Cleaning agent composition

Abstract

The present invention addresses the problem of providing a cleaning agent composition for semiconductor devices, which has excellent long-term stability of the ability to remove organic residues and also has excellent corrosion resistance to metal layers. This cleaning agent composition for semiconductor devices contains: one or more hydroxylamine compounds selected from the group consisting of hydroxylamine and hydroxylamine salts; one or more chelating agents selected from the group consisting of carboxylic acid-based chelating agents other than polyaminocarboxylic acids and phosphonic acid-based chelating agents; and a benzotriazole compound.

Description

[0001] This application is a divisional application of the application number 202080060051.7 filed by the applicant and entitled “Cleaning Composition”. The filing date of the parent application is July 8, 2020, and the priority date is August 23, 2019. Technical Field

[0002] The present invention relates to a cleaning agent composition, and more particularly to a cleaning agent composition that can be preferably used in the manufacture of semiconductor devices. Background Art

[0003] Semiconductor devices such as CCDs (Charge-Coupled Devices) and memories are manufactured using photolithography techniques to form fine electronic circuit patterns on substrates. Specifically, a resist film is formed on a laminate consisting of a metal film serving as wiring material, an etch stop layer, and an interlayer insulating layer on a substrate, and then photolithography and dry etching processes (e.g., plasma etching) are performed to manufacture semiconductor devices.

[0004] The substrate subjected to the dry etching step is subjected to a resist stripping step for stripping the resist film mainly composed of an organic substance by a stripping method such as a dry ashing step (for example, plasma ashing) as needed.

[0005] In substrates that have undergone dry etching and resist stripping steps, since residues containing a large amount of organic components originating from the resist film adhere to their wiring films and / or interlayer insulating films, a cleaning composition is often used to remove the residues to avoid interfering with the next step.

[0006] For example, Patent Document 1 discloses a cleaning composition comprising a redox agent, a first chelating agent polyaminopolycarboxylic acid, a second chelating agent containing at least two nitrogen-containing groups, a metal corrosion inhibitor benzotriazole, an organic solvent, water, and a desired pH adjuster.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application No. 2017-504190 Summary of the Invention

[0010] Technical issues to be solved by the invention

[0011] The present inventors studied cleaning compositions used in semiconductor device manufacturing processes based on the description of Patent Document 1 and found that there is room for further improvement in the performance of removing organic residues after the cleaning compositions have been stored for a period of time.

[0012] Furthermore, cleaning compositions are required to suppress corrosion (corrosion resistance) of wiring metals (for example, one or more metals selected from Cu, W, and Co) forming a metal layer of a semiconductor device to be cleaned.

[0013] Therefore, an object of the present invention is to provide a cleaning composition for semiconductor devices that has excellent temporal stability in the performance of removing organic residues and also has excellent corrosion resistance to metal layers.

[0014] Means for solving technical problems

[0015] The present inventors have conducted intensive studies to achieve the above-mentioned problems and have found that the above-mentioned problems can be solved by the following configuration.

[0016] [1] A cleaning agent composition for semiconductor devices, comprising: one or more hydroxylamine compounds selected from hydroxylamine and hydroxylamine salts; one or more chelating agents selected from carboxylic acid chelating agents other than polyaminocarboxylic acids and phosphonic acid chelating agents; and a benzotriazole compound.

[0017] [2] The cleaning composition according to [1], wherein the chelating agent comprises a phosphonic acid chelating agent.

[0018] [3] The cleaning composition according to [2], wherein the phosphonic acid chelating agent comprises one or more compounds selected from the group consisting of hydroxyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonocarboxylic acid compounds.

[0019] [4] The cleaning composition according to [2] or [3], wherein the phosphonic acid chelating agent comprises an aminophosphonic acid compound.

[0020] [5] The cleaning composition according to [1], wherein the chelating agent comprises a carboxylic acid chelating agent.

[0021] [6] The cleaning composition according to [5], wherein the carboxylic acid chelating agent comprises one or more compounds selected from the group consisting of hydroxy acid compounds, polycarboxylic acid compounds, and aromatic polycarboxylic acid compounds.

[0022] [7] The cleaning composition according to [5] or [6], wherein the carboxylic acid chelating agent comprises a hydroxy acid compound.

[0023] [8] The cleaning composition according to any one of [1] to [7], wherein the hydroxylamine compound comprises one or more selected from hydroxylamine, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, hydroxylamine sulfate, N,N-dimethylhydroxylamine sulfate and N,N-diethylhydroxylamine sulfate.

[0024] [9] The cleaning composition according to any one of [1] to [8], wherein the benzotriazole compound includes a compound represented by the formula (A) described below.

[0025]

[10] The cleaning composition according to any one of [1] to [9], wherein the mass ratio of the content of the hydroxylamine compound to the content of the benzotriazole compound is 1 to 1000.

[0026]

[11] The cleaning composition according to any one of [1] to

[10] , wherein the mass ratio of the content of the hydroxylamine compound to the content of the chelating agent is 0.1 to 100.

[0027]

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

[11] , which is used for cleaning a substrate having a metal layer containing one or more metals selected from copper, tungsten, and cobalt.

[0028] Effects of the Invention

[0029] According to the present invention, a cleaning composition for semiconductor devices can be provided that has excellent temporal stability in the performance of removing organic residues and also has excellent corrosion resistance against metal layers. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a schematic cross-sectional view showing an example of a laminate that can be applied to a cleaning method using a cleaning composition. DETAILED DESCRIPTION

[0031] Hereinafter, the present invention will be described in detail.

[0032] Although the description of the constituent elements described below may be made based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

[0033] In addition, in this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0034] Furthermore, the term "preparation" in this specification includes not only preparation by synthesizing or blending specific materials but also procurement of predetermined materials by purchase.

[0035] In this specification, "ppm" means "parts-per-million (10 -6 )”, “ppb” means “parts-per-billion (10 -9 )”, “ppt” means “parts-per-trillion (10 -12 )”.

[0036] Furthermore, in this specification, (Angstrom) is equivalent to 0.1nm.

[0037] Furthermore, in the notation of groups (atomic groups) in this specification, the notation not indicating substitution or unsubstituted includes both unsubstituted and substituted groups within the scope that does not impair the effects of the present invention. For example, "hydrocarbon group" includes not only hydrocarbon groups without substitution (unsubstituted hydrocarbon groups) but also hydrocarbon groups with substitution (substituted hydrocarbon groups). This also has the same meaning for each compound.

[0038] In this specification, the pH of the cleaning composition is a value measured at room temperature (25° C.) using F-51 (trade name) manufactured by HORIBA, Ltd.

[0039] Furthermore, "radiation" in this specification refers to the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, or electron beams. Furthermore, light in this specification refers to actinic rays or radiation. "Exposure" in the present invention, unless otherwise specified, includes not only exposure using a mercury lamp, far ultraviolet light represented by excimer lasers, X-rays, or EUV light, but also drawing using particle beams such as electron beams or ion beams.

[0040] [Cleaning agent composition]

[0041] The cleaning composition of the present invention is a cleaning composition for semiconductor devices, comprising one or more hydroxylamine compounds selected from hydroxylamine and hydroxylamine salts, one or more chelating agents selected from carboxylic acids (excluding polyaminocarboxylic acids) and phosphonic acids (hereinafter also referred to as "specific chelating agents"), and a benzotriazole compound.

[0042] The present inventors surprisingly found that a cleaning composition having excellent temporal stability in the removal performance of organic residues and excellent corrosion resistance against metal layers can be obtained by containing a hydroxylamine compound, a specific chelating agent, and a benzotriazole compound.

[0043] In this specification, "organic residue" refers to residue primarily composed of organic matter, generated during the semiconductor device manufacturing process. In this context, "mainly composed of organic matter" means that the organic matter content is 50% or greater by mass relative to the total amount of the residue. Furthermore, in this specification, the performance of removing organic residue is simply referred to as "removal performance."

[0044] Hereinafter, each component contained in the cleaning composition will be described.

[0045] 〔Element〕

[0046] <Hydroxyamine Compounds>

[0047] The cleaning composition of the present invention comprises one or more hydroxylamine compounds selected from hydroxylamine and hydroxylamine salts. The hydroxylamine compound has the function of promoting the decomposition and solubilization of organic residues.

[0048] Here, the “hydroxylamine” referred to in the hydroxylamine compound refers to hydroxylamine in a broad sense including substituted or unsubstituted alkylhydroxylamines, and any of these can provide excellent temporal stability of removal performance and excellent corrosion resistance.

[0049] The hydroxylamine compound is not particularly limited, but preferred embodiments include unsubstituted hydroxylamine, hydroxylamine derivatives, and salts thereof.

[0050] The hydroxylamine derivatives are not particularly limited, and examples thereof 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-disulfoethylhydroxylamine.

[0051] The salt of unsubstituted hydroxylamine or a hydroxylamine derivative is preferably an inorganic acid salt or an organic acid salt of the above-mentioned unsubstituted hydroxylamine or a hydroxylamine derivative, more preferably a salt of an inorganic acid bonded to a non-metal atom such as Cl, S, N, or P and a hydrogen atom, and still more preferably a salt with hydrochloric acid, sulfuric acid, or nitric acid. Among these, hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine phosphate, N,N-diethylhydroxylamine sulfate, N,N-diethylhydroxylamine nitrate, or a mixture thereof is preferred.

[0052] Furthermore, organic acid salts of the unsubstituted hydroxylamine or hydroxylamine derivatives can also be used. Examples of organic acid salts include hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride.

[0053] As the hydroxylamine compound, hydroxylamine, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, hydroxylamine sulfate, N,N-dimethylhydroxylamine sulfate or N,N-diethylhydroxylamine sulfate is preferred. From the viewpoint of better removal performance, hydroxylamine or hydroxylamine sulfate is more preferred. From the viewpoint of better corrosion resistance, hydroxylamine is further preferred.

[0054] The hydroxylamine compound may be used alone or in combination of two or more. From the viewpoint of achieving better corrosion resistance, it is preferred to use two or more hydroxylamine compounds.

[0055] The content of the hydroxylamine compound is, for example, 0.1 to 30% by mass relative to the total mass of the cleaning composition.

[0056] Among them, from the viewpoint of better removal performance, the content of the hydroxylamine compound is preferably 0.3% by mass or more, and more preferably 0.5% by mass or more, based on the total mass of the cleaning composition.

[0057] Furthermore, from the viewpoint of achieving better corrosion resistance, the content of the hydroxylamine compound is preferably 20% by mass or less, and more preferably 15% by mass or less, based on the total mass of the cleaning composition.

[0058] The hydroxylamine compound may be used alone or in combination of two or more. When two or more are used, the total content of these compounds is preferably within the above range.

[0059] <Specific Chelating Agents>

[0060] The cleaning composition of the present invention contains, as a specific chelating agent, one or more compounds selected from carboxylic acids other than polyaminocarboxylic acids and phosphonic acid-based chelating agents.

[0061] In this specification, polyaminocarboxylic acid refers to a compound having a plurality of amino groups and one or more carboxyl groups.

[0062] The specific chelating agent contained in the cleaning composition has the function of chelating metals in the cleaning process included in the manufacturing process of semiconductor devices. Among them, compounds having two or more functional groups (ligands) that coordinate with metal ions in one molecule are preferred.

[0063] The number of ligands possessed by the specific chelating agent is not particularly limited, but is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0064] (Phosphonic acid chelating agent)

[0065] The phosphonic acid chelating agent is a compound having one or more phosphonic acid groups and forming a chelate with a metal.

[0066] Examples of the phosphonic acid-based chelating agent include hydroxyphosphonic acid compounds, polyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonocarboxylic acid compounds.

[0067] Among them, hydroxyphosphonic acid compounds, aminophosphonic acid compounds or phosphonocarboxylic acid compounds are preferred, and aminophosphonic acid compounds are more preferred.

[0068] The hydroxyphosphonic acid compound is a compound having one or more phosphonic acid groups and one or more hydroxyl groups in the molecule.

[0069] Furthermore, the polyphosphonic acid compound is a compound having two or more phosphonic acid groups in the molecule. In addition, compounds having any one of a hydroxyl group, an amino group, and a carboxyl group in the molecule are not included in the polyphosphonic acid compound.

[0070] Examples of the hydroxyphosphonic acid compound and the polyphosphonic acid compound include compounds represented by the following formula (1).

[0071] [Chemical Formula 1]

[0072]

[0073] In the formula, X represents a hydroxyl group, R 1 represents a hydrogen atom or an alkyl group.

[0074] R in formula (1) 1 The alkyl group represented may be any of linear, branched, and cyclic, and is preferably linear or branched.

[0075] R 1 The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. 1 The alkyl group represented is preferably ethyl, n-propyl or isopropyl.

[0076] In the specific examples of the alkyl group described in this specification, n- represents the normal form (normal form).

[0077] Examples of the compound represented by formula (1) include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid, and 1-hydroxybutane-1,1-diphosphonic acid.

[0078] Examples of hydroxyphosphonic acid compounds other than the compound represented by formula (1) include 2-hydroxyethane-1,1-diphosphonic acid, 3-hydroxypropane-1,1-diphosphonic acid, glycerol-3-phosphate, and ethanehydroxy-1,1,2-triphosphonic acid.

[0079] The hydroxyphosphonic acid compound is preferably 1-hydroxyethane-1,1-diphosphonic acid or glycerol-3-phosphate. Among them, 1-hydroxyethane-1,1-diphosphonic acid is more preferred from the viewpoint of superior removal performance and corrosion resistance, and glycerol-3-phosphate is more preferred from the viewpoint of superior temporal stability of removal performance.

[0080] The aminophosphonic acid compound is a compound having one or more phosphonic acid groups and one or more amino groups in the molecule. In addition, compounds having a carboxyl group in the molecule are not included in the aminophosphonic acid compound.

[0081] Examples of the aminophosphonic acid compound include compounds represented by the following formula (2) and formula (3).

[0082] [Chemical Formula 2]

[0083]

[0084] In the formula, Q represents a hydrogen atom or -R 3 -PO3H2, R 2 and R 3 Each independently represents an alkylene group, and Y represents a hydrogen atom, -PO3H2 or a group represented by the following formula (4).

[0085] [Chemical Formula 3]

[0086]

[0087] In formula (4), Q and R 3 and Q and R in formula (2) 3 same.

[0088] In formula (2), R 2 The alkylene group represented may be either linear or branched. 2 The alkylene group represented by is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably a methylene group or an ethylene group.

[0089] As Y in formula (2), -PO3H2 or a group represented by formula (4) is preferred, and -PO3H2 is more preferred.

[0090] And, as R in formula (2) 2 and Y, preferably R 2 is a methylene group and Y is a combination of -PO3H2 or R 2 A combination in which ethylene is present and Y is a group represented by formula (4).

[0091] As Q in formulas (2) and (4), -R 3 -PO3H2.

[0092] In formulas (2) and (4), R 3 The alkylene group represented may be either linear or branched. 3 The alkylene group represented by is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, further preferably a methylene group or an ethylene group, and particularly preferably a methylene group.

[0093] Examples of the aminophosphonic acid compound represented by formula (2) include ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrosotri(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), 1,3-propylenediaminebis(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) (EDTPO), ethylenediaminetetra(ethylenephosphonic acid), 1,3-propylenediaminetetra(methylenephosphonic acid) (PDTMP), 1,2-diaminopropanetetra(methylenephosphonic acid) and 1,6-hexamethylenediaminetetra(methylenephosphonic acid).

[0094] [Chemical Formula 4]

[0095]

[0096] Where R 4 and R 5 Each independently represents an alkylene group having 1 to 4 carbon atoms, n represents an integer of 1 to 4, and Z 1 ~Z 4 and n Z 5 At least four of them represent alkyl groups having a phosphonic acid group, and the rest represent alkyl groups.

[0097] In formula (3), R 4 and R 5 The alkylene group having 1 to 4 carbon atoms may be either linear or branched. 4 and R 5 The alkylene group having 1 to 4 carbon atoms represented by is preferably an ethylene group.

[0098] As n in formula (3), 1 or 2 is preferable.

[0099] Z in formula (3) 1 ~Z 5 The alkyl group and the alkyl group having a phosphonic acid group represented by the above may be either a linear alkyl group or a branched alkyl group, and an alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group is more preferred.

[0100] As Z 1 ~Z 5 The number of phosphonic acid groups in the alkyl group having a phosphonic acid group is preferably 1 or 2, more preferably 1.

[0101] As Z 1 ~Z 5 The alkyl group having a phosphonic acid group is preferably a monophosphonomethyl group or a monophosphonoethyl group, and more preferably a monophosphonomethyl group.

[0102] As Z in formula (3) 1 ~Z 5 , preferably Z 1 ~Z 4 and n Z 5 All of them are the above-mentioned alkyl groups having a phosphonic acid group.

[0103] Examples of the aminophosphonic acid compound represented by formula (3) include diethylenetriaminepenta(methylenephosphonic acid) (DEPPO), diethylenetriaminepenta(ethylenephosphonic acid), triethylenetetraaminehexa(methylenephosphonic acid), and triethylenetetraaminehexa(ethylenephosphonic acid).

[0104] As the aminophosphonic acid compound, ethylaminobis(methylenephosphonic acid), nitrosotri(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), ethylenediaminetetra(methylenephosphonic acid) (EDTPO), ethylenediaminetetra(ethylenephosphonic acid), 1,3-propylenediaminetetra(methylenephosphonic acid) (PDTMP) or diethylenetriaminepenta(methylenephosphonic acid) (DEPPO) are preferred, and NTP0 or EDDPO are more preferred.

[0105] The phosphonocarboxylic acid compound is a compound having one or more carboxyl groups and one or more phosphonic acid groups in the molecule.

[0106] Examples of the phosphonocarboxylic acid compound include compounds represented by the following formula (5).

[0107] R 6 (-COOH) i (-PO3H2) j (5)

[0108] In formula (5), R 6 It represents an aliphatic hydrocarbon group with a valence of (i+j), wherein i represents an integer of 1 to 4, and j represents an integer of 1 to 4.

[0109] R 6 The aliphatic hydrocarbon group represented by may be any of linear, branched, and cyclic, but is preferably linear or branched. 6 The aliphatic hydrocarbon group represented may be any of a saturated hydrocarbon and an unsaturated hydrocarbon, but is preferably a saturated hydrocarbon.

[0110] R 6The represented aliphatic hydrocarbon group may have a linking group containing one or more heteroatoms selected from oxygen atoms, nitrogen atoms and sulfur atoms, preferably has an oxygen atom or nitrogen atom linking group or does not have a linking group containing a heteroatom. From the viewpoint of better temporal stability of the removal performance, it is more preferable not to have a linking group containing a heteroatom.

[0111] And, R 6 The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but is preferably 1 to 8, more preferably 2 to 6, and even more preferably 3 to 5.

[0112] In formula (5), i is preferably an integer of 1 to 3.

[0113] In formula (5), j is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0114] The sum of i and j (i+j) in formula (5) is preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.

[0115] Examples of the hydroxyphosphonic acid compound include 2-phosphonobutane-1,2,4-tricarboxylic acid, 4-phosphonobutyric acid, and glycine-N,N-bis(methylenephosphonic acid), with 2-phosphonobutane-1,2,4-tricarboxylic acid, 4-phosphonobutyric acid, and glycine-N,N-bis(methylenephosphonic acid) being preferred.

[0116] Among these, 2-phosphonobutane-1,2,4-tricarboxylic acid or 4-phosphonobutyric acid are more preferred from the perspective of superior temporal stability of removal performance, and 2-phosphonobutane-1,2,4-tricarboxylic acid or glycine-N,N-bis(methylenephosphonic acid) are more preferred from the perspective of superior residue removal performance and corrosion resistance. As the hydroxyphosphonic acid compound, 2-phosphonobutane-1,2,4-tricarboxylic acid is even more preferred.

[0117] A polyphosphonic acid compound is a compound having two or more phosphonic acid groups in its molecule. The above-mentioned hydroxyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonocarboxylic acid compounds are not included in the polyphosphonic acid compound.

[0118] Examples of the polyphosphonic acid compound include compounds represented by the following formula (6).

[0119] R 7 (-PO3H2) k (6)

[0120] In formula (6), R 7 represents a k-valent aliphatic hydrocarbon group, where k represents an integer of 2 to 6.

[0121] R 7The aliphatic hydrocarbon group represented by may be any of linear, branched, and cyclic, preferably linear or branched. 7 The aliphatic hydrocarbon group represented may be any of a saturated hydrocarbon and an unsaturated hydrocarbon, but is preferably a saturated hydrocarbon.

[0122] R 7 The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but is preferably 1 to 10, more preferably 2 to 6.

[0123] k is preferably an integer of 2 to 4, more preferably 2 or 3.

[0124] Examples of the polyphosphonic acid compound include ethylenebisphosphonic acid, propylenebisphosphonic acid, butylenebisphosphonic acid, and isopropylenebisphosphonic acid.

[0125] Furthermore, examples of polyphosphonic acid compounds include compounds ((co)polymers) described in paragraphs

[0031] to

[0046] of International Publication No. 2018 / 030006, and the contents are incorporated into this specification.

[0126] (Carboxylic acid chelating agent)

[0127] Carboxylic acid chelating agents are compounds that have one or more carboxyl groups and chelate with metals. Hereinafter, unless otherwise specified, carboxylic acid chelating agents other than polyaminocarboxylic acids are simply referred to as "carboxylic acid chelating agents." Furthermore, compounds having both a carboxyl group and a phosphonic acid group are not included in carboxylic acid chelating agents but are included in phosphonic acid chelating agents.

[0128] Examples of the carboxylic acid-based chelating agent include polycarboxylic acid compounds, hydroxy acid compounds, aromatic carboxylic acid compounds, and amino acid compounds.

[0129] Among them, polycarboxylic acid compounds, hydroxy acid compounds or aromatic carboxylic acid compounds are preferred, and hydroxy acid compounds are more preferred.

[0130] A polycarboxylic acid compound is a compound having two or more carboxyl groups in its molecule. However, hydroxy acid compounds, aromatic carboxylic acid compounds, and amino acid compounds described below are not included in the polycarboxylic acid compound.

[0131] Examples of the polycarboxylic acid compound include compounds represented by the following formula (7).

[0132] R 8 (-COOH) p (7)

[0133] In formula (7), R 8 represents a p-valent aliphatic hydrocarbon group, where p represents an integer of 2 to 6.

[0134] R8 The aliphatic hydrocarbon group represented by may be any of linear, branched, and cyclic, preferably linear or branched. 8 The aliphatic hydrocarbon group represented may be any of a saturated hydrocarbon and an unsaturated hydrocarbon, but is preferably a saturated hydrocarbon.

[0135] R 8 The aliphatic hydrocarbon group represented may have a linking group containing one or more hetero atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom, but preferably does not have a linking group containing a hetero atom.

[0136] R 8 The number of carbon atoms of the aliphatic hydrocarbon group is not particularly limited, but is preferably 1 to 10, more preferably 2 to 6, and further preferably 2 to 4 from the viewpoint of superior temporal stability of the removal performance.

[0137] p is preferably an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2.

[0138] Examples of the polycarboxylic acid compound include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 3-methyladipic acid, sebacic acid, maleic acid, and 1,3,5-pentanetricarboxylic acid. Preferred are succinic acid, glutaric acid, adipic acid, pimelic acid, 3-methyladipic acid, and 1,3,5-pentanetricarboxylic acid. Succinic acid, glutaric acid, and adipic acid are more preferred from the perspective of superior temporal stability of removal performance. Furthermore, from the perspective of removal performance, 1,3,5-pentanetricarboxylic acid is more preferred.

[0139] Hydroxy acid compounds are compounds having one or more carboxyl groups and one or more hydroxyl groups in their molecules. However, compounds having an aromatic ring in their molecules are not included in the hydroxy acid compounds.

[0140] Examples of the hydroxy acid compound include compounds represented by the following formula (8).

[0141] R 9 (-COOH) m (-OH) n (8)

[0142] In formula (8), R 9 It represents an aliphatic hydrocarbon group with a valence of (m+n), m represents an integer of 1 to 4, and n represents an integer of 1 to 4.

[0143] R 9 The aliphatic hydrocarbon group represented by may be any of linear, branched, and cyclic, but is preferably linear or branched. 9 The aliphatic hydrocarbon group represented may be any of a saturated hydrocarbon and an unsaturated hydrocarbon, but is preferably a saturated hydrocarbon.

[0144] R 9 The aliphatic hydrocarbon group represented may have a linking group containing one or more heteroatoms selected from oxygen atoms, nitrogen atoms, and sulfur atoms, but preferably has an oxygen atom or nitrogen atom linking group or does not have a linking group containing a heteroatom.

[0145] R 9 The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but is preferably 1 to 8, more preferably 2 to 6, and further preferably 3 to 5 from the viewpoint of excellent corrosion resistance.

[0146] In formula (8), m is preferably 1 or 2, and more preferably 1.

[0147] In formula (8), n is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0148] The sum of m and n (m+n) in formula (8) is preferably an integer of 2 to 4, more preferably 2 or 3.

[0149] Examples of the hydroxy acid compound include malic acid, citric acid, glycolic acid, tartaric acid, lactic acid, and diethanolglycine. Malic acid, citric acid, or diethanolglycine is preferred, and citric acid or diethanolglycine is more preferred from the viewpoint of excellent corrosion resistance.

[0150] The aromatic carboxylic acid compound is a compound having one or more carboxyl groups and an aromatic ring in its molecule.

[0151] Examples of the aromatic carboxylic acid compound include compounds represented by the following formula (9).

[0152] Ar(-COOH) q (9)

[0153] In formula (9), Ar represents a q-valent aromatic hydrocarbon group which may have a substituent, and q represents an integer of 1 to 6. When q represents 1, the aromatic hydrocarbon group represented by Ar further has a ligand other than a carboxyl group and a phosphonic acid group.

[0154] Examples of substituents that the aromatic hydrocarbon group represented by Ar may have include one or more ligands selected from the group consisting of a hydroxyl group, an amino group, and a sulfo group, and an aliphatic hydrocarbon group (preferably an alkyl group having 1 to 4 carbon atoms) that may have such ligands. Furthermore, the aliphatic hydrocarbon group represented by Ar may have a carboxyl group as in formula (9).

[0155] The number of carbon atoms in the aromatic hydrocarbon group represented by Ar is not particularly limited, but is preferably 6 to 14, more preferably 6 to 10.

[0156] q is preferably an integer of 1 to 3, more preferably 1 or 2.

[0157] As the aromatic hydrocarbon group represented by Ar, a benzene ring which may have a hydroxyl group is preferable.

[0158] Examples of the aromatic carboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and gallic acid. Isophthalic acid and salicylic acid are preferred, and isophthalic acid is more preferred from the viewpoint of excellent corrosion resistance.

[0159] Amino acid compounds are compounds having one or more carboxyl groups and one or more amino groups as ligands in the molecule. However, the above-mentioned hydroxy acid compounds and aromatic carboxylic acid compounds are not included in amino acid compounds.

[0160] Examples of the amino acid compound include glycine, serine, d-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), leucine, isoleucine, cysteine, ethionine, threonine, aspartic acid, glutamic acid, proline, methionine, phenylalanine, and salts thereof.

[0161] Examples of the salt include alkali metal salts such as sodium salts and potassium salts, ammonium salts, carbonates, and acetates.

[0162] As the specific chelating agent, hydroxyphosphonic acid compounds, aminophosphonic acid compounds, phosphonocarboxylic acid compounds, polycarboxylic acid compounds, hydroxy acid compounds or aromatic carboxylic acid compounds are preferred. From the viewpoint of superior removal performance and temporal stability of removal performance, aminophosphonic acid compounds or hydroxy acid compounds are more preferred.

[0163] The specific chelating agents may be used alone or in combination of two or more.

[0164] From the viewpoint of achieving better temporal stability of the removal performance, the content of the specific chelating agent is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more relative to the total mass of the cleaning composition.

[0165] The upper limit is not particularly limited, but from the viewpoint of better corrosion resistance, it is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably less than 2% by mass relative to the total mass of the cleaning composition.

[0166] In the cleaning composition, the mass ratio of the hydroxylamine compound content to the specific chelating agent content (hydroxylamine compound content / specific chelating agent content) is preferably 0.1 or more, more preferably 1 or more, from the viewpoint of achieving better corrosion resistance.

[0167] Furthermore, from the viewpoint of achieving more excellent temporal stability in removal performance, the mass ratio is preferably 100 or less, and more preferably 10 or less.

[0168] <Benzotriazole compounds>

[0169] The cleaning composition of the present invention contains a benzotriazole compound.

[0170] The benzotriazole compound is not particularly limited as long as it is a compound having a benzotriazole structure, and examples thereof include compounds represented by the following formula (A).

[0171] [Chemical Formula 5]

[0172]

[0173] In formula (A), R 11 represents a substituent.

[0174] R 12 represents a hydrogen atom or a substituent.

[0175] n represents an integer of 0 to 4. When n is 2 or greater, n R 11 It can be the same or different.

[0176] As R in formula (A) 11 Examples of the substituents include alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 14 carbon atoms, groups represented by the following formula (B), hydroxyl groups, mercapto groups, carboxyl groups, and alkoxycarbonyl groups having 1 to 12 carbon atoms.

[0177] And, R 11 The substituent represented may further have one or more substituents selected from the group consisting of a hydroxyl group and a carboxyl group.

[0178] [Chemical Formula 6]

[0179]

[0180] In formula (B), R 13 and R 14 Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group.

[0181] R 15 It represents a single bond or an alkylene group having 1 to 6 carbon atoms.

[0182] *Indicates bonding site.

[0183] R in formula (B) 13 and R 14 A hydrogen atom or an alkyl group having 1 to 3 carbon atoms and having a hydroxyl group is preferred, and a hydrogen atom or a 2-hydroxyethyl group is more preferred.

[0184] R in formula (B) 15A single bond or an alkylene group having 1 to 3 carbon atoms is preferred, and a single bond or an ethylene group is more preferred.

[0185] The group represented by formula (B) is preferably an amino group or an N,N-bis(hydroxyethyl)aminoethyl group.

[0186] As R in formula (A) 11 , preferably a carboxyl group, an amino group or an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

[0187] In formula (A), n is preferably an integer of 0 to 2, and more preferably 0 or 1.

[0188] As R 12 Examples of the substituents include alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 14 carbon atoms, the group represented by the above formula (B), hydroxyl groups, mercapto groups, and alkoxycarbonyl groups having 1 to 12 carbon atoms.

[0189] And, R 12 The substituent represented may further have one or more substituents selected from the group consisting of a hydroxyl group and a carboxyl group.

[0190] As R in formula (A) 12 , preferably a hydrogen atom, a hydroxyl group, a group represented by the above formula (B) or an alkyl group having 1 to 6 carbon atoms which may have a carboxyl group, and more preferably a hydrogen atom or a hydroxyl group.

[0191] As the benzotriazole compound, preferred are benzotriazole, 5-methyl-1H-benzotriazole, 5-aminobenzotriazole, 1-hydroxybenzotriazole, 4-carboxybenzotriazole, 5,6-dimethylbenzotriazole, 1-[N,N-bis(hydroxyethyl)aminoethyl]benzotriazole, 1-(1,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole or 2,2'-{[(methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, and more preferred are benzotriazole, 5-methyl-1H-benzotriazole or 1-hydroxybenzotriazole.

[0192] The benzotriazole compounds may be used alone or in combination of two or more.

[0193] From the viewpoint of achieving better corrosion resistance, the content of the benzotriazole compound is preferably 0.0001% by mass or more, and more preferably 0.001% by mass or more, based on the total mass of the cleaning composition.

[0194] The upper limit is not particularly limited, but from the viewpoint of better residue removal performance, it is preferably 10% by mass or less, more preferably 3% by mass or less, and even more preferably 0.5% by mass or less, based on the total mass of the cleaning composition.

[0195] In the cleaning composition, the mass ratio of the hydroxylamine compound content to the benzotriazole compound content (hydroxylamine compound content / benzotriazole compound content) is preferably 1 or more, more preferably 10 or more, from the viewpoint of achieving better residue removal performance.

[0196] Furthermore, from the viewpoint of achieving better corrosion resistance, the mass ratio is preferably 1000 or less, and more preferably 100 or less.

[0197] <Solvent>

[0198] The medical solution may contain a solvent.

[0199] Examples of the solvent include water and organic solvents, and water is preferred.

[0200] (water)

[0201] The cleaning composition preferably comprises water.

[0202] The type of water used in the cleaning composition is not particularly limited as long as it does not adversely affect the semiconductor substrate. Examples include distilled water, deionized water (DI (deionized) water), and pure water (ultrapure water). Pure water is preferred because it contains almost no impurities and has less impact on the semiconductor substrate during the semiconductor device manufacturing process.

[0203] The water content in the cleaning composition is not particularly limited, but is preferably 60% by mass or greater, more preferably 70% by mass or greater, and even more preferably 85% by mass or greater, relative to the total mass of the cleaning composition. The upper limit is not particularly limited, but is preferably 99% by mass or less, and more preferably 95% by mass or less.

[0204] (Organic solvent)

[0205] The cleaning composition may contain an organic solvent.

[0206] As the organic solvent, a water-soluble organic solvent is preferred, an alcohol solvent, a ketone solvent or an amide solvent is more preferred, and an alcohol solvent is further preferred.

[0207] Examples of the alcohol solvent include alkanediol, alkylene glycol, alkoxy alcohol, saturated or unsaturated aliphatic alcohol, and trivalent or higher alcohol.

[0208] Examples of the alkanediol include glycol, 2-methyl-1,3-propanediol, 1,2-propanediol, 1,3-propanediol (1,3-dihydroxypropane), 2-methyl-2,4-pentanediol, 2,2-dimethyl-1,3-hexanediol, 1,4-butanediol (1,4-dihydroxybutane), 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 2,5-dihydroxy-2,5-dimethylhexane, pinacol, and alkylene glycol.

[0209] Examples of the alkylene glycol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

[0210] Examples of the alkoxy alcohol include alkylene glycol monoalkyl ether and alkylene glycol dialkyl ether.

[0211] Examples of the alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, and 1-methoxy-2-butanol.

[0212] Examples of the alkylene glycol dialkyl ether include diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether.

[0213] The alkylene glycol monoalkyl ether and alkylene glycol dialkyl ether used in the cleaning composition preferably have 3 to 16 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0214] Examples of the saturated or unsaturated aliphatic alcohol include methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butyl alcohol, 2-pentanol, tert-amyl alcohol, 1-hexanol, allyl alcohol, propargyl alcohol, 2-butenol, 3-butenol, and 4-penten-2-ol.

[0215] Examples of trivalent or higher alcohols include glycerin.

[0216] As the alcohol solvent, alkoxy alcohol is preferable. As the alkoxy group, for example, alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy and butoxy are preferable.

[0217] Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0218] Examples of the amide solvent include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0219] As the organic solvent, alkylene glycol monoalkyl ether is preferred, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether or ethylene glycol monobutyl ether is more preferred, and ethylene glycol monobutyl ether is further preferred.

[0220] The organic solvent may be used alone or in combination of two or more.

[0221] When the cleaning composition contains an organic solvent, the content of the organic solvent is preferably 0.001 to 10% by mass, more preferably 0.1 to 5% by mass, relative to the total mass of the cleaning composition.

[0222] pH adjuster

[0223] In order to adjust the pH of the cleaning composition, the cleaning composition may contain a pH adjuster.

[0224] Examples of the pH adjuster include inorganic acids, organic acids (except for specific chelating agents), organic bases, and inorganic bases.

[0225] Examples of inorganic acids include sulfuric acid, acetic acid, nitric acid, phosphoric acid, and hydrofluoric acid. Examples of organic acids include lower (carbon 1-4) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid. Furthermore, the carboxylic acid-based chelating agents described above can also function as pH adjusters to lower the pH of the cleaning composition.

[0226] Examples of the organic base include quaternary ammonium salt compounds, nitrogen-containing heterocyclic compounds, and water-soluble amines.

[0227] As the quaternary ammonium salt compound, quaternary ammonium hydroxide is preferred, and a compound represented by the following formula (10) is more preferred.

[0228] [Chemical Formula 7]

[0229]

[0230] In formula (10), R 4A ~R 4DEach independently represents an alkyl group having 1 to 6 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, or a butyl group), a hydroxyalkyl group having 1 to 6 carbon atoms (preferably a hydroxymethyl group, a hydroxyethyl group, or a hydroxybutyl group), a benzyl group, or an aryl group (preferably a phenyl group, a naphthyl group, or a naphthalene group). Among them, an alkyl group having 1 to 6 carbon atoms, a hydroxyethyl group having 1 to 6 carbon atoms, or a benzyl group is preferred.

[0231] Examples of the compound represented by formula (10) include tetramethylammonium hydroxide (TMAH), ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), dimethyldipropylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methyltri(hydroxyethyl)ammonium hydroxide, tetra(hydroxyethyl)ammonium hydroxide, trimethylbenzylammonium hydroxide, bishydroxyethyldimethylammonium hydroxide, and choline. Among these, TMAH, ETMAH, TEAH, and TBAH are preferred.

[0232] In the present specification, the nitrogen-containing heterocyclic compound is a compound having a heterocyclic ring in which at least one of the atoms constituting the ring is a nitrogen atom, and refers to a compound excluding the above-mentioned benzotriazole compound.

[0233] Examples of the nitrogen-containing heterocyclic compound include azole compounds other than benzotriazole compounds, pyridine compounds, pyrazine compounds, pyrimidine compounds, piperazine compounds, and cyclic amidine compounds, and cyclic amidine compounds are preferred.

[0234] The cyclic amidine compound is a compound having a heterocyclic ring containing an amidine structure (>NC=N-) within the ring.

[0235] Examples of the cyclic amidine compound include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) and 1,5-diazabicyclo[4.3.0]nonene-5 (DBN).

[0236] In this specification, a water-soluble amine refers to an amine that can dissolve 50 g or more in 1 L of water. The pKa of the water-soluble amine is not particularly limited, but is preferably 7.5 to 13.0. Water-soluble amines do not include the aforementioned hydroxylamine compounds and ammonia.

[0237] Examples of water-soluble amines having a pKa of 7.5 to 13.0 include diglycolamine (DGA) (pKa = 9.80), methylamine (pKa = 10.6), ethylamine (pKa = 10.6), propylamine (pKa = 10.6), butylamine (pKa = 10.6), pentylamine (pKa = 10.0), monoethanolamine (pKa = 9.3), monopropanolamine (pKa = 9.3), monobutanolamine (pKa = 9.3), methoxyethylamine (pKa = 10.0), methoxypropylamine (pKa = 10.0), dimethylamine (pKa = 10.8), diethylamine (pKa = 10.9), dipropylamine (pKa = 10.8), trimethylamine (pKa = 9.80), and triethylamine (pKa = 10.72).

[0238] Examples of the inorganic base include alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia.

[0239] Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide, and examples of the alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, and barium hydroxide.

[0240] As the pH adjuster for lowering the pH of the cleaning composition, quaternary ammonium hydroxide, nitrogen-containing heterocyclic compounds, water-soluble amines or ammonia are preferred, and quaternary ammonium hydroxide, cyclic amidine compounds or water-soluble amines represented by the above formula (10) are more preferred.

[0241] The pH adjusters may be used alone or in combination of two or more.

[0242] The type and content of the pH adjuster can be appropriately selected and adjusted to maintain the pH of the cleaning composition within the preferred range described below. However, when an inorganic base is used as the pH adjuster, the content of the inorganic base is preferably 0.1% by mass or less relative to the total mass of the cleaning composition.

[0243] <Additives>

[0244] The cleaning composition may contain additives other than the above-mentioned components as needed.

[0245] Examples of such additives include surfactants, reducing agents, defoaming agents, rust inhibitors, and antiseptics.

[0246] The cleaning composition may contain a surfactant.

[0247] The type of surfactant is not particularly limited, and examples thereof include ionic surfactants (anionic surfactants, cationic surfactants, and amphoteric surfactants) and nonionic surfactants.

[0248] When the cleaning composition contains a surfactant, the content of the surfactant is preferably 1 mass ppm or more and 3 mass % or less relative to the total mass of the cleaning composition.

[0249] The cleaning composition may contain other components in addition to the above components as long as the effects of the present invention and the functions of the components are not impaired.

[0250] The contents of the above components in the cleaning composition can be measured by known methods such as gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), and ion-exchange chromatography (IC).

[0251] pH

[0252] The pH of the cleaning composition is not particularly limited, but is preferably higher than 7, more preferably higher than 8, from the viewpoint of achieving better temporal stability of the removal performance and better corrosion resistance.

[0253] The upper limit of pH is not particularly limited, but is preferably 14 or lower, more preferably 12 or lower.

[0254] The pH of the cleaning composition may be adjusted using the above-mentioned pH adjuster.

[0255] In this specification, the pH of the cleaning composition is obtained by measuring at 25° C. using a pH meter (manufactured by HORIBA, Ltd., F-51 (trade name)).

[0256] [Manufacturing method]

[0257] The method for producing the cleaning composition is not particularly limited, and the composition can be produced, for example, by mixing the above-mentioned components. The order and / or timing of mixing the above-mentioned components is not particularly limited.

[0258] For example, a method of preparing a cleaning composition by sequentially adding a hydroxylamine compound, a specific chelating agent, a benzotriazole compound, and optional components to a mixer or other agitator containing purified pure water and then stirring the mixture thoroughly to mix the components can be used.

[0259] It is preferable to use raw materials classified as semiconductor grade or raw materials classified as high purity grade equivalent thereto for each raw material used in the preparation of the cleaning composition.

[0260] Furthermore, one or more of the raw materials used to produce the cleaning composition may be purified in advance by distillation, ion exchange, or filtration.

[0261] The purification method is not particularly limited, and examples include passage through an ion exchange resin or RO membrane (reverse osmosis membrane), distillation, and filtration. More specifically, a method includes primary purification through a reverse osmosis membrane, followed by secondary purification through a purification device using a cation exchange resin, an anion exchange resin, or a mixed-bed ion exchange resin.

[0262] <Kit and Concentrate>

[0263] The cleaning composition can be prepared as a kit in which the raw materials thereof are divided into a plurality of parts.

[0264] Although not particularly limited, a specific method for preparing the cleaning composition into a kit includes, for example, preparing a solution composition containing a hydroxylamine compound, a specific chelating agent, and a benzotriazole compound as a first solution, and preparing a solution composition containing other components as a second solution.

[0265] Furthermore, the cleaning composition can be prepared as a concentrated solution. When preparing a concentrated cleaning composition, the concentration ratio can be appropriately determined depending on the composition, but is preferably 5 to 2000 times. Specifically, the concentrated solution is diluted 5 to 2000 times before use. Furthermore, to further improve the temporal stability of the removal performance, it is preferable to minimize the amount of water that causes the decomposition of the hydroxylamine compound and to prepare a composition containing a large amount of an alcoholic solvent.

[0266] <Container (Storage Container)>

[0267] The cleaning composition can be stored, transported, and used in any container, as long as it does not cause problems (whether in the kit or the concentrate) such as corrosiveness. Containers designed for semiconductor applications are preferred, offering high cleanliness and minimal impurity release. Examples of suitable containers include, but are not limited to, the "Clean Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and the "Pure Bottle" series manufactured by KODAMA PLASTICS CO., LTD.

[0268] The container should preferably be cleaned before being filled with the cleaning composition. The liquid used for cleaning should preferably contain minimal metallic impurities. The cleaning composition can also be transported and stored in containers such as gallon bottles or coated bottles after production.

[0269] <Clean Room>

[0270] All operations, including the preparation of the cleaning composition, the opening and / or cleaning of the container, and the filling of the cleaning composition, as well as processing, analysis, and measurement, are preferably performed in a clean room. The clean room preferably meets the 14644-1 clean room standard, more preferably any of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, further preferably ISO Class 1 or ISO Class 2, and particularly preferably ISO Class 1.

[0271] Cleaning method

[0272] Examples of cleaning methods using a cleaning composition include a method comprising a cleaning step (hereinafter also referred to as "cleaning step B") of cleaning a semiconductor substrate having a metal layer using the cleaning composition. Furthermore, the cleaning method may include a cleaning composition preparation step (hereinafter also referred to as "cleaning composition preparation step A") of preparing the cleaning composition prior to cleaning step B.

[0273] In the following description of the cleaning method, the case where the cleaning composition preparation 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 method may be performed using the cleaning composition prepared in advance.

[0274] <Objects to be cleaned>

[0275] The cleaning object is not particularly limited as long as it is used in the manufacturing process of semiconductor devices. For example, a semiconductor substrate having a metal layer formed using a metal wiring material can be used. Examples of the metal wiring material include Cu (copper), W (tungsten), and Co (cobalt).

[0276] A more specific example of the object to be cleaned is a laminate comprising at least the aforementioned metal layer, an interlayer insulating layer, and a metal hard mask in this order on a substrate. The laminate is further subjected to a dry etching step to form a hole extending from the surface (opening) of the metal hard mask toward the substrate, thereby exposing the surface of the metal layer.

[0277] The method for manufacturing the stack having holes as described above is not particularly limited. For example, the following method can be cited: for a pre-processed stack having a substrate, a metal layer, an interlayer insulating layer and a metal hard mask in sequence, a dry etching process is performed using the metal hard mask as a mask to etch the interlayer insulating layer to expose the surface of the metal layer, thereby providing a hole that passes through the metal hard mask and the interlayer insulating layer.

[0278] The method for manufacturing a metal hard mask is not particularly limited. For example, the following method can be cited: first, a metal film containing a specified component is formed on an interlayer insulating layer, and a resist film of a specified pattern is formed thereon. Then, the resist film is used as a mask to etch the metal film, thereby manufacturing a metal hard mask (i.e., a film in which the metal film is patterned).

[0279] After the metal hard mask is formed, a resist stripping step is performed to strip the resist film by dry ashing such as plasma ashing.

[0280] In a substrate that has been subjected to dry etching and resist stripping steps, residues containing organic components derived from the resist film adhere to the metal layer and / or interlayer insulating layer. The above-mentioned cleaning composition is used to remove these adhered residues from the laminate.

[0281] The laminate may have layers other than the above-mentioned layers, and examples thereof include an etching stopper layer and an antireflection layer.

[0282] Figure 1 This is a schematic cross-sectional view showing an example of a laminated object to be cleaned in the cleaning method using the above-mentioned cleaning composition.

[0283] Figure 1 The laminate 10 shown has a metal layer 2, an etching stop layer 3, an interlayer insulating layer 4, and a metal hard mask 5 in this order on a substrate 1. Holes 6 are formed at predetermined positions to expose the metal layer 2 through a dry etching process. Figure 1 The laminate 10 shown is a laminate comprising a substrate 1, a metal layer 2, an etching stop layer 3, an interlayer insulating layer 4, and a metal hard mask 5 in this order, and a hole 6 penetrating from the surface of the metal hard mask 5 to the surface of the metal layer 2 is provided at the position of the opening of the metal hard mask 5. Figure 1 The laminate 10 shown is subjected to a resist stripping process, and the resist film is removed.

[0284] The inner wall 11 of the hole 6 is composed of a cross-sectional wall 11 a including the etching stop layer 3 , the interlayer insulating layer 4 , and the metal hard mask 5 , and a bottom wall 11 b including the exposed metal layer 2 , and residue 12 is attached thereto.

[0285] The cleaning method can be preferably used for cleaning to remove these residues 12. That is, the cleaning composition has excellent performance in removing the residues 12 and excellent corrosion resistance to the inner wall 11 (eg, metal layer 2) of the cleaning object.

[0286] Hereinafter, the constituent materials of each layer of the above-mentioned laminate will be described.

[0287] (Metal Hard Mask)

[0288] The metal hard mask preferably contains at least one component selected from Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx. Here, x and y are numbers represented by x=1 to 3 and y=1 to 2, respectively.

[0289] Examples of the material of the metal hard mask include TiN, WO 2 , and ZrO 2 .

[0290] (Interlayer insulation layer)

[0291] The material of the interlayer insulating layer is not particularly limited, and for example, a material having a dielectric constant k of preferably 3.0 or less, and more preferably 2.6 or less can be cited.

[0292] Specific examples of the material of the interlayer insulating layer include SiO 2 , SiOC-based materials, and organic polymers such as polyimide.

[0293] (Etch stop layer)

[0294] The material of the etching stop layer is not particularly limited. Specific examples of the material of the etching stop layer include SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx.

[0295] (Metal layer)

[0296] The wiring material forming the metal layer is not particularly limited. For example, metals containing one or more selected from Cu (copper), W (tungsten), and Co (cobalt) can be used. The wiring material may be a metal consisting solely of Cu, W, or Co, or an alloy of Cu, W, or Co with another metal. Among them, metals containing W or Co are preferred, and metals containing Co are more preferred.

[0297] Furthermore, the wiring material may further include a metal, metal nitride, or alloy other than Cu, W, and Co, and may further include, for example, one or more selected from titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxide, and aluminum.

[0298] (Substrate)

[0299] The “substrate” mentioned here includes, for example, a semiconductor substrate composed of a single layer and a semiconductor substrate composed of multiple layers.

[0300] The material constituting the semiconductor substrate composed of a single layer is not particularly limited, but is preferably composed of a Group III-V compound such as silicon, silicon germanium, GaAs, or any combination thereof.

[0301] When a semiconductor substrate is composed of multiple layers, its composition is not particularly limited. For example, it may include an integrated circuit structure in which interconnect features such as metal lines and dielectric materials are exposed on a semiconductor substrate such as silicon. Examples of metals and alloys used in the interconnect features include, but are not limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. Furthermore, layers such as interlayer dielectric layers, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide may be present on the semiconductor substrate.

[0302] <Processing process>

[0303] Hereinafter, the cleaning composition preparation step A and the cleaning step B will be described in detail.

[0304] (Cleaning Agent Composition Preparation Step A)

[0305] The cleaning composition preparation step A is a step for preparing the cleaning composition. The components used in this step are as described above.

[0306] The steps of this step are not particularly limited. For example, a method of preparing the cleaning composition by adding a hydroxylamine compound, a specific chelating agent, a benzotriazole compound, and other optional components and stirring and mixing them can be used. Furthermore, the components can be added all at once or in multiple additions.

[0307] Furthermore, the components contained in the cleaning composition are preferably semiconductor-grade components or components classified as high-purity grades based thereon. Furthermore, it is preferred that components be subjected to filtration to remove foreign matter and / or ion content reduction using ion exchange resins. Furthermore, after mixing the raw material components, it is further preferred to perform filtration to remove foreign matter and / or ion content reduction using ion exchange resins.

[0308] When a concentrated solution of the cleaning composition is prepared, the concentrated solution is diluted to obtain a diluted solution before performing the cleaning step B, and the diluted solution is used to perform the cleaning step B. In this case, the dilution is preferably performed using a dilution solution containing water.

[0309] (Cleaning process B)

[0310] As the cleaning object to be cleaned in the cleaning step B, the above-mentioned laminated object can be cited. As described above, the laminated object 10 having holes formed therein by performing the dry etching step and the dry ashing step can be exemplified (see Figure 1 ). In addition, the stacked product 10 has residue 12 attached to the holes 6.

[0311] <Cleaning method>

[0312] The method for bringing the cleaning composition into contact with the object to be cleaned is not particularly limited. Examples include immersing the object to be cleaned in the cleaning composition in a container, spraying the cleaning composition onto the object to be cleaned, flowing the cleaning composition over the object to be cleaned, and combinations thereof. From the perspective of cleaning performance, immersing the object to be cleaned in the cleaning composition is preferred.

[0313] The temperature of the cleaning composition is preferably 90°C or lower, more preferably 25 to 80°C, further preferably 30 to 75°C, and particularly preferably 40 to 70°C.

[0314] The cleaning time can be adjusted according to the cleaning method used and the temperature of the cleaning composition.

[0315] When washing by a batch immersion method (a batch method in which a plurality of washing objects are immersed in a treatment tank), the washing time is, for example, within 60 minutes, preferably 1 to 60 minutes, more preferably 3 to 20 minutes, and even more preferably 4 to 15 minutes.

[0316] When cleaning is performed in a single-wafer manner, 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 further preferably 20 seconds to 2 minutes.

[0317] In addition, in order to further enhance the cleaning ability of the cleaning composition, a mechanical stirring method may be used.

[0318] Examples of mechanical stirring methods include a method of circulating the cleaning composition on the object to be cleaned, a method of flowing or spraying the cleaning composition on the object to be cleaned, and a method of stirring the cleaning composition by ultrasonic or megasonic waves.

[0319] (Rinsing process B2)

[0320] The method for cleaning a substrate using a cleaning composition may further include a step of rinsing the object to be cleaned with a solvent after the cleaning step (hereinafter referred to as "rinsing step B2").

[0321] The rinsing step B2 is preferably performed after the cleaning step, and is preferably performed by rinsing with a rinsing solvent (rinsing liquid) for 5 seconds to 5 minutes. The rinsing step B2 can be performed using the mechanical stirring method described above.

[0322] The rinse solvent is not particularly limited, and examples thereof include deionized (DI) water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Furthermore, aqueous rinse solutions with a pH exceeding 8 (e.g., diluted aqueous ammonium hydroxide) may also be used.

[0323] As the rinse solvent, aqueous ammonium hydroxide solution, DI water, methanol, ethanol or isopropyl alcohol is preferred, aqueous ammonium hydroxide solution, DI water or isopropyl alcohol is more preferred, and aqueous ammonium hydroxide solution or DI water is further preferred.

[0324] As a method for bringing the rinse solvent into contact with the object to be cleaned, the above-mentioned method for bringing the cleaning composition into contact with the object to be cleaned can be applied in the same manner.

[0325] The temperature of the rinse solvent in the rinse step B2 is preferably 16 to 27°C.

[0326] (Drying Step B3)

[0327] The method for cleaning a substrate using a cleaning composition may include a drying step of drying the cleaning object after the rinsing step.

[0328] The drying method is not particularly limited, and examples thereof include a spin drying method, a method of flowing a dry gas over the surface of the object to be cleaned, a method of heating the substrate by a heating mechanism such as a hot plate or an infrared lamp, a Marangoni drying method, a Rotagoni drying method, an IPA (isopropyl alcohol) drying method, and combinations thereof.

[0329] The drying time varies depending on the drying method, but is preferably 30 seconds to several minutes.

[0330] The cleaning method for a substrate using a cleaning composition is not limited to the aforementioned laminated product comprising at least a metal layer, an interlayer insulating layer, and a metal hard mask in this order on a substrate. For example, the composition can also be used to remove residues originating from a resist film that adhere to a laminated product comprising at least a metal layer, an interlayer insulating layer, and a resist film in this order on a substrate.

[0331] Example

[0332] Hereinafter, the present invention will be described in further detail with reference to the examples. The materials, usage amounts, ratios, treatment contents, and treatment steps shown in the following examples can be appropriately modified without departing from the purpose of the present invention. Therefore, the scope of the present invention should not be interpreted restrictively by the examples shown below. In addition, unless otherwise specified, "%" means "mass %."

[0333] [Preparation of cleaning composition]

[0334] The cleaning agent compositions were prepared according to the following steps. In each cleaning agent composition, the contents of various components (all by mass) are as shown in the table.

[0335] 〔raw material〕

[0336] The raw materials used in the preparation of the cleaning composition are shown below. In addition, the compounds used in the preparation of the cleaning composition were all classified as semiconductor grade compounds or compounds classified as high purity grades based thereon.

[0337] <Hydroxyamine Compound (or Redox Agent)>

[0338] HA: Hydroxylamine

[0339] HAS: Hydroxylamine sulfate

[0340] DEHA: N,N-diethylhydroxylamine

[0341] H2O2: Hydrogen peroxide (not a hydroxylamine compound)

[0342] <Specific Chelating Agents>

[0343] (Aminophosphonic acid compound)

[0344] 1-a: Nitrosotris(methylenephosphonic acid)

[0345] 1-b: Ethylenediaminetetrakis(methylenephosphonic acid)

[0346] (Hydroxy acid compound)

[0347] 2-a: Diethanolglycine

[0348] 2-b: Citric acid

[0349] 2-c: Malic acid

[0350] (Phosphonocarboxylic acid compound)

[0351] 3-a: 2-phosphonobutane-1,2,4-tricarboxylic acid

[0352] 3-b: 4-phosphonobutyric acid

[0353] 3-c: Glycine-N,N-bis(methylenephosphonic acid)

[0354] (Aromatic carboxylic acid compound)

[0355] 4-a: Isophthalic acid

[0356] 4-b: Salicylic acid

[0357] (Polycarboxylic acid compound)

[0358] 5-a: Glutaric acid

[0359] 5-b: 1,3,5-pentanetricarboxylic acid

[0360] 5-c: 3-Methyladipic acid

[0361] 5-d: N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid monohydrochloride hydrate (not included in specific chelating agents)

[0362] (hydroxyphosphonic acid compound)

[0363] 6-a: 1-hydroxyethane-1,1-diphosphonic acid

[0364] 6-b: glycerol 3-phosphate

[0365] <pH regulator>

[0366] DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene

[0367] MEA: monoethanolamine

[0368] TMAH: tetramethylammonium hydroxide

[0369] <organic solvent>

[0370] EGBE: ethylene glycol monobutyl ether

[0371] EGME: ethylene glycol monomethyl ether

[0372] <water>

[0373] Water: DI water

[0374] 〔Evaluation〕

[0375] The following various evaluations were conducted on each of the cleaning agent compositions prepared above.

[0376] <Removal performance of organic residues>

[0377] A multilayer substrate was prepared in which a resist film, a metal hard mask (TiN layer), an etch stop layer (Al2O3 layer), a C o layer, and an interlayer dielectric (ILD) were sequentially laminated on the surface of the substrate. The multilayer substrate was subjected to lithography-based patterning, etching using a metal plasma etching apparatus, and removal of the resist film based on oxygen plasma ashing to produce a multilayer substrate for evaluation tests (hereinafter, also referred to as "test piece"). The obtained test pieces were cleaned using the cleaning agent compositions of each of the examples and each of the comparative examples.

[0378] A 500 mL glass beaker was filled with 200 mL of the cleaning composition. While stirring with a stirrer, the temperature of the cleaning composition was raised to 65°C. Next, the test piece prepared above was immersed in the cleaning composition at a liquid temperature of 65°C for 5 minutes while stirring, thereby cleaning the test piece. While the test piece was immersed in the cleaning composition, the test piece was held using 4-inch plastic locking pins so that the surface of the test piece where the photoresist was removed faced the stirrer.

[0379] After the cleaning time has elapsed, the test piece is immediately removed from the cleaning composition, placed in a 500 mL plastic beaker, and placed in 400 mL of DI water (17°C) while being gently stirred. After immersing the test piece in the DI water for 30 seconds, the test piece is immediately removed and rinsed under a stream of 17°C DI water for 30 seconds.

[0380] Next, the test piece was exposed to a nitrogen gas flow to blow off the liquid droplets adhering to the surface of the test piece, thereby drying the surface of the test piece.

[0381] After the nitrogen drying step, the test piece was removed from the holding portion of the plastic tweezers and stored in a plastic storage box with a lid with the component surface facing upward.

[0382] The surface composition of the resulting test pieces was analyzed using X-ray photoelectron spectroscopy (XPS). The surface of the resulting test pieces was measured using an XPS apparatus (manufactured by Ulvac-PHI, trade name Quantera SXM). The reduction in the amount of fluorine atoms contained in the organic residue of the measured test pieces before and after treatment was calculated and used as the residue removal rate. The organic residue removal performance was evaluated according to the following evaluation criteria.

[0383] 5: Removal rate is more than 95%

[0384] 4: Removal rate is more than 80% and less than 95%

[0385] 3: Removal rate is more than 75% and less than 80%

[0386] 2: Removal rate is more than 50% and less than 75%

[0387] 1: Removal rate is less than 50%

[0388] <Temporal Stability of Removal Performance>

[0389] Next, a storage test was performed using the cleaning compositions of the examples and comparative examples as test solutions, and the temporal stability of the removal performance of each cleaning composition was evaluated.

[0390] A 250 mL high-density polyethylene container was filled with 200 mL of each test solution prepared by the above method and sealed, and the container filled with the test solution was stored in an environment of 60° C. for 24 hours.

[0391] A removal performance evaluation test was performed according to the above-mentioned removal performance evaluation method, except that the cleaning composition after the storage test was used, and the temporal stability of each cleaning composition was evaluated.

[0392] <Corrosion resistance>

[0393] A substrate (a substrate having a metal layer formed thereon) was prepared, in which a layer composed of Co (Co layer) was formed on one surface of a substrate (silicon wafer (diameter: 12 inches)) by CVD (Chemical Vapor Deposition). The substrate having the Co layer formed thereon was then immersed in the cleaning compositions of Examples and Comparative Examples (65°C) for 5 minutes.

[0394] The etching rate of the Co layer by the cleaning composition was calculated based on the difference in the thickness of the Co layer before and after immersion in the cleaning composition. The lower the etching rate (ER) of the Co layer measured in this test, the better the corrosion resistance of the Co layer.

[0395] Based on the measured ER, the corrosion resistance of the Co layer was evaluated according to the following criteria.

[0396] A:ER<

[0397] B: ≤ER<

[0398] C: ≤ER<

[0399] D: ≤ER<

[0400] E: ≤ER

[0401] 〔result〕

[0402] The composition and evaluation results of each cleaning composition are shown in Tables 1 to 7 below.

[0403] In the table, "HA compound" means "hydroxylamine compound" and "BTA compound" means "benzotriazole compound".

[0404] The mark "Yes" in the "pH Adjuster" column indicates that each cleaning composition contains a pH adjuster. The content of the pH adjuster in each cleaning composition is an amount such that the pH of the final cleaning composition becomes the value shown in the "pH" column in the table.

[0405] The description "balance" shown as the water content means that the finally obtained cleaning composition contains components other than the pH adjuster in the content shown in the table and the pH adjuster in an amount to achieve the pH shown in the table, and the remainder is water.

[0406] In the table, the "Ratio 1" column represents the ratio (mass ratio) of the content of the hydroxylamine compound (or redox agent) to the content of the chelating agent, and the "Ratio 2" column represents the ratio (mass ratio) of the content of the hydroxylamine compound (or redox agent) to the content of the benzotriazole compound.

[0407] In the table, the "Removal Performance" column shows the evaluation results of the organic residue removal performance of the cleaning compositions of each Example and each Comparative Example. The "After Preparation" column of the "Removal Performance" column shows the removal performance evaluation results immediately after the preparation of each cleaning composition, and the "After Storage" column of the "Removal Performance" column shows the removal performance evaluation results of each cleaning composition after the storage test.

[0408] [Table 1]

[0409] [Table 1]

[0410]

[0411] [Table 2]

[0412] [(Continued) Table 1]

[0413]

[0414] [Table 3]

[0415] [Table 2]

[0416]

[0417] [Table 4]

[0418] [(Continued) Table 2]

[0419]

[0420] [Table 5]

[0421] [Table 3]

[0422]

[0423] [Table 6]

[0424] [Table 4]

[0425]

[0426] [Table 7]

[0427] [Table 5]

[0428]

[0429] [Table 8]

[0430] [Table 6]

[0431]

[0432] [Table 9]

[0433] [Table 7]

[0434]

[0435] From the results shown in the table, it was confirmed that the problems of the present invention can be solved by using the cleaning composition of the present invention.

[0436] The results shown in the table confirm that when the content of the specific chelating agent is 0.1% by mass or more relative to the total mass of the cleaning composition, the temporal stability of the removal performance is more excellent, and when it is 0.5% by mass or more, the temporal stability of the removal performance is further excellent (comparison of Examples 1 to 3, and comparison of Examples 23, 24, and 27).

[0437] Furthermore, it was confirmed that when the content of the specific chelating agent was 10% by mass or less relative to the total mass of the cleaning composition, the corrosion resistance was further improved (comparison between Examples 4 and 5).

[0438] It was confirmed that when the content of the specific chelating agent is 0.1% by mass or more relative to the total mass of the cleaning composition, the temporal stability of the removal performance is more excellent, and when it is 0.5% by mass or more, the temporal stability of the removal performance is further excellent (comparison of Examples 1 to 3, and comparison of Examples 24, 25, and 27).

[0439] Furthermore, it was confirmed that when the content of the specific chelating agent was 10% by mass or less relative to the total mass of the cleaning composition, the corrosion resistance was further improved (comparison between Examples 4 and 5).

[0440] It was confirmed that when the ratio 1 (the mass ratio of the content of the hydroxylamine compound to the content of the specific chelating agent) in the cleaning composition is 100 or less, the temporal stability of the removal performance is more excellent, and when the ratio 1 is 10 or less, the temporal stability of the removal performance is further excellent (comparison of Examples 1 to 3, comparison of Examples 24, 25 and 27).

[0441] Furthermore, it was confirmed that when the ratio 1 was 0.1 or more, the corrosion resistance was more excellent, and when the ratio 1 was 1 or more, the corrosion resistance was further excellent (comparison of Examples 2, 4, and 5, and comparison of Examples 28 and 35).

[0442] It was confirmed that when the content of the benzotriazole compound was 0.5% by mass or less relative to the total mass of the cleaning composition, the residue removal performance was more excellent (comparison between Examples 2 and 8).

[0443] It was confirmed that when the ratio 2 (the mass ratio of the content of the hydroxylamine compound to the content of the benzotriazole compound) in the cleaning composition was 1000 or less, the corrosion resistance was more excellent (comparison between Examples 7 and 12).

[0444] Furthermore, it was confirmed that when the ratio 2 was 10 or more, the residue removal performance was more excellent (comparison between Examples 2 and 8).

[0445] The results in Table 2 confirmed that the removal performance was more excellent when hydroxylamine or hydroxylamine sulfate was used among the hydroxylamine compounds (comparison of Examples 24, 39, and 40).

[0446] Furthermore, it was confirmed that when two or more hydroxylamine compounds were used, corrosion resistance was more excellent than when a hydroxylamine compound was used alone (comparison of Examples 24, 39, and 41).

[0447] The results in Tables 1 to 6 indicate that the removal performance and the temporal stability of the removal performance are superior when aminophosphonic acid compounds or hydroxy acid compounds among specific chelating agents are used (comparison of Examples 2, 16, 24, 35, 36, 45, 47, 48, 50, 52, 54, 56, 57, 59, and 61).

[0448] The results in Table 3 indicate that the temporal stability of the removal performance is superior when 2-phosphonobutane-1,2,4-tricarboxylic acid or 4-phosphonobutyric acid among the phosphonocarboxylic acid compounds is used (comparison of Examples 45, 47, and 48), and that the residue removal performance is superior when 2-phosphonobutane-1,2,4-tricarboxylic acid or glycine-N,N-bis(methylenephosphonic acid) is used (comparison of Examples 45, 47, and 48).

[0449] The results in Table 5 indicate that the temporal stability of the removal performance is superior when glutaric acid is used among the polycarboxylic acid compounds (comparison of Examples 54, 56, and 57), and that the removal performance is superior when 1,3,5-pentanetricarboxylic acid is used (comparison of Examples 54, 56, and 57).

[0450] According to the results in Table 6, it was confirmed that when 1-hydroxyethane-1,1-diphosphonic acid among the hydroxyphosphonic acid compounds was used, the removal performance and corrosion resistance were better (comparison of Examples 59 and 61), and when glycerol 3-phosphate was used, the time stability of the removal performance was better (comparison of Examples 59 and 61).

[0451] Explanation of symbols

[0452] 1-substrate, 2-metal layer, 3-etch stop layer, 4-interlayer insulating layer, 5-metal hard mask, 6-hole, 10-stack, 11-inner wall, 11a-cross-section wall, 11b-bottom wall, 12-residue.

Claims

1. A cleaning composition for semiconductor devices, comprising: One or more hydroxylamine compounds selected from hydroxylamine and hydroxylamine salts; One or more chelating agents selected from carboxylic acid chelating agents and phosphonic acid chelating agents other than polyaminocarboxylic acids; and Benzotriazole compounds, The content of the benzotriazole compound is 0.5% by mass or less based on the total mass of the cleaning composition.

2. The cleaning composition according to claim 1, wherein The chelating agent includes the phosphonic acid-based chelating agent.

3. The cleaning composition according to claim 2, wherein The phosphonic acid chelating agent includes one or more compounds selected from the group consisting of hydroxyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonocarboxylic acid compounds.

4. The cleaning composition according to claim 2 or 3, wherein The phosphonic acid chelating agent includes an aminophosphonic acid compound.

5. The cleaning composition according to claim 1, wherein The chelating agent includes the carboxylic acid chelating agent.

6. The cleaning composition according to claim 5, wherein The carboxylic acid chelating agent includes one or more compounds selected from the group consisting of hydroxy acid compounds, polycarboxylic acid compounds, and aromatic polycarboxylic acid compounds.

7. The cleaning composition according to claim 5 or 6, wherein The carboxylic acid chelating agent includes a hydroxy acid compound.

8. The cleaning composition according to claim 1 or 2, wherein The hydroxylamine compound includes at least one selected from the group consisting of hydroxylamine, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, hydroxylamine sulfate, N,N-dimethylhydroxylamine sulfate, and N,N-diethylhydroxylamine sulfate.

9. The cleaning composition according to claim 1 or 2, wherein The benzotriazole compound includes a compound represented by the following formula (A): In formula (A), R 11 represents a carboxyl group, an amino group, or an alkyl group having 1 to 6 carbon atoms, n represents an integer from 0 to 2, R 12 represents a hydrogen atom or a hydroxyl group.

10. The cleaning composition according to claim 1 or 2, wherein The mass ratio of the content of the hydroxylamine compound to the content of the benzotriazole compound is 1 to 1000.

11. The cleaning composition according to claim 1 or 2, wherein The mass ratio of the content of the hydroxylamine compound to the content of the chelating agent is 0.1 to 100. 12 . The cleaning composition according to claim 1 , which is used for cleaning a substrate having a metal layer containing at least one metal selected from copper, tungsten and cobalt.

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