-billion: one billionth ( 10-9)", "ppt" refers to "parts-per-trillion: one trillionth (10-12)". In this specification, 1Å (Angstrom) is equivalent to 0.1nm. Among the notations of groups (atomic groups) in this specification, notation of substituted and unsubstituted notation includes notions of not having a substituent together with not having a substituent within the range not impairing the effect of the present invention. For example, "hydrocarbon group" includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group), but also a hydrocarbon group having a substituent (substituted hydrocarbon group). Here, the meaning of each compound is also the same. In this specification, "light" refers to actinic rays or radiation. In addition, in this specification, "radiation" means, for example, extreme ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, or electron beams represented by the bright line spectrum of a mercury lamp, and an excimer laser. In this specification, "exposure" includes not only the bright line spectrum of a mercury lamp, exposure based on far ultraviolet rays, X-rays, or EUV light represented by excimer lasers, but also exposure based on particle beams such as electron beams or ion beams, unless otherwise specified. Delineation is also included in the exposure. [Composition] The composition of the present invention (hereinafter also referred to as "this composition") is a composition containing at least alcohol, aprotic polar solvent, azole compound, alkanolamine and water. The inventors of the present invention found that when the composition contains a combination of the above-mentioned components, the residue removal property (especially, the residue removal property after dry etching) is excellent (hereinafter also referred to as "the effect of the present invention is excellent"), and completed The present invention.

[0014] Hereinafter, each component contained in this composition will be described.

[0015] [Alcohol] The alcohol contained in this composition is a compound having at least one alcoholic hydroxyl group. In addition, in this specification, the alkanolamine and azole compound mentioned later are not included in alcohol.

[0016] Examples of alcohols include compounds having a main chain skeleton including a chain or cyclic aliphatic hydrocarbon group and at least one alcoholic hydroxyl group. In addition, in the above-mentioned main chain skeleton, at least one methanediyl group (-CH2-) constituting the chain or cyclic aliphatic hydrocarbon group may be substituted with a heteroatom. As a hetero atom, -O- and -S- are mentioned, for example. Also, alcoholic hydroxyl groups are bonded to the main chain skeleton.

[0017] The alcohol may be a monoalcohol having one alcoholic hydroxyl group or a polyol having two or more alcoholic hydroxyl groups. The alcohol is preferably a monoalcohol or a polyol having two or three alcoholic hydroxyl groups, more preferably a monoalcohol or a polyol having two alcoholic hydroxyl groups, and even more preferably a monoalcohol.

[0018] In terms of the more excellent effects of the present invention, the alcohol has a main chain skeleton that does not contain heteroatoms such as ether groups (-O-) and contains an aliphatic hydrocarbon group and an alcoholic hydroxyl group bonded to the main chain skeleton. Compounds (monoalcohols or polyalcohols) are preferred. Moreover, since the corrosion resistance to the metal layer containing Co (Co corrosion resistance) is more excellent, as a main chain skeleton of an alcohol, the chain main chain skeleton which does not have a ring structure is preferable. That is, as an alcohol, a compound having a main chain skeleton and an alcoholic hydroxyl group bonded to the main chain skeleton, and the main chain skeleton is preferably a main chain skeleton containing an aliphatic hydrocarbon group and / or a chain main chain skeleton. Among them, A compound having a main chain skeleton containing a chain aliphatic hydrocarbon group and an alcoholic hydroxyl group that does not contain a heteroatom is more preferable. The carbon number of the aliphatic hydrocarbon group constituting the main chain skeleton is not particularly limited, but 1-8 is preferable, and 2-6 is more preferable.

[0019] Examples of monoalcohols having a main chain skeleton containing a chain aliphatic hydrocarbon group include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 1-butanol, 2-butanol alcohol, isobutanol, tertiary butyl alcohol, 2-pentanol, tertiary pentanol, 1-hexanol, allyl alcohol, propargyl alcohol, 2-butenol, 3-butenol and 4-pentenol En-2-ol. Examples of polyhydric alcohols having a main chain skeleton containing a chain aliphatic hydrocarbon group include ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl -1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol and pinacol. Examples of the alcohol having an aliphatic hydrocarbon group in the main chain skeleton and having a cyclic structure include cyclopentanol, cyclohexanol, and 1,3-cyclopentanediol.

[0020] Alcohols having a main chain structure in which at least one carbon atom constituting a chain aliphatic hydrocarbon group is substituted by an ether group (-O-) include, for example, mono- or poly(alkoxy)alkane Base ethers, more specifically, ethylene glycol monoalkyl ether, diethylene glycol, diethylene glycol monoalkyl ether, triethylene glycol, triethylene glycol monoalkyl ether, tetraethylene glycol Alcohol, hexanediol, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, Propylene glycol mono-n-propyl ether, dipropylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether. Examples of alcohols having a ring structure and a main chain structure in which one or more carbon atoms constituting an aliphatic hydrocarbon group are substituted with ether groups (—O—) include tetrahydrofurfuryl alcohol.

[0021] As alcohol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 1-pentanol, 3-pentanol or cyclopentanol are relatively Excellent, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 1-pentanol, 3-pentanol or cyclopentanol are more preferred, 1-butanol , 2-butanol or tertiary butanol are further preferred.

[0022] Also, as the alcohol, a hydrophilic alcohol is preferable. In the present specification, hydrophilic means that 0.1 g or more is dissolved in 100 g of water under the condition of 25°C. Among them, under the condition of 25°C, more than 10 g of alcohol can be dissolved in 100 g of water, or an alcohol that can be uniformly mixed with water at any mixing ratio is preferable.

[0023] Alcohols may be used alone or in combination of two or more. As an alcohol when using 2 or more types together, the combination etc. of the said alcohol are mentioned as an example. The alcohol content is not particularly limited, but is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and 55 to 75% by mass based on the total mass of the composition for better cleaning performance. for further improvement.

[0024] [Aprotic polar solvent] This composition contains an aprotic polar solvent. In this specification, an aprotic polar solvent refers to a compound that does not have a proton (hydrogen ion) donating property and has an electrical bias in the molecule.

[0025] Examples of the aprotic polar solvent include sulfur-containing solvents and ketone-based solvents. Examples of the sulfur-containing solvent include dimethylsulfone, dimethylsulfoxide, and cyclobutane. As a ketone solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned, for example.

[0026] As the aprotic polar solvent, a sulfur-containing solvent is preferred, dimethylsulfoxide or cyclobutane is more preferred, and cyclobutane is further preferred.

[0027] The aprotic polar solvent may be used alone or in combination of two or more. In terms of better residue removal performance, the content of the aprotic polar solvent is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass, and 5 to 15% by mass based on the total mass of the composition. for further improvement. [Azole compound] An azole compound is a compound containing at least one nitrogen atom and an aromatic hetero 5-membered ring. The number of nitrogen atoms contained in the hetero 5-membered ring of the azole compound is not particularly limited, preferably 1-4, more preferably 2-4.

[0029] The azole compound may have substituents on the hetero5-membered ring. Examples of such substituents include hydroxyl groups, carboxyl groups, mercapto groups, amino groups, and substituted or unsubstituted hydrocarbon groups. Also, when two substituents are adjacent to each other on the hetero 5-membered ring, these two substituents may be bonded to each other to form a ring. Examples of the hydrocarbon group having a hetero5-membered ring as a substituent include alkyl (preferably 1 to 12 carbons, more preferably 1 to 6 carbons), alkenyl (preferably 2 to 12 carbons, carbon 2-6 is better), alkynyl (2-12 carbons is better, 2-6 carbons is better), aryl (6-18 carbons is better, 6-10 carbons is more preferably) and aralkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 11 carbon atoms). As a substituent which the said hydrocarbon group has, a hydroxyl group, a carboxyl group, and -N(Ra)(Rb) are mentioned, for example. Ra and Rb independently represent a hydrogen atom, an alkyl group (preferably with 1 to 6 carbons, more preferably with 1 to 4 carbons) or hydroxyalkyl (preferably with 1 to 6 carbons, with 1 to 4 carbons) for better).

[0030] The ring formed by the bonding of two adjacent substituents on the heterocyclic 5-membered ring is not particularly limited, and the aromatic ring (which can be any one of monocyclic and polycyclic) is preferred, and benzene Ring is better. The ring formed by bonding the above two substituents may have a substituent. It does not specifically limit as a substituent, For example, what was illustrated as the substituent of the hydrocarbon group which a hetero 5-membered ring has. As the azole compound, for example, an imidazole compound in which one of the atoms constituting the azole ring is a nitrogen atom, a pyrazole compound in which two of the atoms constituting the azole ring are nitrogen atoms, among the atoms constituting the azole ring A thiazole compound in which one of the atoms constituting the azole ring is a nitrogen atom and the other is a sulfur atom, a triazole compound in which three of the atoms constituting the azole ring are nitrogen atoms, and a tetrazole compound in which four of the atoms constituting the azole ring are nitrogen atoms.

[0032] As the imidazole compound, for example, imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-di Methyl-2-mercaptoimidazole, 4-hydroxyimidazole, 2,2'-bisimidazole, 4-imidazolecarboxylic acid, histamine and benzimidazole.

[0033] As the pyrazole compound, for example, pyrazole, 4-pyrazolecarboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-amine Basepyrazole and 4-aminopyrazole.

[0034] Examples of thiazole compounds include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole.

[0035] The triazole compound includes, for example, a compound having a benzotriazole skeleton in which two adjacent substituents on the triazole ring are bonded to each other to form a benzene ring. Examples of compounds having a benzotriazole skeleton include 1H-benzotriazole, 2H-benzotriazole, and benzene and / triazole rings in 1H-benzotriazole or 2H-benzotriazole. The upper substitution is at least one selected from the group consisting of an alkyl group (preferably an alkyl group with 1 to 8 carbon atoms), an amino group, a hydroxyl group, a carboxyl group, a halogen atom, an aryl group, and a combination thereof Compounds made of substituents. More specifically, 1H-benzotriazole, 2H-benzotriazole, 5-methyl-1H-benzotriazole (CAS registration number: 136-85-6), tolyltriazole ( CAS registration number: 29385-43-1), 5-aminobenzotriazole, 1-hydroxybenzotriazole, carboxybenzotriazole (for example, benzotriazole-5-carboxylic acid and 4-carboxybenzene triazole, etc.), 5,6-dimethylbenzotriazole, 1-[N,N-bis(hydroxyethyl)aminoethyl]benzotriazole, 1-(1,2-dicarboxy Ethyl)benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-[N,N-bis(2-ethylhexyl)amino Methyl]methylbenzotriazole and 2,2'-{[(methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol. Examples of triazole compounds other than compounds having a benzotriazole skeleton include 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3-amino-1, 2,4-triazole, 1,2,3-triazole and 1-methyl-1,2,3-triazole.

[0036] As a tetrazole compound, for example, 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1H-tetrazole, 5-amino-1H-tetrazole, 1 ,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole and 1-(2-dimethylaminoethyl)-5-mercaptotetrazole.

[0037] As the azole compound, a triazole compound or a tetrazole compound is preferably selected from the group consisting of 1,2,4-triazole, 1,2,3-triazole, 1H-tetrazole, 5-aminotetrazole , 1H-benzotriazole, tolyltriazole, 5-methyltriazole, carboxybenzotriazole and 2,2'-[{(methyl-1H-benzotriazol-1-yl)methyl}imino] diethanol group is more preferably at least one, 1,2,4-triazole, 1H-benzotriazole, tolyltriazole, 5-methyltriazole or, 2, 2'-[{(methyl-1H-benzotriazol-1-yl)methyl}imino]bisethanol is further preferred. In addition, in this specification, the said azole compound is what includes this tautomer.

[0038] The azole compound may be used alone or in combination of two or more. In terms of excellent corrosion resistance to metal layers such as cobalt-containing layers and tungsten-containing layers, the content of the azole compound is preferably 0.01-10% by mass relative to the total mass of the composition, and 0.1-6% by mass is More preferably, 0.1-5 mass % is still more preferable, and 0.2-3 mass % is still more preferable.

[0039] [Alkanolamine] This composition contains alkanolamine. The alkanolamine is an amine compound having at least one amine group and at least one hydroxyl group (preferably a hydroxyalkyl group) in the molecule. Examples of alkanolamines include compounds having a main chain structure containing a chain aliphatic hydrocarbon group, at least one amine group bonded to the main chain structure, and at least one alcoholic hydroxyl group bonded to the main chain structure. In addition, in the above-mentioned main chain skeleton, one or more methanediyl groups (-CH2-) constituting the chain aliphatic hydrocarbon group may be substituted with a heteroatom. Examples of the hetero atom include -O-, -S- and -NH-, and -O- or -NH- is preferable.

[0040] The number of amino groups contained in the alkanolamine is, for example, 1 to 5, preferably 1 to 3, more preferably 1 or 2, and more preferably 1. As the amine group of alkanolamine, it can be any one of primary amine group (-NH2), secondary amine group (>NH) and tertiary amine group (>N-), but alkanolamine has optional At least one kind selected from the group consisting of a primary amino group and a secondary amino group is preferable, and it is more preferable that all the amino groups contained in the alkanolamine are primary amino groups or secondary amino groups. The number of hydroxyl groups in the amino alcohol is, for example, 1 to 5, preferably 1 to 3, more preferably 1 or 2.

[0041] As alkanolamines, for example, 2-aminoethanol, diethanolamine (DEA), triethanolamine (TEA), trismethylolaminomethane (Tris), 2-(2-aminoethoxy base) ethanol, 2-(2-aminoethylamino)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methylethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-dipropanol, 2-amino-2-ethyl-1 ,3-dipropanol and 2-(methylamino)-2-methyl-1-propanol. Among them, diethanolamine, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethoxy)ethanol, triethanolamine, 2-aminoethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine or N-methylethanolamine are preferred, diethanolamine, 2-(2-aminoethoxy)ethanol, 2- Aminoethanol, 2-(2-aminoethylamino)ethanol, N,N-dimethylethanolamine or N-methylethanolamine are more preferred.

[0042] The alkanolamines may be used alone or in combination of two or more. In terms of superior Co corrosion resistance, the content of the alkanolamine is preferably 0.1 to 30% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.3 to 10% by mass relative to the total mass of the composition. Preferably, 1-10 mass % is still more preferable.

[0043] (Water) This composition contains water. The water is not particularly limited, and distilled water, deionized water, and pure water (ultrapure water) can be used. Pure water is preferable in that it contains almost no impurities and has less influence on the semiconductor substrate in the manufacturing steps of the semiconductor substrate. As pure water, deionized water (DIW) with reduced inorganic anions and metal ions is better, derived from Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn It is more preferable that the ion concentration of metal atoms is reduced. Among them, when used to prepare the composition, it is preferable that the concentration of ions derived from metal atoms in water is at or below the ppt level (in one form, the metal content is less than 0.001 ppt by mass). As a method of adjustment, purification using a filtration membrane or an ion exchange membrane, or purification by distillation is preferable. As the method of adjustment, for example, the method described in paragraphs

[0074] to

[0084] of JP-A-2011-110515 and the method described in JP-A-2007-254168 are mentioned.

[0044] The content of water is not particularly limited, and relative to the total mass of the composition, for example, it is 1 to 90% by mass, preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 35% by mass for further improvement.

[0045] Furthermore, the water used in the embodiment of the present invention is preferably prepared as described above. The above-mentioned water is preferably used not only for the composition but also for cleaning of the storage container, and is also preferably used for the production steps of the composition, component measurement of the composition, and measurement for evaluation of the composition. [Optional Components] The composition may contain components other than the above-mentioned components. Hereinafter, optional components that may be contained in the composition will be described.

[0047] <Component A> The composition may further contain component A selected from the group consisting of cyclobutene and dipropylene, and it is preferable to contain component A in terms of excellent Co corrosion resistance. In addition, the term "cyclobutene" is a general term including all isomers such as 2-cyclobutene and 3-cyclobutene, and cyclobutene includes all isomers. The composition preferably contains a compound selected from the group consisting of 2-cyclobutene and dipropylene as component A.

[0048] The composition may contain one type of component A alone, or may contain two or more types. When the composition contains Component A, the content of Component A is not particularly limited, but it is preferably 10 mass ppt or more, and 100 mass ppt relative to the total mass of the composition in terms of better Co corrosion resistance. Above is more preferable, and above 1000 quality ppt is still more preferable. The upper limit is not particularly limited, but it is preferably 1000 mass ppm or less relative to the total mass of the composition, more preferably 100 mass ppm or less, and further preferably 10 mass ppm or less in terms of excellent defect suppression ability. good.

[0049] Also, when the composition contains component A, the ratio of the content of the azole compound to the content of component A (content of the azole compound / content of component A) is 1.0 in terms of excellent defect suppression ability. Preferably, it is ×102-1.0×1012, More preferably, it is 1.0×103-1.0×1010, More preferably, it is 1.0×104-1.0×108.

[0050] Also, when the composition contains component A, in terms of the corrosion resistance (W corrosion resistance) of the metal layer containing tungsten is more excellent, the content of the aprotic polar solvent and component A The ratio of content (content of aprotic polar solvent / content of component A) is preferably 1.0×103~1.0×1012, more preferably 1.0×104~1.0×1010, and 1.0×104~1.0×109 Further better.

[0051] <chelating agent> The composition may contain a chelating agent. Chelating agents are compounds that have the function of chelating metal elements. Due to the function of the chelating agent, the performance of removing residues such as etching residues and ashing residues is further improved, so it is preferable that the composition contains a chelating agent. When the composition contains a chelating agent, the above-mentioned residue can be removed in a short time, so it is also preferable from the viewpoint of corrosion resistance to the metal layer. The chelating agent is not particularly limited as long as it is a compound that has the function of chelating with a metal element, and a compound having two or more functional groups (ligands) that coordinately bond with a metal element in one molecule is better. In addition, in this specification, the compound corresponding to the above-mentioned alkanolamine is not included in a chelating agent.

[0052] Examples of the ligand possessed by the chelating agent include acid groups and cationic groups. As an acidic group, a carboxyl group, a phosphonic acid group, a phosphoric acid group, a sulfo group, and a phenolic hydroxyl group are mentioned, for example. As a cationic group, an amino group is mentioned, for example. The chelating agent contained in the composition preferably has a ligand selected from the group consisting of carboxyl group, phosphonic acid group, phosphoric acid group and amine group, more preferably has a carboxyl group.

[0053] The chelating agent is preferably low molecular weight. Specifically, the molecular weight of the chelating agent is preferably 600 or less, more preferably 450 or less, and more preferably 300 or less. The lower limit is not particularly limited, and it is preferably 85 or higher. Also, the carbon number of the chelating agent is preferably 15 or less, more preferably 12 or less, and still more preferably 8 or less. The lower limit is not particularly limited, and 1 or more is preferable. Examples of the chelating agent include a carboxylic acid-based chelating agent having a carboxyl group, a phosphonic acid-based chelating agent having a phosphonic acid group, a phosphoric acid-based chelating agent having a phosphoric acid group, and a polyamine-based chelating agent having a plurality of amine groups. (Carboxylic acid-based chelating agent) A carboxylic acid-based chelating agent is a chelating agent having a carboxyl group as a ligand in the molecule, such as polycarboxylic acid, amino polycarboxylic acid, amino acid and hydroxycarboxylic acid .

[0055] A polycarboxylic acid is a compound having a plurality of carboxyl groups in the molecule. However, the amino polycarboxylic acid described later is not included in the polycarboxylic acid. Examples of the polycarboxylic acid include citric acid, malonic acid, maleic acid, succinic acid, malic acid, tartaric acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, and sebacic acid.

[0056] The amino polycarboxylic acid is a compound having one or more amino groups and a plurality of carboxyl groups in the molecule. As the amino polycarboxylic acid, polyamino polycarboxylic acid having a plurality of amine groups and a plurality of carboxyl groups in the molecule is preferable. Examples of polyaminopolycarboxylic acids include mono- or polyalkylenepolyaminepolycarboxylic acids and polyaminoalkanepolycarboxylic acids. More specific examples of polyaminopolycarboxylic acids include butanediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3- Diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexane Tetraacetic acid (Cy-DTA), ethylenediaminediacetic acid, ethylenediaminedipropionic acid, diaminopropane tetraacetic acid and 1,4,7,10-tetraazacyclododecane-tetraacetic acid. Examples of aminopolycarboxylic acids other than polyaminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, aspartic acid, and glutamic acid.

[0057] Examples of the amino acid include compounds having one or more amino groups and one carboxyl group in the molecule. More specifically, examples of amino acids include glycine, serine, α-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), lysine , leucine, isoleucine, cystine, cysteine, ethionine, threonine, tryptophan, tyrosine, valine, histidine, histidine derivatives, Asparagine, glutamine, arginine, proline, methionine, phenylalanine, compounds described in paragraphs

[0021] to

[0023] of JP-A-2016-086094 and the salt. In addition, as a histidine derivative, the compound described in Unexamined-Japanese-Patent No. 2015-165561 and Unexamined-Japanese-Patent No. 2015-165562 can be used, These content is incorporated in this specification. Moreover, examples of salts include alkali metal salts such as sodium salts and potassium salts, ammonium salts, carbonates, and acetates.

[0058] Hydroxycarboxylic acid is a compound having one carboxyl group and one or more hydroxyl groups in the molecule. Examples of the hydroxycarboxylic acid include gluconic acid, heptanoic acid, glycolic acid, and lactic acid.

[0059] As the carboxylic acid-based chelating agent, polycarboxylic acid or amino polycarboxylic acid is preferred, and polycarboxylic acid or polyamino polycarboxylic acid is more preferred.

[0060] (Phosphonic acid-based chelating agent) The phosphonic acid-based chelating agent is a chelating agent having at least one phosphonic acid group as a ligand in the molecule. Among them, chelating agents having both a phosphonic acid group and a carboxyl group are classified into carboxylic acid-based chelating agents.

[0061] As a phosphonic acid chelating agent, for example, ethylene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropylene-1,1 '-diphosphonic acid, 1-hydroxybutylene-1,1'-diphosphonic acid, ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrogen Tris(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), 1,3-propanediaminebis(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) phosphonic acid) (EDTPO), ethylenediaminetetrakis(ethylenephosphonic acid), 1,3-propanediaminetetrakis(methylenephosphonic acid) (PDTMP), 1,2-diaminopropanetetra(ethylene methylphosphonic acid), 1,6-hexamethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) (DEPPO), diethylenetriaminepenta(methylenephosphonic acid) ethylphosphonic acid), ethylenetetramine hexa(methylene phosphonic acid) and ethylenetetramine hexa(ethylene phosphonic acid).

[0062] As the phosphonic acid chelating agent used in the composition, not only the above-mentioned compounds can be used, but also the compounds described in paragraphs

[0026] to

[0036] of the specification of International Publication No. The compounds ((co)polymers) described in paragraphs

[0031] to

[0046] of Specification No. 2018 / 030006 are disclosed, and these contents are incorporated in this specification.

[0063] The number of phosphonic acid groups in the phosphonic acid-based chelating agent is preferably 2-5, more preferably 2-4, and even more preferably 2 or 3. The carbon number of the phosphonic acid-based chelating agent is preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. The lower limit is not particularly limited, and 1 or more is preferable. As the phosphonic acid-based chelating agent, HEDPO, NTPO, EDTPO, or DEPPO is more preferable, and EDTPO is still more preferable. A phosphonic-acid-type chelating agent may be used individually by 1 type, and may use it in combination of 2 or more types. (Phosphoric acid-based chelating agent) Examples of the phosphoric acid-based chelating agent include condensed phosphoric acid and its salts, and more specifically, pyrroline acid, tripolyphosphoric acid, hexametaphosphoric acid, and their salts.

[0065] (Polyamine-based chelating agent) The polyamine-based chelating agent is a chelating agent having only a plurality of amine groups as ligands in the molecule. Examples of polyamine-based chelating agents include ethylenediamine (EDA), 1,3-propanediamine (PDA), 1,2-propanediamine, 1,3-butanediamine, and 1,4- Lower alkylenediamines such as butanediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), bis(aminopropyl)ethylenediamine (BAPEDA) and tetraethylenepentamine, etc. polyalkylene polyamines. Among them, lower alkylenediamine is preferable, and 1,4-butanediamine is more preferable.

[0066] Examples of polyamine-based chelating agents other than the above include at least one biguanide compound selected from the group including compounds having a biguanide group and salts thereof. The number of biguanide groups that a biguanide compound has is not particularly limited, and may have a plurality of biguanide groups. As the biguanide compound, compounds described in paragraphs

[0034] to

[0055] of JP 2017-504190 A can also be used, and the contents described in the above documents are incorporated in the present specification.

[0067] As a compound having a biguanide group, for example, ethylenylbiguanide, propylenylbiguanide, tetramethylenebiguanide, pentamethylenebiguanide, hexamethylenebiguanide, heptamethene Dibiguanide, octamethylenebiguanide, 1,1'-hexamethylenebis(5-(p-chlorophenyl)biguanide) (lohecidine), 2-(benzyloxymethyl)pentamethylene Alkane-1,5-bis(5-hexylbiguanide), 2-(phenylthiomethyl)pentane-1,5-bis(5-phenylethylbiguanide), 3-(phenylthio)hexane- 1,6-bis(5-hexylbiguanide), 3-(phenylthio)hexane-1,6-bis(5-cyclohexylbiguanide), 3-(benzylthio)hexane-1,6-bis (5-hexylbiguanide) and 3-(benzylthio)hexane-1,6-bis(5-cyclohexylbiguanide). As a salt of a compound having a biguanide group, hydrochloride, acetate or gluconate are preferred.

[0068] As other chelating agents other than the above, compounds represented by the following formula (A) and compounds represented by the following formula (B) can also be mentioned.

[0069] [chemical formula 1]

[0070] In the above formula (A), R1A to R5A independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxyl group, a carboxyl group or a substituted or unsubstituted amino group. Wherein, the structure contains at least one group selected from hydroxyl, carboxyl and substituted or unsubstituted amino groups. In the above formula (B), R1B to R4B each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

[0071] Examples of the compound represented by the formula (A) include 1-thioglycerol and mercaptosuccinic acid. Examples of the compound represented by the formula (B) include catechol and tertiary butylcatechol.

[0072] As a chelating agent, carboxylic acid-based chelating agent or phosphonic acid-based chelating agent is better, carboxylic acid-based chelating agent is better, polycarboxylic acid or amino polycarboxylic acid is further preferred, polyamino polycarboxylate Acids or polycarboxylic acids are particularly preferred.

[0073] The chelating agent may be used alone or in combination of two or more. The ligands possessed by the chelating agent have different specificities for the metals adsorbed by the type, so the composition contains two or more types of ligands that are different from each other in terms of better removability of residues containing multiple metals. A combination of chelating agents is preferred. When the composition contains a combination of the above two or more chelating agents, the mass ratio of the content of other chelating agents to the content of one chelating agent is preferably 0.01-100, more preferably 0.1-10.

[0074] When the composition contains a chelating agent, the content of the chelating agent is preferably 0.01 to 10% by mass, 0.05 to 5% by mass relative to the total mass of the composition in terms of better residue removal performance. More preferably, 0.1 to 3% by mass is further more preferable. Also, when the object to be cleaned is a dry etching residue and the residue contains a large amount of metal, the chelating agent has the effect of further improving the residue removability of the composition. Therefore, it is preferable to use a composition containing a chelating agent for the treatment of such objects to be cleaned.

[0075] <Basic Compound> The composition may contain a basic compound. Basic compounds refer to compounds whose solution pH exceeds 7 when dissolved in water. The basic compound functions as a pH adjuster for adjusting the pH of the composition.

[0076] The basic compound is not particularly limited, for example, ammonium hydroxide, amine compound (except for the above-mentioned azole compound, the above-mentioned alkanolamine and the above-mentioned compound contained in the chelating agent.) and quaternary ammonium compound .

[0077] (Ammonium Hydroxide) The composition may contain ammonium hydroxide (NH4OH) as a basic compound. When the composition contains ammonium hydroxide, the content is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5.0% by mass, based on the total mass of the composition.

[0078] (Amine compound) In this specification, an amine compound refers to a compound having an amine group in the molecule and is not included in the above-mentioned azole compound, the above-mentioned alkanolamine, and the above-mentioned chelating agent. Examples of amine compounds include primary amines having a primary amine group (-NH2) in the molecule, secondary amines having a secondary amine group (>NH) in the molecule, and tertiary amines having a tertiary amine group in the molecule. (>N-) tertiary amines and their salts. As the salt of the amine compound, for example, a salt of an inorganic acid bonded to hydrogen with at least one nonmetal selected from the group consisting of Cl, S, N, and P, hydrochloride, sulfate, or Nitrates are preferred. Also, the amine compound is preferably a water-soluble amine capable of dissolving 50 g or more in 1 L of water. Examples of the amine compound include alicyclic amine compounds, hydroxylamine compounds, and other amine compounds other than these compounds.

[0079] The alicyclic amine compound refers to a compound having an alicyclic (non-aromatic ring) structure in the molecule among amine compounds. Examples of alicyclic amine compounds include 1,8-diacribicyclo[5.4.0]-7-undecene (DBU), ε-caprolactam, the following compound 1, the following compound 2, The following compounds 3, 1,4-diacribicyclo[2.2.2]octane (DABCO), tetrahydrofurfurylamine, N-(2-aminoethyl)piperone, hydroxyethylpiperone, piperazine, 2-Methylpiperone, trans-2,5-dimethylpiperone, cis-2,6-dimethylpiperone, 2-piperidinemethanol, cyclohexylamine and 1,5-diazepine [4,3,0]-5-nonene.

[0080] [chemical formula 2]

[0081] The hydroxylamine compound is at least one compound selected from the group consisting of hydroxylamine (NH2OH), hydroxylamine derivatives and these salts. The hydroxylamine derivatives are not particularly limited, and examples include O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,O-dimethylhydroxylamine, N -Ethylhydroxylamine, N,N-diethylhydroxylamine, N,O-diethylhydroxylamine, O,N,N-trimethylhydroxylamine, N,N-dicarboxyethylhydroxylamine, and N,N-disulfo Ethylhydroxylamine, etc. Salts of hydroxylamine and hydroxylamine derivatives include inorganic acid salts or organic acid salts, preferably inorganic acid salts with non-metallic atoms such as Cl, S, N, or P that can be bonded to hydrogen atoms, such as hydrochloric acid, sulfuric acid, or nitric acid The salt of any acid in is more preferred. Examples of primary amines other than alicyclic amine compounds and hydroxylamine compounds in amine compounds include methylamine, ethylamine, propylamine, butylamine, pentylamine, methoxyethylamine, and methoxylamine. Propylamine. Examples of secondary amines other than the alicyclic amine compound and the hydroxylamine compound include dimethylamine, diethylamine, dipropylamine, and dibutylamine (DBA). Examples of tertiary amines other than alicyclic amine compounds and hydroxylamine compounds include trimethylamine, triethylamine, and tributylamine (TBA).

[0083] The amine compound may be used alone or in combination of two or more. When the composition contains an amine compound, its content is not particularly limited, but is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total mass of the composition.

[0084] (Quaternary ammonium compound) The composition may contain a compound having one quaternary ammonium cation in the molecule or a quaternary ammonium compound as a salt thereof. The quaternary ammonium compound is not particularly limited as long as it is a compound or a salt thereof having one quaternary ammonium cation in which four hydrocarbon groups (preferably alkyl groups) are substituted by nitrogen atoms. Examples of quaternary ammonium compounds include quaternary ammonium hydroxide, quaternary ammonium fluoride, quaternary ammonium bromide, quaternary ammonium iodide, quaternary ammonium acetate, and quaternary ammonium carbonate. .

[0085] As the quaternary ammonium compound, quaternary ammonium hydroxide is preferred, and a compound represented by the following formula (a1) is more preferred.

[0086] [chemical formula 3]

[0087] In the above formula (a1), Ra1 to Ra4 independently represent an alkyl group with 1 to 16 carbons, an aryl group with 6 to 16 carbons, an aralkyl group with 7 to 16 carbons, or an aralkyl group with 1 to 16 carbons of hydroxyalkyl groups. At least two of Ra1 to Ra4 may be bonded to each other to form a ring structure. The above-mentioned alkyl group may be linear, branched or cyclic. As the compound represented by the above formula (a1), for example, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide (TBAH), Methyltripropylammonium Hydroxide, Methyltributylammonium Hydroxide, Ethyltrimethylammonium Hydroxide, Dimethyldiethylammonium Hydroxide, Benzyltrimethylammonium Hydroxide (BzTMAH), Cetyl Hydroxide Trimethylammonium, (2-hydroxyethyl)trimethylammonium hydroxide, and spiro-(1,1')-bipyrrolidinium hydroxide.

[0089] The quaternary ammonium compound may be used alone or in combination of two or more. When the composition contains a quaternary ammonium compound, its content is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total mass of the composition.

[0090] The basic compound may be used alone or in combination of two or more. When the composition contains a basic compound, its content is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total mass of the composition.

[0091] <Acidic Compound> The composition may contain an acidic compound as a pH adjuster. The acidic compound may be an inorganic acid or an organic acid (except the above-mentioned chelating agent). Examples of the inorganic acid include sulfuric acid, hydrochloric acid, acetic acid, nitric acid, and phosphoric acid, and sulfuric acid, hydrochloric acid, or acetic acid is preferred. Examples of the organic acid include lower (1 to 4 carbon atoms) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid. In addition, the above-mentioned chelating agent may also function as an acidic compound.

[0092] The acidic compound may be used alone or in combination of two or more. What is necessary is just to select the kind and content of an acidic compound suitably so that the pH of a composition may fall in the range mentioned later, and to adjust a content.

[0093] <Fluorine-containing compound> The composition may contain a fluorine-containing compound. Examples of the fluorine-containing compound include hydrofluoric acid (hydrofluoric acid), ammonium fluoride, tetramethylammonium fluoride, and tetrabutylammonium fluoride, and hydrofluoric acid is preferred. A fluorine-containing compound may be used individually by 1 type, and may use it in combination of 2 or more types. When the composition contains a fluorine-containing compound, its content is preferably 0.01 to 5.0% by mass relative to the total mass of the composition.

[0094] <Metal Component> The composition may contain a metal component. Examples of the metal component include metal particles and metal ions. For example, when referring to the content of a metal component, it means the total content of metal particles and metal ions. The composition may contain either one of metal particles and metal ions, or may contain both.

[0095] As the metal atom contained in the metal component, for example, the group consisting of Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Metal atoms in the group of Mg, Mn, Mo, Na, Ni, Pb, Sn, Sr, Ti and Zn. A metal component may contain 1 type of metal atom, and may contain 2 or more types. Metal particles can be single or alloy, and metal can also exist in the form of combination with organic matter. The metal component may be a metal component that is inevitably included in each component (raw material) contained in the composition, or may be a metal component that is inevitably contained in the manufacture, storage and / or transfer of the composition, or may be intentionally included. Add to. When the composition contains a metal component, the content of the metal component is usually 0.01 mass ppm to 10 mass ppm relative to the total mass of the composition, preferably 0.1 mass ppt to 1 mass ppm, and 0.1 mass ppt to 100 mass ppb. better.

[0096] The type and content of metal components in the composition can be measured by ICP-MS (Inductively Coupled Plasma Mass Spectrometry) method. In the ICP-MS method, the content of the metal component to be measured is measured regardless of its existing form. Therefore, the total mass of the metal particles and metal ions to be measured is quantified as the content of the metal component. For measurement by the ICP-MS method, for example, Agilent Technologies Japan, Ltd., Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200), Agilent 8900, and PerkinElmer Co., Ltd. can be used . Made NexION350S.

[0097] The method of adjusting the content of each metal component in the composition is not particularly limited. For example, the content of metal components in the composition can be reduced by performing a known treatment for removing metals from the composition and / or raw materials including the components used to prepare the composition. Also, by adding a compound containing metal ions to the composition, the content of the metal component in the composition can be increased.

[0098] <Preservative> It is preferable that the composition contains a preservative. The corrosion inhibitor forms a film by coordinating with the surface of the metal layer (especially W-containing layer or Co-containing layer) that becomes the wiring of the semiconductor element, etc., and has the function of preventing corrosion of the metal layer caused by excessive etching or the like. In addition, in this specification, the above-mentioned azole compounds and chelating agents (compounds having chelating ability) are not included in preservatives.

[0099] As preservatives, for example, tricresyl phosphate, adenine, cytosine, guanine, thymine, phosphate inhibitors, propanethiol, silanes, benzohydroxamic acids, heterocyclic Nitrogen inhibitors, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, potassium ethyl xanthate, dodecylphosphonic acid, boric acid, 2,3 , 5-trimethylpyrrole, 2-ethyl-3,5-dimethylpyrrole, quinoxaline, acetylpyrrole, pyrrole, histadine, pyrrole, glutathione ( Reduction type), thiophene, mercaptopyridine N-oxide, thiamine HCl, tetraethylamine disulfide methylthiol and phenol.

[0100] As a preservative, for example, a substituted or unsubstituted tetrazole can also be mentioned.

[0101] The substituted or unsubstituted tetrazole includes, for example, a tetrazole having an unsubstituted tetrazole and a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group as substituents. Among them, as the substituent when the amino group is substituted, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.

[0102] The preservatives may be used alone or in combination of two or more. When the composition contains a preservative, the content of the preservative is preferably 0.01 to 5% by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.1 to 3% by mass, based on the total mass of the composition.

[0103] It is better to use a high-purity preservative, and it is better to use it after further purification. The purification method of the preservative is not particularly limited. For example, known methods such as filtration, ion exchange, distillation, adsorption purification, recrystallization, reprecipitation, sublimation, and purification using a column can be used, and these methods can also be used in combination.

[0104] The composition may contain additives other than the above-mentioned components. As an additive, a surfactant, an antifoaming agent, a rust inhibitor, and an antiseptic are mentioned, for example.

[0105] [Physical properties of the composition] <pH> This composition is preferably used at a pH of 7 or higher. The pH of the composition is preferably 9-11. When pH is 9-11, the composition which is more excellent in the corrosion resistance with respect to the metal layer which consists of wiring materials, such as Co and W, can be obtained. The pH of the composition is preferably from 9.2 to 11, and more preferably from 9.5 to 11, since the Co corrosion resistance and the W corrosion resistance are more excellent. The pH of the composition is a value measured at 25° C. using a known pH meter.

[0106] <Coarse particles> It is preferable that the composition does not substantially contain coarse particles. Coarse particles refer to, for example, particles having a diameter of 0.2 μm or more when the particle shape is regarded as a sphere. In addition, "substantially not including coarse particles" refers to 10 or less particles of 0.2 μm or more in 1 mL of the composition when the composition is measured using a commercially available measuring device in a light-scattering particle measurement method in liquid. Furthermore, the coarse particles included in the composition are particles such as dust, dust, organic solid matter, and inorganic solid matter contained as impurities in the raw material, and dust, dust, organic solid matter, etc. that are brought in as pollutants during the preparation of the composition. Particles such as solid matter and inorganic solid matter correspond to those that exist as particles without being dissolved in the final composition. The amount of coarse particles present in the composition can be measured in the liquid phase using a commercially available measuring device in a light-scattering liquid particle measurement system using a laser as a light source. As a method of removing coarse particles, treatment such as filtration may be mentioned, for example.

[0107] [Kit and Concentrate] The above-mentioned composition can be used as a kit for preparing a composition by dividing its raw material into a plurality. As a kit for preparing the composition, for example, a kit including a first liquid containing at least an azole compound and an alkanolamine and a second liquid containing at least an aprotic polar solvent (hereinafter also referred to as " Set A".). The first liquid of kit A may contain components other than azole compounds and alkanolamines, but preferably does not contain aprotic polar solvents. In addition, the second solution of the set A may contain components other than the aprotic polar solvent, but it is preferable not to contain any azole compound or alkanolamine.

[0108] The content of each component contained in the first liquid and the second liquid contained in the kit is not particularly limited, and the content of each component in the composition prepared by mixing the first liquid and the second liquid is the above-mentioned The amount of the preferred content is preferred. The pH of the first liquid and the second liquid included in the kit is not particularly limited, and each pH may be adjusted so that the pH of the composition prepared by mixing the first liquid and the second liquid falls within the above range.

[0109] Furthermore, the composition can also be prepared as a concentrate. In this case, it can be used by diluting with a diluent at the time of use. The diluent is not particularly limited, and diluents containing alcohols, aprotic polar solvents, water, or mixtures thereof are exemplified. That is, the kit for preparing the composition may be a kit having the above-mentioned composition in the form of a concentrate and the above-mentioned diluent.

[0110] [Application] Next, the application of the composition of the above embodiment will be described. The above composition is a composition for a semiconductor device. In this specification, "for a semiconductor element" means used when manufacturing a semiconductor element. The above-mentioned composition can be used in any step for manufacturing a semiconductor device, for example, it can be used in the treatment of insulating films, resists, antireflection films, etching residues, ashing residues, etc. present on a substrate. In addition, in this specification, an etching residue and an ashing residue are collectively called a residue. In addition, the above-mentioned composition can be used for the treatment of the substrate after chemical mechanical polishing, and can also be used as an etching solution. Specifically, the composition can be used as a solution (for example, removal solution, stripping solution, etc.) ), etc., that is, pre-wetting liquid applied to the substrate in order to improve the applicability of the composition, a composition used to remove residues adhering to the metal layer, etc., used to remove various Solutions of various photoresist films (such as removing liquid and stripping liquid, etc.) and permanent films (such as color filters, transparent insulating films, and resin lenses). Furthermore, the semiconductor substrate after removal of the permanent film may be used again in the manufacture of the semiconductor device, so the removal of the permanent film is also included in the manufacturing steps of the semiconductor device. In addition, the above-mentioned composition can also be used as a composition for removing residues such as metal impurities and fine particles from a substrate after chemical mechanical polishing. In addition, the composition described above can also be used as an etching solution for metal oxides such as cobalt oxide and copper oxide (including composite oxides composed of a plurality of metal oxides). The composition can be suitably used especially as a composition for removing residue adhering to the metal layer (among them, the Co-containing layer or the W-containing layer) in the above-mentioned use. The composition may be used for only one of the above-mentioned uses, or may be used for two or more uses.

[0111] [Production method of composition] <Composition production step> The production method of the above-mentioned composition is not particularly limited, and known production methods can be used. As a method for producing the above-mentioned composition, for example, a method including at least a composition preparation step of mixing the above-mentioned components to prepare a composition is exemplified. In the preparation step of the composition, the order of mixing the components is not particularly limited. It is also preferable to manufacture the concentrated liquid and each liquid included in the set by the same method as above. The production method of the kit is not particularly limited, for example, by separately preparing the above-mentioned first liquid and the second liquid and storing the first liquid and the second liquid in different containers to make a kit for preparing the composition .

[0112] <Metal Removal Step> Before using in the composition preparation step, each component is preferably subjected to a metal removal step of removing metal from a raw material containing each component to obtain a purified product containing each component. By performing a metal removal step on each component and using each component contained in the obtained purified product to prepare a composition, the content of the metal component contained in the composition can be further reduced. There is no particular limitation as a method for removing metals from raw materials (hereinafter also referred to as "purified products") comprising each component, and at least There are known methods such as a method of resin and a method of passing a substance to be purified through a metal ion adsorption filter.

[0113] The components to be the object of the metal removal step are not particularly limited as long as they are components contained in the above-mentioned composition (however, metal components are excluded). When the composition contains a chelating agent, the content of the metal component contained in the raw material containing the chelating agent tends to be higher than that of other components, so the composition obtained by performing a metal removal step on the raw material containing the chelating agent is used It is better to prepare the composition from the purified product of the chelating agent. The object to be purified in the metal removal step may contain compounds other than the target object, and preferably contains a solvent. As a solvent, water and an organic solvent are mentioned, Water is preferable. The content of the object in the object to be purified can be appropriately adjusted according to the type of object and the specific metal removal treatment, for example, it can be 1-100% by mass, preferably 10-50% by mass relative to the total mass of the object to be purified.

[0114] There is no particular limitation on the method of making the purified substance pass through at least one resin selected from the group comprising chelating resins and ion exchange resins, and it is possible to enumerate the chelating resin that makes the purified substance pass through the container. And / or the method of ion exchange resin. The chelate resin and / or the ion exchange resin through which the substance to be purified passes may be used alone or in combination of two or more. In addition, the substance to be purified may be passed through the same chelate resin and / or ion exchange resin two or more times. In the metal removal step, both a chelate resin and an ion exchange resin can be used. In this case, a chelate resin and an ion exchange resin can also be used in a multiple bed or a mixed bed. As the container, there is no particular limitation as long as it can be filled with chelating resin and / or ion exchange resin and the purified substance is passed through the filled chelating resin and / or ion exchange resin, for example, column, core and Fill the tower.

[0115] Examples of the ion exchange resin used in the metal removal step include cation exchange resins and anion exchange resins. The cation exchange resin can be used in a single bed, and the cation exchange resin and anion exchange resin can also be used in multiple beds or mixed beds. Known cation exchange resins can be used as the cation exchange resin, and examples thereof include sulfonic acid type cation exchange resins and carboxylic acid type cation exchange resins. The material of the cation exchange resin is not particularly limited, and gel-type cation exchange resin is preferred. As the cation exchange resin, commercially available products can be used, for example, Amberlite (registered trademark, hereinafter the same) IR-124, Amberlite IR-120B, Amberlite IR-200CT, Orlite (registered trademark, hereinafter the same) DS-1 and Orlite DS-4 (manufactured by ORGANO CORPORATION above); Duolite (registered trademark, same below) C20J, Duolite C20LF, Duolite C255LFH and Duolite C-433LF (manufactured by Sumika Chemtex Company, Limited above); DIAION (registered trademark, same below) SK- 110. DIAION SK1B and DIAION SK1BH (above, manufactured by Mitsubishi Chemical Corporation); and, Purolite (registered trademark, the same below) S957 and Purolite S985 (above, manufactured by Purolite).

[0116] The chelating resin is not particularly limited as long as it is a resin containing a chelating group capable of chelating metals. As the chelating group, for example, aminophosphonic acid groups such as iminodiacetic acid group, iminopropionic acid group, aminomethylenephosphonic acid group (-NH-CH3-PO3H2), polyamine groups, Glucosamine group such as N-methylglucosamine group, aminocarboxyl group, dithiocarbamic acid group, thiol group, amidoxime group and pyridyl group, iminodiacetic acid group or aminophosphonic acid group Preferably, an aminophosphonic acid group is more preferred. These chelate groups may form a salt together with a counter ion, but it is preferable not to form a salt at the point which can further reduce a metal content. That is, the chelating resin H type chelating resin is preferred. The H-type chelating resin is obtained by making Na-type, Ca-type, and Mg-type metal ion-type chelating resins contact mineral acid and acid treatment. The matrix of the chelating resin is not particularly limited, and examples thereof include styrene-divinylbenzene copolymers and styrene-ethylstyrene-divinylbenzene copolymers. As chelate resin, can use commercially available product, for example can enumerate Duolite ES371N, Duolite C467, Duolite C747UPS, Sumichelate (registered trademark, hereinafter same) MC760, Sumichelate MC230, Sumichelate MC300, Sumichelate MC850, Sumichelate MC640, Sumichelate MC900 and Sumichelate MC960 (manufactured by Sumika Chemtex Company, Limited); Purolite S106, Purolite S910, Purolite S914, Purolite S920, Purolite S930, Purolite S950, Purolite S957, and Purolite S985 (manufactured by Purolite); and Orlite DS- 21. Amberlite IRC748 and Amberlite IRC747 (manufactured by ORGANO CORPORATION above).

[0118] In the case where the composition contains a chelating agent, from the viewpoint of being able to further reduce the content of metal components in the composition, the metal removal step for the raw material containing the chelating agent includes making the purified product pass through a process selected from the group consisting of chelating The step of at least one resin in the group of resin and ion exchange resin is preferable, and the step of passing the purified substance through a chelating resin is more preferable. Among them, it is further preferable to include a step of passing the purified product through a chelating resin having an aminophosphonic acid group from the viewpoint of further reducing the content of Ca and / or Zn contained in the raw material containing the chelating agent. Commercially available chelating resins having aminophosphonic acid groups include Duolite C467, Duolite C747UPS, Sumichelate MC960, Purolite S950, Orlite DS-21, and Amberlite IRC747, with Orlite DS-21 being preferred. Furthermore, Orlite DS-21 is an H-type chelating resin formed by introducing aminomethylphosphonic acid groups into a base material composed of styrene-ethylstyrene-divinylbenzene copolymer as a chelating group. It is commercially available in a state containing 30 to 45% by mass of the above-mentioned chelate resin and 55 to 70% by mass of water.

[0119] The conditions for passing the purified product through the ion exchange resin are not particularly limited, and it can be carried out according to known methods. The space velocity (SV: Space Velocity) at which the purified product passes while being in contact with the ion exchange resin is preferably 1-20, more preferably 1-10. The temperature of the purified product in contact with the ion exchange resin is preferably 10-40°C, more preferably 15-30°C.

[0120] As the metal removal step of the product to be purified, the adsorption purification treatment step using the metal component of silicon carbide described in International Publication No. 2012 / 043496 can be implemented, and this description is incorporated in this specification. In addition, as the metal removal step of the object to be purified, metal particles contained in the object to be purified can be removed by using a filter mentioned as a filter used in the filtering step described later.

[0121] The metal to be removed from the product to be purified by the metal removal step is not particularly limited, and examples thereof include metals such as Li, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Ni, Zn, and Pb. The above metal content is reduced in the purified product obtained by the metal removal step compared to the purified product. The content of the metal in the purified product is not particularly limited. For example, the ratio of the content of each metal element of each metal component in the purified product containing a chelating agent to the content of the chelating agent is 1.0×10-6 or less in terms of mass ratio. More preferably, it is not more than 1.0×10-7, and it is still more preferably not more than 1.0×10-8. Also, in the purified product containing the chelating agent obtained in the metal removal step, the ratio of the content of the Ca component to the content of the Na component is 1.0 or more in terms of mass ratio (the content of the Ca component is greater than the content of the Na component). Good, 1.1 or higher is more preferable, 1.2 or higher is still more preferable. The upper limit is not particularly limited, and the ratio of the content of the Ca component to the content of the Na component is preferably 50 or less in terms of mass ratio. In addition, the type and content of the metal in the object to be purified and the purified product can be measured according to the method described as the method for measuring the type and content of the metal component in the composition.

[0122] <Filtering Step> The above-mentioned production method preferably includes a filtering step of filtering the liquid in order to remove foreign matter and coarse particles from the liquid. The filtering method is not particularly limited, and known filtering methods can be used. Among them, filtration using a filter is preferable.

[0123] The filter used for filtration can be used without particular limitation as long as it is conventionally used for filtration purposes and the like. Examples of materials constituting the filter include fluorine resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high molecular weight ), and Jufangqi, etc. Among them, polyamide-based resins, PTFE, polypropylene (including high-density polypropylene) and polyarylate are preferred. By using a filter formed of these raw materials, it is possible to more effectively remove highly polar foreign matter that tends to cause defects from the composition.

[0124] The critical surface tension of the filter is preferably at least 70 mN / m as the lower limit, and preferably at least 95 mN / m as the upper limit. In particular, the critical surface tension of the filter is preferably 75 to 85 mN / m. Furthermore, the value of the critical surface tension is the manufacturer's nominal value. By using a filter having a critical surface tension within the above-mentioned range, it is possible to more effectively remove highly polar foreign matter that tends to cause defects from the composition.

[0125] The pore size of the filter is preferably about 0.001-1.0 μm, more preferably about 0.02-0.5 μm, and still more preferably about 0.01-0.1 μm. By setting the pore diameter of the filter within the above range, it is possible to reliably remove fine foreign matter contained in the composition while suppressing filter clogging.

[0126] When using filters, different filters can be combined. At this time, the filtration with the first filter may be performed only once, or may be performed two or more times. When performing two or more filtrations by combining different filters, the filters may be of the same type or different from each other, but the types are preferably different from each other. Typically, it is preferable that the first filter and the second filter differ in at least one of the pore size and constituent materials. It is preferable that the pore diameter after the second time is the same as that of the first filtration or smaller than that of the first filtration. Moreover, it is also possible to combine the 1st filter which differs in a pore diameter within the said range. The pore size can refer to the nominal value of the filter manufacturer. As a commercially available filter, it can select from various filters provided by NIHON PALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (Formerly Nippon Mykrolis Corporation), KITZ MICROFILTER CORPORATION, etc., for example. In addition, "P-Nylon filter (pore size: 0.02μm, critical surface tension: 77mN / m)" made of polyamide; (manufactured by NIHON PALL LTD.), "PE Clean filter (pore size: 0.02μm)”; (manufactured by NIHON PALL LTD.) and “PE・clean filter (pore size: 0.01μm)” made of high-density polyethylene; (manufactured by NIHON PALL LTD.).

[0127] As the second filter, a filter made of the same material as the above-mentioned first filter can be used. A filter having the same pore diameter as the above-mentioned first filter can be used. When using the pore size of the second filter smaller than that of the first filter, the ratio of the pore size of the second filter to the pore size of the first filter (pore size of the second filter / pore size of the first filter) is 0.01~ 0.99 is preferable, 0.1-0.9 is more preferable, 0.3-0.9 is still more preferable. By setting the pore size of the second filter within the above-mentioned range, it is possible to more reliably remove fine foreign matter mixed into the composition.

[0128] For example, after filtering a liquid mixture containing a part of the composition with the first filter and mixing the remaining components therein to prepare the composition, it is also possible to perform filtration with the second filter. Also, it is preferable that the filter used is treated before filtering the composition. The liquid used in this treatment is not particularly limited, but a liquid containing components contained in a composition, a concentrate, and a composition is preferable.

[0129] When performing filtration, the upper limit of the temperature during filtration is preferably below room temperature (25°C), more preferably below 23°C, and still more preferably below 20°C. Moreover, the lower limit of the temperature during filtration is preferably 0°C or higher, more preferably 5°C or higher, and still more preferably 10°C or higher. Filtration can remove particulate foreign matter and / or impurities, but if it is carried out at the above temperature, the amount of particulate foreign matter and / or impurities dissolved in the composition will be reduced, so filtering is more effective.

[0130] <Destaticization step> The above-mentioned manufacturing method may further include a destaticization step of destaticizing at least one selected from the group consisting of a composition, a concentrate, and a kit. In addition, the specific method about static elimination is mentioned later.

[0131] Moreover, all the steps of the above-mentioned manufacturing method are preferably carried out in a clean room. It is better if the clean room meets the 14644-1 clean room standard. It is preferable to satisfy any one of ISO (International Organization for Standardization) level 1, ISO level 2, ISO level 3, and ISO level 4, it is more preferable to satisfy ISO level 1 or ISO level 2, and it is still more preferable to satisfy ISO level 1.

[0132] <Container> The container for storing the above-mentioned composition, concentrate or kit is not particularly limited as long as the liquid is not corrosive, and known containers can be used. As the above-mentioned container, when used for semiconductor applications, the cleanliness inside the container is high and the elution of impurities is small. As a commercial item of the said container, the "Clean-Bottle" series by AICELLO CHEMICAL CO., LTD. and "Pure bottle" by KODAMA PLASTICS Co., Ltd. are mentioned, for example. In addition, for the purpose of preventing impurities from mixing (contaminating) raw materials and liquid medicines, a 6-layer structure of the container inner wall consisting of 6 types of resins, that is, a multi-layer container, and a 7-layer structure of the container inner wall consisting of 6 types of resins, that is, a multi-layer container, are used. Also better. Examples of such containers include those described in JP 2015-123351 A, but are not limited thereto. The inner wall of the container is made of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, resins different from them, and stainless steel, Hoechst alloy, and Inconel alloy. It is preferable to form or coat with metals such as Monel alloy.

[0133] As the above-mentioned different resins, fluorine-based resins (perfluororesins) can be preferably used. Thus, compared with the case of using a container whose inner wall is formed or coated with polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin, by using a container whose inner wall is formed of a fluorine-based resin or coated with a fluororesin , it is possible to suppress the generation of disadvantages such as elution of oligomers of ethylene or propylene. As a specific example of a container having such an inner wall, for example, a FluoroPure PFA composite column manufactured by Entegris, Inc., etc. are mentioned. In addition, it is also possible to use the 4th page of JP-A-3-502677, the 3rd page of the International Publication No. 2004 / 016526 pamphlet, and the 9th and 16th pages of the International Publication No. 99 / 46309 pamphlet. Recorded container.

[0134] Also, for the inner wall of the container, in addition to the above-mentioned fluorine-based resin, it is also preferable to use quartz and an electrolytically polished metal material (ie, an electrolytically polished metal material). The metal material used in the manufacture of the above-mentioned electropolished metal material contains at least one kind selected from the group including chromium and nickel, and the metal material whose total content of chromium and nickel exceeds 25% by mass relative to the total mass of the metal material Preferable examples include stainless steel, nickel-chromium alloys, and the like. The total content of chromium and nickel in the metal material is preferably 25% by mass or more, more preferably 30% by mass or more, based on the total mass of the metal material. In addition, the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but usually it is preferably 90% by mass or less.

[0135] The stainless steel is not particularly limited, and known stainless steels can be used. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable. Examples of austenitic stainless steel include SUS (Steel Use Stainless) 304 (Ni content: 8% by mass, Cr content: 18% by mass), SUS304L (Ni content: 9% by mass, Cr content: 18% by mass), SUS316 (Ni content: 10% by mass, Cr content: 16% by mass), SUS316L (Ni content: 12% by mass, Cr content: 16% by mass), and the like.

[0136] The nickel-chromium alloy is not particularly limited, and known nickel-chromium alloys can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferable. Examples of nickel-chromium alloys include Hoechst alloy (the same product name is hereinafter), Monel alloy (the same product name is hereinafter), Inconel alloy (the same product name is hereinafter), and the like. More specifically, Hoechst alloy C-276 (Ni content: 63% by mass, Cr content: 16% by mass), Hoechst alloy-C (Ni content: 60% by mass, Cr content content: 17% by mass), Hoechst alloy C-22 (content of Ni: 61% by mass, content of Cr: 22% by mass), and the like. In addition, the nickel-chromium alloy may contain boron, silicon, tungsten, molybdenum, copper, cobalt, etc. in addition to the above-mentioned alloys as needed.

[0137] The method of electropolishing the metal material is not particularly limited, and known methods can be used. For example, the methods described in paragraphs

[0011] -

[0014] of JP-A-2015-227501 and paragraphs

[0036] -

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

[0138] It is speculated that by performing electrolytic polishing on the metal material, the content of chromium in the passivation layer on the surface becomes larger than the content of chromium in the parent phase. Therefore, it is difficult to bleed out metal elements into the composition from the inner wall coated with the electropolished metal material, so it is presumed that a composition with a reduced specific metal element can be obtained. Furthermore, it is preferable that the metal material is polished. The polishing method is not particularly limited, and known methods can be used. The size of the abrasive grains used for fine polishing is not particularly limited, but #400 or less is preferable from the viewpoint that the unevenness on the surface of the metal material can be easily reduced. Furthermore, polishing is preferably performed before electrolytic polishing. In addition, metal materials can also be processed by combining one or two or more stages of polishing, acid cleaning, and magnetic fluid polishing performed by changing the size of abrasive grains.

[0139] The containers are preferably cleaned inside of the container prior to filling. The liquid used for cleaning may be appropriately selected depending on the application, but a liquid containing at least one of the above-mentioned composition, a liquid diluted from the above-mentioned composition, or a component added to the above-mentioned composition is preferable.

[0140] In order to prevent changes in the composition of the composition 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 higher. In particular, gas with a low water content is preferable. Also, the liquid container may be transported and stored at room temperature, but the temperature may be controlled within a range of -20°C to 20°C in order to prevent deterioration.

[0141] [Substrate processing method] In the substrate processing method using this composition (hereinafter also referred to as "this processing method"), the above-mentioned composition can typically be combined with a metal-based material having a metal-containing material. used for substrate contact. In this case, the substrate may contain a plurality of metal-based materials. Also, the composition can dissolve at least one of a plurality of metal-based materials that can be contained.

[0142] Metal-based materials have metal atoms (cobalt (Co), ruthenium (Ru), molybdenum (Mo), aluminum (Al), copper (Cu), titanium (Ti), tungsten (W) and / or tantalum (Ta ) etc.), for example, single metals, alloys, metal oxides (may be composite oxides) and metal nitrides (may be composite nitrides). In addition, as the metal-based material included in the substrate, at least one material selected from the group consisting of simple metals, alloys, metal oxides, and metal nitrides, and materials selected from the group consisting of metal oxides as dopants can also be mentioned. A material of at least one element of the group of carbon, nitrogen, boron, and phosphorus. The content of metal atoms in the metal-based material is preferably from 30 to 100% by mass, more preferably from 40 to 100% by mass, and still more preferably from 50 to 100% by mass, based on the total mass of the metal-based material. When the metal-based material contains the above-mentioned dopant, the content of the metal-atom dopant is preferably 0.1-50% by mass, more preferably 10-40% by mass, based on the total mass of the metal-based material. Also, in this case, the content of the metal atoms in the metal-based material is preferably 30 to 99.9% by mass, more preferably 60 to 90% by mass, based on the total mass of the metal-based material. [Method for cleaning substrate] As this processing method, there may be mentioned a method for cleaning a substrate having a cleaning step B of cleaning a substrate having a metal layer using the composition described above (hereinafter, also referred to simply as "cleaning method"). . The cleaning method of the above-mentioned substrate may also include the composition manufacturing step A of preparing the above-mentioned composition before the cleaning step B. In the following description of the cleaning method of the substrate, the case where the composition manufacturing step A is performed before the cleaning step B is shown as an example, but the present invention is not limited thereto, and the cleaning of the substrate can be performed using the above-mentioned composition prepared in advance. [Object to be cleaned] The object to be cleaned by the cleaning method is not particularly limited as long as it is a substrate having a metal layer, and a substrate having a metal layer containing at least Co or W is preferred. Also, as the object to be cleaned, a substrate having a metal layer containing Cu is also preferable, and a substrate including a SiOx layer in addition to the metal layer is also preferable. Examples of the object to be cleaned include, for example, a laminate including at least a metal layer, an interlayer insulating film, and a metal hard mask in this order on a substrate. The laminate may have a hole formed from the surface (opening) of the metal hard mask toward the substrate by exposing the surface of the metal layer through a dry etching step or the like. The manufacturing method of the above-mentioned laminated body having holes is not particularly limited, and generally, the following method is used, that is, a metal hard mask is used as a mask to sequentially have a substrate, a metal layer, and an interlayer insulating film. and the treatment of the metal hard mask. The laminated body is subjected to a dry etching step, and the interlayer insulating film is etched to expose the surface of the metal layer, so as to form a hole penetrating through the metal hard mask and the interlayer insulating film. . Furthermore, the manufacturing method of the metal hard mask is not particularly limited, for example, the following method is mentioned: firstly, a metal layer containing a predetermined composition is formed on the interlayer insulating film, and a photoresist film with a predetermined pattern is formed thereon. Next, using the photoresist film as a mask, the metal layer is etched, thereby producing a metal hard mask (ie, a film in which the metal layer is patterned). In addition, the laminate may have layers other than the above-mentioned layers, for example, may have layers such as an etching stopper film, a barrier layer, and / or an antireflection layer.

[0145] FIG. 1 shows a schematic cross-sectional view of an example of a laminate that is an object to be cleaned in the method for cleaning the substrate described above. The laminated body 10 shown in FIG. 1 has a metal layer 2, an etch stop layer 3, an interlayer insulating film 4, and a metal hard mask 5 sequentially on a substrate 1, and a metal layer is formed at a specific position through a dry etching step. The hole 6 of the metal layer 2 is exposed. That is, the object to be cleaned shown in FIG. 1 is a laminated body comprising a substrate 1, a metal layer 2, an etch stop layer 3, an interlayer insulating film 4, and a metal hard mask 5 in this order. A hole 6 penetrating from the surface to the surface of the metal layer 2 is provided at the position of the opening. The inner wall 11 of the hole 6 is composed of a section wall 11a composed of the etching stop layer 3, an interlayer insulating film 4, and a hard metal mask 5, and a bottom wall 11b composed of the exposed metal layer 2. Formula etching residue 12.

[0146] The cleaning method can be preferably used for cleaning for the purpose of removing the dry etching residue 12. That is, the dry etching residue 12 is excellent in removal performance (residue removability) and also excellent in corrosion resistance against the inner wall 11 of the object to be cleaned (for example, the metal layer 2 , etc.). Moreover, the cleaning method of the said board|substrate can also be implemented to the laminated body which performed the dry ashing process after a dry etching process. Hereinafter, the materials constituting each layer of the above-mentioned laminate will be described.

[0147] <Metal Hard Mask> The metal hard mask contains at least one material selected from the group consisting of copper, cobalt, cobalt alloy, tungsten, tungsten alloy, ruthenium, ruthenium alloy, tantalum, tantalum alloy, aluminum oxide, aluminum nitride, nitrogen Compositions in the group of aluminum oxide, titanium aluminum oxide, titanium, titanium nitride, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide and yttrium alloy (preferably YSiOx) are preferred. Among them, x and y are preferably numbers represented by x=1-3 and y=1-2 respectively. Examples of materials for the metal hard mask include TiN, WO2, and ZrO2.

[0148] <Interlayer insulating film> The material of the interlayer insulating film is not particularly limited, and for example, one having a dielectric constant k of 3.0 or less, more preferably 2.6 or less is used. Specific examples of materials for the interlayer insulating film include organic polymers such as SiOx, SiN, SiOC, and polyimide. Furthermore, x is preferably a number represented by 1-3.

[0149] <Etching Stop Layer> The material of the etching stop layer is not particularly limited. Specific materials of the etching stop layer include SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx. Furthermore, x is preferably a number represented by 1-3.

[0150] <Metal layer> The material forming the metal layer as the wiring material and / or plug material is not particularly limited, and it is preferably one or more selected from the group consisting of cobalt, tungsten, molybdenum, and copper. . In addition, the material forming the metal layer may be cobalt, tungsten, molybdenum, or an alloy of copper and other metals. The metal layer may also include metals other than cobalt, tungsten, molybdenum, and copper, metal nitrides, and / or alloys. Examples of metals other than cobalt, tungsten, molybdenum, and copper that may be contained in the metal layer include titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxide, and aluminum. The metal layer may contain at least one dopant selected from the group consisting of carbon, nitrogen, boron, and phosphorus in addition to one or more types selected from the group consisting of cobalt, tungsten, molybdenum, and copper.

[0151] <Substrate> The "substrate" mentioned here includes, for example, a semiconductor substrate composed of a single layer and a semiconductor substrate composed of multiple layers. The material constituting the single-layer semiconductor substrate is not particularly limited, and generally silicon, silicon germanium, Group III-V compounds such as GaAs, or any combination thereof are preferred. In the case of a semiconductor substrate composed of multiple layers, its structure is not particularly limited. For example, exposed integrated bodies such as metal lines and interconnect features of dielectric materials may also be provided on the above-mentioned silicon and other semiconductor substrates. circuit structure. As metals and alloys used in interconnection structures, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten can be mentioned, but are not limited to these . In addition, layers such as an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide may be provided on the semiconductor substrate.

[0152] (Barrier layer) The laminate may have a barrier layer. The barrier layer is a layer formed between a metal layer serving as a wiring material and / or a plug material provided on a substrate and an interlayer insulating film, and is used to prevent diffusion of a wiring material and / or a plug material. layer (membrane). As the material of the barrier layer, low-resistance metal materials can be mentioned, preferably containing at least one selected from the group consisting of tantalum or tantalum compounds, titanium or titanium compounds, tungsten or tungsten compounds, and ruthenium. At least one of the group consisting of TiN, TiW, Ta, TaN, W, WN, and Ru is more preferable, and TiN is still more preferable.

[0153] The method of manufacturing the object to be cleaned is not particularly limited as long as it is a known method in the field of semiconductor substrates. Examples of methods for forming a metal layer (metal-containing film or metal-containing wiring) on ​​a substrate include sputtering, physical vapor deposition (PVD: Physical Vapor Deposition), and atomic layer deposition (ALD: Atomic Layer Deposition). method, chemical vapor deposition (CVD: Chemical Vapor Deposition) method and molecular beam epitaxy (MBE: Molecular Beam Epitaxy) method. Furthermore, when the metal-containing film is formed by sputtering, PVD, ALD, CVD, etc., the back surface of the substrate having the metal-containing film (the surface opposite to the side of the metal-containing film) may be Metallic objects are also attached. In addition, the above-mentioned method may be implemented through a predetermined mask to form metal-containing wiring on the substrate. In addition, after the metal layer is formed on the substrate, the substrate may be used as an object to be processed in this processing method after being subjected to a different step or treatment. For example, a substrate having a metal layer can also be subjected to dry etching to manufacture a substrate having dry etching residues containing metal. Dry etching residues are by-products produced by performing dry etching such as plasma etching, and examples include organic residues from photoresists, Si-containing residues from interlayer insulating films, and metal-containing residues. residue. Also, a substrate having a metal layer may be provided to CMP to manufacture a substrate having a metal-containing object.

[0154] Hereinafter, the method for cleaning the substrate will be described step by step.

[0155] [Composition Manufacturing Step A] The composition manufacturing step A is a step of preparing the above-mentioned composition. The components used in this step are as described above. In addition, the details of this step are as described in the above-mentioned column of [Production Method of Composition]. The order of this step is not particularly limited, for example, a method of preparing a composition by stirring and mixing specific ingredients can be mentioned. In addition, each component may add collectively, and may divide and add in plural times. In addition, each component contained in the composition is classified into a semiconductor level or a high-purity level based on it, and the foreign matter removal by filtration and / or the reduction of ion components by ion exchange resin, etc. are used. better. In addition, after mixing the raw material components, it is preferable to further perform removal of foreign matter by filtration and / or reduction of ion components by ion exchange resin or the like.

[0156] Also, when the composition is a concentrated solution, before performing the cleaning step B, the concentrated solution is diluted 5 to 2000 times to obtain a diluted solution, and then the cleaning step B is performed using the diluted solution. As a solvent for diluting the concentrate, at least one selected from the group consisting of water, alcohol, and aprotic polar solvent contained in the composition is preferable. [Cleaning step B] As the cleaning object to be cleaned in the cleaning step B, the above-mentioned laminate can be mentioned, and more specifically, a product having a compound selected from the group consisting of Co and W can be mentioned. A substrate with a metal layer of at least one metal. In addition, as an object to be cleaned, a laminate 10 (see FIG. 1 ) in which holes are formed by performing the dry etching step as described above can be exemplified. Furthermore, in this laminated body 10 , dry etching residue 12 adheres to the inside of hole 6 . In addition, after the dry etching step, the laminate subjected to the dry ashing step may also be used as an object to be cleaned.

[0158] The method of contacting the composition with the object to be cleaned is not particularly limited, for example, the method of immersing the object to be cleaned in the composition placed in a container such as a tank, and spraying the composition on the object to be cleaned The method, the method of flowing the composition on the object to be cleaned, and any combination thereof. From the viewpoint of residue removability, the method of immersing the object to be cleaned in the composition is preferable.

[0159] The temperature of the composition is preferably below 90°C, more preferably 25-80°C, further preferably 30-75°C, and particularly preferably 40-65°C.

[0160] The cleaning time can be adjusted according to the cleaning method used and the temperature of the composition. In the case of cleaning by batch immersion method (batch method in which multiple pieces of objects to be cleaned are dipped in a treatment tank for treatment), the cleaning time is, for example, within 90 minutes, preferably 10 to 90 minutes, and 5 to 60 minutes More preferably, 10 to 45 minutes is still more preferable.

[0161] In the case of cleaning with a single chip, the cleaning time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, and 20 seconds to 2 minutes for further improvement.

[0162] In addition, in order to further enhance the cleaning ability of the composition, a mechanical stirring method can also be used. Examples of mechanical agitation methods include a method of circulating the composition on the object to be cleaned, a method of flowing or spraying the composition on the object to be cleaned, and a method of agitating the composition with ultrasonic or megafrequency. [Rinsing step B2] The substrate cleaning method of the present invention may further include a step of washing the object to be cleaned with a solvent after the cleaning step B (hereinafter referred to as "rinsing step B2"). Rinsing step B2 and cleaning step B are carried out continuously, and the step of rinsing with a rinsing solvent (rinsing solution) for 5 seconds to 5 minutes is preferred. The rinsing step B2 can also be carried out using the above-mentioned mechanical agitation method.

[0164] As the rinse solvent, for example, deionized water (DIW), methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethylsulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. As a solvent for the rinse solution, DIW, methanol, ethanol, isopropanol or a mixture thereof is preferred, and DIW, isopropanol or a mixture of DIW and isopropanol is more preferred.

[0165] As the method of bringing the rinse solvent into contact with the object to be cleaned, the method of bringing the above-mentioned composition into contact with the object to be cleaned can also be applied in the same manner. The temperature of the rinsing solvent in the rinsing step B2 is preferably 10-40°C.

[0166] [Drying Step B3] The substrate cleaning method of the present invention may include a drying step B3 of drying the object to be cleaned after the rinsing step B2. The drying method is not particularly limited. As the drying method, for example, spin drying method, method of flowing dry gas over the object to be cleaned, method of heating the substrate by a heating mechanism such as a heating plate or an infrared lamp, Marangoni drying method, Nuo Tagani drying, IPA (isopropanol) drying, and any combination of these. The drying time in the drying step B3 depends on the specific drying method, preferably 20 seconds to 5 minutes. The heating temperature for drying by heating the substrate is not particularly limited, for example, it is 50-350°C, preferably 150-250°C. [Coarse Particle Removal Step H] It is preferable that the cleaning method of the substrate includes a coarse particle removal step H for removing coarse particles in the composition after the composition production step A and before the cleaning step B. By reducing or removing the coarse particles in the composition, the amount of coarse particles remaining on the object to be cleaned after the cleaning step B can be reduced. As a result, damage to the pattern due to coarse particles on the object to be cleaned can be suppressed, and the influence of reduced yield and reduced reliability of devices can also be suppressed. Specific methods for removing coarse particles include, for example, a method of filtering and purifying the composition obtained through the composition production step A using a particle-removing membrane having a specific particle-removing diameter. It should be noted that the definition of coarse particles is as described above. [Destaticization steps I, J] The cleaning method of the above-mentioned substrate comprises the step I of destaticizing the water used to prepare the composition before the above-mentioned composition manufacturing step A and the above-mentioned composition manufacturing step. After the step A and before the cleaning step B, at least one step in the group of the static elimination step J for eliminating the static electricity of the composition is preferred. The material of the liquid contact portion for supplying the composition to the object to be cleaned is preferably formed or coated with a material that does not elute metal from the composition. Examples of the above-mentioned material include those described as materials that can be used for the inner wall of the container of the liquid container. Furthermore, the above-mentioned material may be resin. In the case where the above-mentioned material is resin, the resin often has low electrical conductivity and is insulating. Therefore, for example, when the above-mentioned composition is passed through a pipe whose inner wall is formed or coated with resin, or when it is filtered and purified through a resin-made particle removal membrane and a resin-made ion-exchange resin membrane, the charge potential of the composition increase and there is a risk of causing an electrostatic disaster. Therefore, in the cleaning method of the substrate of the present invention, it is preferable to implement at least one of the above-mentioned static elimination step I and static elimination step J to lower the charge potential of the composition. In addition, by performing static elimination, it is possible to further suppress adhesion of foreign matter (coarse particles, etc.) to the substrate and / or damage (corrosion) to the object to be cleaned. As a static elimination method, the method of bringing water and / or a composition into contact with a conductive material is mentioned specifically,. The contact time for bringing water and / or the composition into contact with the conductive material is preferably 0.001 to 1 second, more preferably 0.01 to 0.1 second. Examples of resins include high-density polyethylene (HDPE), high-density polypropylene (PP), 6,6-nylon, tetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether ( PFA), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), ethylene-tetrafluoroethylene copolymer (ETFE) and tetrafluoroethylene-hexafluoropropylene copolymer (FEP) . Examples of the conductive material include stainless steel, gold, platinum, diamond, and glassy carbon.

[0169] The cleaning method of the substrate comprises: a composition manufacturing step A, a cleaning step B, a drainage recovery step C of recovering the drainage of the composition used in the cleaning step B, and a drainage cleaning step using the recovered composition. The cleaning step D of the prepared substrate having a specific layer and the drainage recovery step E of recovering the drainage of the above-mentioned composition used in the cleaning step D may also be repeated implementation of the cleaning step D and the drainage recovery step E to recover the substrate cleaning method of the drain of the above composition.

[0170] In the substrate cleaning method described above, aspects of the composition production step A and the cleaning step B are as described above. In addition, it is preferable to have the above-mentioned coarse particle removal step H and static electricity removal steps I and J in the aspect of reusing the above-mentioned discharged liquid.

[0171] The aspect of the cleaning step D in which the substrate is cleaned using the drain of the recovered composition is described as the cleaning step B. The drainage recovery mechanism in the drainage recovery steps C and E is not particularly limited. It is preferable to store the recovered effluent in the above-mentioned container in the above-mentioned de-static step J, and the same de-static step as the de-static step J can also be performed at this time. In addition, a step of removing impurities by filtering the recovered effluent may also be provided. [Example]

[0172] Hereinafter, the present invention will be described in further detail based on examples. Materials, usage amounts, proportions, processing contents, processing order, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. However, the scope of the present invention is not limitedly interpreted by the Examples shown below. [Examples 1 to 30, Comparative Example 1] [Preparation of Composition] The components listed in Table 1 were prepared, added and mixed at the blending ratios listed in Table 1, and Examples and Comparative Examples were prepared. Each composition of the example. Furthermore, in each composition, the contents of each component (all are based on mass) are as described in the table. Among them, the various components shown in Table 1 were classified into semiconductor grades or those classified into high-purity grades based on them.

[0174] <Components> Various components listed in Table 1 are shown below.

[0175] (alcohol) ・Tertiary butanol・1-butanol・2-butanol・cyclopentanol・ethanol・2-propanol (IPA) ・Diethylene glycol monobutyl ether (DEGBE) ・tetrahydrofurfuryl alcohol (THFA)

[0176] (Aprotic polar solvents (referred to as "specific solvents" in the table)) ・Dimethylsulfone (DMSO) ・Cyclobutane

[0177] (azole compound) ・1,2,4-triazole ・1H-benzotriazole ・tolyltriazole

[0178] (alkanolamine) ・2-aminoethanol ・diethanolamine ・2-(2-aminoethoxy)ethanol (AEE)

[0179] (Water) ・Deionized water (DIW)

[0180] (Component A) ・Dipropylene ・2-Cyclobutene

[0181] [Evaluation] [Residue Removability] A laminate was prepared in which a SiO2 film with a thickness of 100 nm, a metal hard mask (TiN) and a photoresist film were sequentially laminated on a substrate (Si). This laminate was subjected to patterning by lithography, dry etching using a plasma etching device for metal, and removal of the photoresist film by oxygen plasma ashing to fabricate a metal hard mask. A laminate for evaluation tests with a predetermined opening. Using the obtained laminate, plasma etching was performed using a metal hard mask as a mask with a gas containing fluorine, and the SiO2 film was etched by about 50 nm, thereby manufacturing a grid-like pattern with a square of 2 cm. Test piece for evaluation test. When the etched bottom surface was analyzed by X-ray photoelectron spectroscopy (XPS: X-ray Photoelectron Spectroscopy), fluorine presumably derived from dry etching residue was detected. It is presumed that the dry etching residue formed by plasma etching using the gas containing fluorine mentioned above is an organic / inorganic mixed residue having Si and O derived from SiO2 and C and F derived from the etching gas.

[0182] Next, the residue removability of each composition was evaluated in the following order. A 500-mL glass beaker was filled with 200 mL of the composition. Stirring was performed using a stir bar and the temperature of the composition was raised to 40°C. Next, while stirring, the test piece prepared above was immersed in a composition having a liquid temperature of 40° C. for 2 minutes, thereby cleaning the test piece. While immersing the test piece in the composition, the test piece was held with 4-inch-long plastic locking tweezers so that the surface of the side from which the residue of the test piece was removed faced the stirring bar.

[0183] Immediately after the cleaning time, the test piece was taken out from the composition, filled in a plastic beaker with a capacity of 500mL, and placed in 400mL of DI water (water temperature 20°C) that was stirred stably. While immersing the test piece in DI water, the test piece was held with 4-inch-long plastic locking tweezers so that the surface of the side from which the residue of the test piece was removed faced the stirring bar. Immediately after immersing the test piece in DI water for 30 seconds, the test piece was taken out and rinsed under 20° C. DI water flow for 30 seconds. During rinsing of the test piece under the DI water flow, the test piece was held using 4-inch length plastic locking tweezers with the surface of the side from which the residue of the test piece was removed facing the DI water flow. Next, the surface of the test piece was dried by exposing the test piece to a nitrogen stream to blow off the liquid droplets adhering to the surface of the test piece. After this nitrogen gas drying step, the test piece was removed from the holding portion of the plastic tweezers, and the test piece was placed in a plastic storage box with a lid with the device side up, and stored.

[0184] The composition analysis of the surface of the obtained test piece was carried out by XPS. The surface of the test piece was measured using an XPS device (manufactured by Ulvac-PHI, product name QuanteraSXM), and the residue removability was evaluated from the measurement results of the fluorine atom content (atomic %) of the dry etching residue on the surface of the test piece. (removability of dry etching residue). It can be said that when the atomic weight of fluorine on the surface of the test piece is small, the residue removability is excellent, and when the atomic weight of fluorine is large, the residue removability is poor.

[0185] (Residue Removability Evaluation Criteria) A: The content of fluorine atoms on the surface of the test piece is less than 1 atomic % B: The content of fluorine atoms on the surface of the test piece is 1 atomic % or more and less than 1.5 atomic % C: The content of fluorine atoms on the surface of the test piece is 1.5 atomic % or more and less than 2.5 atomic % D: The content of fluorine atoms on the surface of the test piece is 2.5 atomic % or more

[0186] [Corrosion Resistance] A substrate in which a cobalt-containing film (Co film) was formed on one surface of a commercially available silicon wafer (diameter: 12 inches) by a CVD (Chemical Vapor Deposition) method was prepared. The thickness of the formed Co film was 30 nm. The etching process of the obtained Co film was performed using each composition of an Example and a comparative example. Specifically, after immersing the Co film in the compositions of Examples and Comparative Examples for 10 minutes, rinsing treatment by immersing in pure water for 15 seconds was performed twice, and then, the substrate was dried with nitrogen gas. The etching rate (Å / min) was calculated from the film thickness difference of the Co film before and after immersion in the composition. The corrosion resistance of the composition was evaluated by measuring the etching rate of each film. It can be said that when the etching rate is low, the corrosion resistance is excellent, and when the etching rate is high, the corrosion resistance is poor.

[0187] In the same manner as above, prepare substrates having a film containing W (W film), a film containing TiN (TiN film), a film containing AlOx (AlOx film), and a film containing Mo (Mo film). , each substrate was immersed in each composition, and the etching rate (Å / min) of each film was measured. Furthermore, the W film, the TiN film, and the AlOx film are formed by a CVD method, and the Mo film is formed by a PVD (Physical Vapor Deposition, physical vapor deposition) method.

[0188] Furthermore, the thickness of each film formed on the substrate was measured by the following method. The thicknesses of the Co film, the W film, and the TiN film were measured by a fluorescent X-ray analysis device (“AZX400” manufactured by Rigaku Corporation) by a fluorescent X-ray analysis method (XRF: X-ray Fluorescence method). The thickness of the AlOx film was measured using ellipsometry (Spectroscopic ellipsometer, product name "Vase", manufactured by J.A. Woollam Japan Co., Inc.) under the conditions of a measurement range of 250-1000 nm and a measurement angle of 70 degrees and 75 degrees. Measurement. The thickness of the Mo film was measured by a 4-terminal method using a specific resistance measuring device (“VR300DE” manufactured by Kokusai Electric Semiconductor Service Inc.). Table 1 summarizes the respective measurement results.

[0189] [Defect suppression] The number of particles with a diameter of 19 nm or more existing on the surface of a silicon substrate (wafer) with a diameter of 300 mm and The address of each particle. Then, the above-mentioned wafer whose number of particles existing on the surface of the silicon substrate was measured was set on a rotary wafer processing apparatus (manufactured by Ekc Technologies, Inc.). Next, the respective compositions of Examples and Comparative Examples adjusted to 40° C. were discharged to the surface of the installed wafer at a flow rate of 1.5 L / min for 1 minute. Thereafter, water was discharged onto the surface of the wafer at a flow rate of 1 L / min for 1 minute to perform spin drying of the wafer. With regard to the obtained dried wafer, the number and address of particles with a diameter of 19 nm or more on the wafer were measured using a wafer surface inspection device, and the number of particles with a diameter of 19 nm or more increased before and after cleaning using each composition was measured. Table 1 shows the measurement results of the increased number of particles having a diameter of 19 nm or more.

[0190] Table 1 below shows the composition and evaluation results of the compositions used in each of the examples and each of the comparative examples. In the table, the "ratio 1" column shows the ratio of the content of the azole compound to the content of component A in each composition (azole compound / component A) by mass ratio, and the column "ratio 2" shows the ratio by mass ratio The ratio of the content of the protic polar solvent to the content of component A in each composition (aprotic polar solvent / component A). For example, the display of "5.0E+04" in the column of "Ratio 1" in Example 8 means that the above-mentioned ratio 1 (azole compound / component A) is "5.0×104" in terms of mass ratio. The column of "pH" shows the pH at 25° C. of each composition measured with a pH meter.

[0191] [Table 1] Table 1 (1) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Composition alcohol Tertiary butanol 65.0 60.0 52.0 60.0 49.0 67.0 65.0 1-butanol 2-butanol Cyclopentanol 65.0 ethanol 65.0 IPA 65.0 DEGBE THFA specific solvent DMSO cyclotin 10.0 10.0 10.0 18.0 10.0 10.0 1.0 10.0 10.0 10.0 Azole compound 1,2,4-triazole 1.0 1.0 1.0 3.0 0.2 3.0 1.0 5.0 6.0 1.0 1H-Benzotriazole Tolyltriazole alkanolamine 2-aminoethanol 1.0 2.6 3.0 6.2 0.2 6.2 1.5 6.2 6.2 1.7 Diethanolamine AEE DIW 23.0 26.4 21.0 20.8 29.6 31.8 31.5 11.8 12.8 22.3 Component A Dipropylene 2-Cyclobutene 100ppm 300ppm Ratio 1 5.0E+04 2.0E+04 Ratio 2 1.0E+05 3.3E+04 pH 10.25 10.50 10.60 10.50 9.20 10.50 10.30 10.50 10.50 10.40 evaluate Residue removal A A A A A A A A A A Corrosion resistance (Å / min) co 0.6 0.6 0.8 1.5 2.2 1.5 0.6 1.5 0.3 0.5 W 3.4 4.2 4.9 4.5 2.2 5.3 4.8 4.5 4.4 4.8 TiN 0.4 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 AlOx 1.4 2.4 2.4 1.8 0.6 1.8 2.0 1.8 1.8 2.0 Mo 137.2 158.0 161.0 113.2 N.D. 113.2 N.D. N.D. N.D. N.D. defect suppression 301 251 298 401 332 318 265 139 1511 298

[0192] [Table 2] Table 1 (2) Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Composition alcohol Tertiary butanol 65.0 60.0 78.0 60.0 65.0 65.0 60.0 60.0 60.0 1-butanol 55.0 2-butanol Cyclopentanol ethanol IPA DEGBE THFA specific solvent DMSO 10.0 10.0 10.0 10.0 cyclotin 10.0 10.0 0.5 10.0 10.0 10.0 Azole compound 1,2,4-triazole 1.0 0.2 1.0 3.0 0.2 0.2 0.2 1.0 1H-Benzotriazole 0.1 0.3 Tolyltriazole alkanolamine 2-aminoethanol 2.6 0.5 2.0 2.6 6.2 1.0 9.0 9.0 Diethanolamine 1.9 2.0 AEE DIW 21.4 29.3 10.0 37.2 21.4 15.8 28.8 20.8 20.8 32.0 Component A Dipropylene 2-Cyclobutene 10ppm 10ppm 10ppt 1000ppm 100ppt Ratio 1 1.0E+05 1.0E+04 1.0E+11 3.0E+03 2.0E+09 Ratio 2 1.0E+06 1.0E+06 1.0E+12 1.0E+04 1.0E+11 pH 10.50 9.50 10.50 10.30 10.50 10.50 10.00 10.90 10.90 10.40 evaluate Residue removal A A A A A A A A A A Corrosion resistance (Å / min) co 0.6 1.5 2.3 0.3 2.7 1.3 1.5 0.7 0.7 0.6 W 4.2 3.0 4.1 8.0 4.2 4.1 6.0 8.0 7.0 3.8 TiN 0.2 0.3 0.3 0.2 0.2 0.2 0.3 0.3 0.3 0.3 AlOx 2.4 1.0 N.D. 6.2 2.4 1.8 1.8 4.0 4.5 1.9 Mo N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. defect suppression 101 299 156 301 189 1060 287 201 366 319

[0193] [Table 3] Table 1 (3) Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Comparative example 1 Composition alcohol Tertiary butanol 41.0 60.0 60.0 52.0 35.0 75.0 1-butanol 60.0 60.0 2-butanol 40.0 Cyclopentanol ethanol IPA DEGBE 50.0 THFA 50.0 specific solvent DMSO 15.0 cyclotin 10.0 10.0 11.0 10.0 10.0 10.0 10.0 18.0 10.0 Azole compound 1,2,4-triazole 3.0 1.0 3.0 1.0 3.0 1.0 1H-Benzotriazole 0.5 0.1 0.3 0.3 Tolyltriazole 0.2 alkanolamine 2-aminoethanol 1.0 1.0 1.0 0.2 12.0 1.0 Diethanolamine 8.1 1.9 1.9 AEE 2.0 2.5 DIW 37.9 47.0 26.6 28.0 27.3 21.0 38.0 26.8 42.7 23.0 Component A Dipropylene 10ppm 2-Cyclobutene 10ppb 10ppm Ratio 1 5.0E+04 1.0E+04 3.0E+05 Ratio 2 1.1E+09 l.0E+06 1.5E+06 pH 10.70 10.40 10.50 10.50 10.30 10.00 10.10 10.30 8.50 11.30 10.25 evaluate Residue removal A A A A A A B B A A D. Corrosion resistance (Å / min) co 1.5 2.7 0.6 0.6 0.4 0.7 3.1 1.2 7.0 0.3 5.0 W 4.1 6.0 4.1 4.1 3.4 5.0 5.5 4.1 2.5 11.0 3.4 TiN 0.4 0.2 0.3 0.3 0.4 0.3 0.2 0.2 0.2 0.2 0.4 AlOx 2.1 N.D. N.D. N.D. N.D. 1.8 2.1 2.3 0.8 6.2 1.4 Mo N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. 89.0 N.D. 137.2 defect suppression 309 401 105 167 341 186 405 332 368 387 387

[0194] From the results in Table 1, it was confirmed that the composition of this invention is more excellent in the effect of the present invention than the composition of each comparative example.

[0195] It was confirmed that when the main chain skeleton of the alcohol is a main chain skeleton containing an aliphatic hydrocarbon group or does not have a ring structure, the residue removal property and Co corrosion resistance are more excellent (comparison of Examples 1 to 28) . It was confirmed that when pH is 9-11, Co corrosion resistance and W corrosion resistance are more excellent (comparison of Examples 1-30).

[0196] [Examples 31-41] [Preparation of Composition] Prepare tertiary butanol, cyclobutane, 1,2,4-triazole, 2-aminoethanol, deionized water and the following The chelating agent of Table 2 was mixed to prepare each composition of Examples 31-41. The contents of tertiary butanol, cyclobutane, 1,2,4-triazole, and deionized water contained in each composition of Examples 31 to 41 were the same as those in the composition of Example 2 in Table 1. The content of each ingredient contained is the same. The content of 2-aminoethanol was adjusted so that the pH of each composition of Examples 31 to 41 became the value described in the "pH" column of Table 2. Moreover, the kind and content of the chelating agent contained in each composition are shown in Table 2.

[0197] The chelating agents used to prepare the compositions of Examples 31 to 41 are shown below. As the chelating agent, a compound classified as a semiconductor grade or a compound classified as a high-purity grade equivalent thereto was used.

[0198] (chelating agent) ・CA1: ethylenediaminetetraacetic acid ・CA2: ethylenediaminepentaacetic acid ・CA3: citric acid ・CA4: N,N,N',N'-ethylenediaminetetra(methylene phosphonic acid) ・CA5: gluconic acid ・CA6: malonic acid ・CA7: iminodiacetic acid [Evaluation] Regarding the compositions of Examples 31 to 41 and the composition of Reference Example 2, the residue removal performance, corrosion resistance and defect suppression performance were evaluated. Regarding the evaluation of the residue removal property, the time for immersing the produced test piece in each composition at a liquid temperature of 40°C was changed from 2 minutes to 1 minute. In addition, the production, procedure, analysis method and evaluation standard of the test piece were also included. , was evaluated by the same method as the method for evaluating the residue removability of the compositions of Examples 1 to 30. Moreover, regarding the evaluation of corrosion resistance and defect suppression, it evaluated by the method similar to the evaluation method of the composition of Examples 1-30.

[0200] Table 2 shows the evaluation results of the compositions of the respective examples. The meaning of each column in Table 2 other than the column of "chelating agent" is the same as that of Table 1.

[0201] [Table 4] Table 2 Example 2 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Composition Chelating agent CA1 0.1 1 5 CA2 0.1 0.05 0.1 CA3 0.1 CA4 0.1 CA5 0.1 CA6 0.1 CA7 0.1 0.1 pH 10.50 10.50 10.50 10.50 10.50 10.50 10.50 10.50 10.50 10.50 10.50 10.50 evaluate Residue removal B A A A A A A A A A A A Corrosion resistance (Å / min) co 0.6 0.4 0.5 0.6 0.4 0.5 0.4 0.5 0.7 0.7 0.5 0.6 W 4.2 4.1 3.8 5.0 3.2 3.4 4.9 5.2 3.4 5.2 5.4 5.2 TiN 0.2 0.4 0.5 0.3 0.3 0.2 0.3 0.4 0.4 0.4 0.6 0.4 AlOx 2.4 2.1 2.3 2.2 2.5 2.2 2.3 2.3 2.3 2.4 2.5 2.3 Mo 158.0 163.0 142.0 180.0 121.0 155.0 167.0 189.0 173.0 157.0 171.0 189.0 defect suppression 251 220 215 226 298 311 229 256 301 255 211 265

[0202] As shown in Table 2, it was confirmed that the compositions of Examples 31 to 41 had good residue removal properties as in Example 2. Therefore, it can be seen that the compositions of Examples 31 to 41 are more excellent in residue removal performance than the composition of Comparative Example 1. Also, when the composition contains a chelating agent, compared with the composition of Example 2, the evaluation result of the residue removal property is A even if it is immersed for a short time, so it is confirmed that the residue removal property is more excellent (Example 2 2 and 31-41 comparison). Moreover, it was also confirmed that it was excellent similarly to Example 2 about the evaluation result of corrosion resistance and defect suppression property.

[0203] [Examples 42 to 45] [Preparation of Compositions] The compositions of Examples 42 to 45 were prepared by the following procedure. In addition, the same thing as the chelating agent used for the preparation of the composition of Examples 31-41 was used for a chelating agent. The description of each chelating agent is also the same as above.

[0204] In the formula of Example 11, the content of deionized water is adjusted, and 0.1% by mass of CA1 is added as a chelating agent, and the pH of the composition is adjusted to 10.5 by the content of 2-aminoethanol. In the same manner as the composition of Example 11, the composition of Example 42 was prepared. In the formulation of Example 42, the composition of Example 43 was adjusted in the same manner as in Example 42 except that the chelating agent was changed to 1.0% by mass of CA1. In the formulation of Example 42, the composition of Example 44 was adjusted in the same manner as in Example 42 except that the chelating agent was changed to 0.1% by mass of CA3. In the formulation of Example 42, the composition of Example 45 was adjusted in the same manner as in Example 42 except that the chelating agent was changed to a mixture of 0.05% by mass of CA2 and 0.05% by mass of CA6.

[0205] [Evaluation] The composition of Examples 42 to 45 and the composition of Example 11 for reference were evaluated by the same method as the evaluation method of residue removal in the composition of Examples 31 to 41. Residue removal. It was confirmed that the compositions of Examples 42 to 45 had less fluorine atom content on the surface of the test piece and better residue removability than the composition of Example 11. Moreover, as a result of evaluating the corrosion resistance and defect suppression by the same method as the evaluation method of the composition of Examples 1-30, it was confirmed that it was excellent similarly to the composition of Example 11. [Simple description of the diagram]

[0010] FIG. 1 is a schematic cross-sectional view showing an example of a laminate as an object to be cleaned as a substrate cleaning method.

Claims

1. A composition for a semiconductor device, comprising an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, and water, wherein the aforementioned alcohol comprises a monool having a main chain backbone containing aliphatic hydrocarbon groups and alcoholic hydroxyl groups, or a polyol having a main chain backbone containing aliphatic hydrocarbon groups and alcoholic hydroxyl groups. The content of the aforementioned alcohol is 50-80% by mass relative to the total mass of the aforementioned semiconductor device composition, the content of the aforementioned aprotic polar solvent is 1-20% by mass relative to the total mass of the aforementioned semiconductor device composition, the content of the aforementioned azole compound is 0.1-5% by mass relative to the total mass of the aforementioned semiconductor device composition, the content of the aforementioned alkanolamine is 0.3-10% by mass relative to the total mass of the aforementioned semiconductor device composition, the content of the aforementioned water is 10-40% by mass relative to the total mass of the aforementioned semiconductor device composition, wherein the pH is 9-11, and the aforementioned semiconductor device composition further contains component A selected from at least one of the group including cyclobutene and dipropene, wherein the aforementioned component A is different from the aforementioned aprotic polar solvent, and the content of the aforementioned component A is more than 10 ppt by mass and less than 1000 ppm by mass relative to the total mass of the aforementioned semiconductor device composition.

2. The semiconductor device composition as claimed in claim 1, wherein the aforementioned aprotic polar solvent comprises at least one selected from the group consisting of dimethyl sulfoxide and cyclobutane.

3. The semiconductor device composition as described in claim 1, wherein the aforementioned aprotic polar solvent comprises cyclobutane.

4. The semiconductor device composition as described in claim 1, wherein the content of the aforementioned component A is 100 ppt or more and 100 ppm or less relative to the total mass of the aforementioned semiconductor device composition.

5. The semiconductor device composition as described in claim 1 or claim 4, wherein the mass ratio of the content of the aforementioned azole compound to the content of the aforementioned component A is 1.0 × 10³ to 1.0 × 10¹⁰.

6. The semiconductor device composition as described in claim 1 or claim 4, wherein the mass ratio of the content of the aforementioned aprotic polar solvent to the content of the aforementioned component A is 1.0 × 10⁴ to 1.0 × 10¹⁰.

7. The semiconductor device composition as claimed in claim 1, wherein the aforementioned alcohol comprises at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tributanol, 1-pentanol, 3-pentanol and cyclopentanol.

8. A semiconductor device composition as claimed in claim 1, wherein the aforementioned azole compound comprises at least one selected from the group consisting of 1,2,4-triazole, 1,2,3-triazole, 1H-tetrazole, 5-aminotetrazole, 1H-benzotriazole, tolyltriazole, 5-methyltriazole, carboxybenzotriazole and 2,2'-[{(methyl-1H-benzotriazole-1-yl)methyl}imino]diethanol.

9. The semiconductor device composition as claimed in claim 1, wherein the aforementioned alkanolamine comprises at least one selected from the group consisting of diethanolamine, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethoxy)ethanol, triethanolamine, 2-aminoethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and N-methylethanolamine.

10. The semiconductor device composition as described in claim 1 further contains a chelating agent.

11. The semiconductor device composition as claimed in claim 10, wherein the aforementioned chelating agent has a ligand selected from at least one of the group consisting of carboxyl, phosphonic, phosphate and amino groups.

12. The semiconductor device composition as claimed in claim 10, wherein the aforementioned chelating agent comprises at least one selected from the group consisting of amino polycarboxylic acids and polycarboxylic acids.

13. A method for cleaning a substrate, comprising a cleaning step of cleaning a substrate having a metal layer using a semiconductor element composition as described in any one of claims 1 to 12.

Images