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 with application number 202080060051.7, the title of which is "Cleaning agent composition". The filing date of the parent application of this application is July 8, 2020, and the priority date is August 23, 2019. TECHNICAL FIELD

[0002] The present application relates to a cleaning agent composition. In particular, it relates to a cleaning agent composition that can be preferably used for the manufacture of semiconductor devices. BACKGROUND

[0003] Semiconductor devices such as CCDs (Charge-Coupled Devices), memories, etc. are manufactured using photolithography technology to form fine electronic circuit patterns on substrates. Specifically, semiconductor devices are manufactured by forming a resist film on a laminate of a metal film that becomes a wiring material, an etching stopper layer, and an interlayer insulating layer on a substrate, and performing a photolithography process and a dry etching process (e.g., plasma etching treatment).

[0004] For substrates that have undergone a dry etching process, an etching resist stripping process for stripping an etching resist film mainly composed of organic matter is performed as needed by a stripping method such as a dry ashing process (e.g., plasma ashing treatment), etc.

[0005] In substrates that have undergone a dry etching process and an etching resist stripping process, since a large amount of residue containing organic components derived from the etching resist film is attached to the wiring film and / or the interlayer insulating film thereof, cases where a treatment for removing the residue using a cleaning agent composition is performed so as not to hinder the next process are often seen.

[0006] For example, in Patent Literature 1, a cleaning composition is disclosed that contains an oxidation-reduction agent, a first chelating agent polyamino polycarboxylic 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] Prior Art Documents

[0008] Patent Literature

[0009] Patent Literature 1: Japanese Patent Application Laid-Open No. 2017-504190 SUMMARY

[0010] Technical Problem to be Solved by the Invention

[0011] The present inventors, etc. have studied a cleaning agent composition used in the manufacturing process of semiconductor devices in light of the description of Patent Literature 1, and as a result, found that there is room for further improvement regarding the removal performance of organic matter residue after the cleaning agent composition is stored over time.

[0012] Further, the cleaning agent composition is required to inhibit corrosion (corrosion resistance) of a wiring metal of a metal layer possessed by a semiconductor device as a cleaning target, the wiring metal being, for example, a metal selected from one or more of Cu, W, and Co.

[0013] Therefore, an object of the present application is to provide a cleaning agent composition for a semiconductor device, which is excellent in removal performance of organic matter residues over time and also excellent in corrosion resistance to a metal layer.

[0014] Means for solving the technical problem

[0015] As a result of intensive studies made by the present inventors and others in order to achieve the above object, it has been found that the above object can be solved by the following configuration.

[0016] 〔1〕 A cleaning agent composition, which is a cleaning agent composition for a semiconductor device, the cleaning agent composition comprising: one or more hydroxylamine compounds selected from a hydroxylamine and a hydroxylamine salt; one or more chelating agents selected from a carboxylic acid-based chelating agent other than a polyaminocarboxylic acid and a phosphonic acid-based chelating agent; and a benzotriazole compound.

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

[0018] 〔3〕 The cleaning agent composition according to 〔2〕, wherein the phosphonic acid-based chelating agent comprises one or more compounds selected from a hydroxyphosphonic acid compound, an aminophosphonic acid compound, and a phosphono carboxylic acid compound.

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

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

[0021] 〔6〕 The cleaning agent composition according to 〔5〕, wherein the carboxylic acid-based chelating agent comprises one or more compounds selected from a hydroxy acid compound, a polycarboxylic acid compound, and an aromatic polycarboxylic acid compound.

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

[0023] 〔8〕 The cleaning agent composition according to any one of <1> to <7>, wherein the hydroxylamine compound contains one or more selected from the group consisting of hydroxylamine, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, hydroxylamine sulfate, N,N-dimethylhydroxylamine sulfate, and N,N-diethylhydroxylamine sulfate.

[0024] 〔9〕 The cleaning agent composition according to any one of <1> to <8>, wherein the benzotriazole compound contains a compound represented by the following formula (A).

[0025] 〔10〕 The cleaning agent 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 agent 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 agent composition according to any one of <1> to <11>, which is used for cleaning of a substrate having a metal layer containing one or more selected from the group consisting of copper, tungsten, and cobalt.

[0028] Effects of Invention

[0029] According to the present application, it is possible to provide a cleaning agent composition for semiconductor devices, which has excellent temporal stability of removal performance of organic residue and also excellent corrosion resistance to a metal layer. BRIEF DESCRIPTION OF DRAWINGS

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

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

[0032] The following description of the components is sometimes made according to the representative embodiment of the present application, but the present application is not limited to this embodiment.

[0033] In addition, in the present specification, the numerical range indicated using "to" means a range including the lower limit value and the upper limit value of the numerical values recited before and after "to".

[0034] Also, in the present specification, when referred to as "preparation", it means that in addition to the preparation of synthesizing or blending a specific material, it also includes the procurement of a prescribed material by purchase.

[0035] Also, in the present specification, "ppm" means "parts-per-million (10 -6 )", "ppb" means "parts-per-billion (10 -9 )", and "ppt" means "parts-per-trillion (10 -12 )".

[0036] Also, in the present specification, (Angstrom) corresponds to 0.1 nm.

[0037] Also, in the present specification, the notation of a group (a group of atoms) not marked with a notation of substitution and non-substitution includes a group having no substituent, and also includes a group having a substituent, within a range not impairing the effects of the present application. 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). The same applies to each compound.

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

[0039] Also, in the present specification, "radiation" means the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, or electron beams. Also, in the present specification, light means actinic rays or radiation. "Exposure" in the present application includes not only exposure using a mercury lamp, far ultraviolet rays typified by excimer laser, X-rays, or EUV light, but also drawing using a particle ray such as an electron beam or an ion beam, unless specifically specified.

[0040] [Cleaning agent composition]

[0041] The cleaning agent composition of the present application is a cleaning agent composition for semiconductor devices, which contains a hydroxylamine compound selected from one or more of hydroxylamine and a hydroxylamine salt, a chelating agent (hereinafter also referred to as "specific chelating agent") selected from one or more of a carboxylic acid (wherein, a polyamino carboxylic acid is excluded) and a phosphonic acid, and a benzotriazole compound.

[0042] The present inventors have surprisingly obtained the insight that, by containing a hydroxylamine compound, a specific chelating agent, and a benzotriazole compound, a cleaning agent composition having excellent stability over time in the removal performance of organic matter residues and also excellent corrosion resistance to a metal layer can be obtained.

[0043] Further, in the present specification, "organic matter residue" refers to a residue mainly composed of organic matter generated in a manufacturing process of a semiconductor device. In this case, "mainly composed of organic matter" means that the content of organic matter is 50% by mass or more with respect to the total amount of the residue. Further, in the present specification, the removal performance of the organic matter residue is also simply referred to as "removal performance".

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

[0045] [Component]

[0046] [Hydroxylamine compound]

[0047] The cleaning agent composition of the present application contains a hydroxylamine compound selected from one or more of hydroxylamine and hydroxylamine salts. The hydroxylamine compound has a function of promoting decomposition and solubilization of the organic matter residue.

[0048] Here, "hydroxylamine" in relation to the hydroxylamine compound refers to a broad sense of hydroxylamine including substituted or unsubstituted alkylhydroxylamine, and either of them can achieve excellent stability of removal performance over time and excellent corrosion resistance.

[0049] The hydroxylamine compound is not particularly limited, and as a preferable form, unsubstituted hydroxylamine and hydroxylamine derivatives and salts of these can be given.

[0050] The hydroxylamine derivative is not particularly limited, and for example, 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 can be given.

[0051] As a salt of unsubstituted hydroxylamine or a hydroxylamine derivative, an inorganic acid salt or an organic acid salt of the above unsubstituted hydroxylamine or hydroxylamine derivative is preferable, and a salt of an inorganic acid bonded to a nonmetal atom such as Cl, S, N, or P and a hydrogen atom is more preferable, and a salt of any one of hydrochloric acid, sulfuric acid, and nitric acid is further preferable. Among them, hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine phosphate, N,N-diethylhydroxylamine sulfate, N,N-diethylhydroxylamine nitrate, or a mixture of these is preferable.

[0052] Further, an organic acid salt of the above unsubstituted hydroxylamine or hydroxylamine derivative can also be used. As the organic acid salt, for example, hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride can be given.

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

[0054] The hydroxylamine compound can be used singly or two or more kinds thereof can be used. From the viewpoint of more excellent corrosion resistance, two or more kinds of the hydroxylamine compound are preferably used.

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

[0056] Here, from the viewpoint of more excellent removal performance, the content of the hydroxylamine compound is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the cleaning agent composition.

[0057] Also, from the viewpoint of more excellent corrosion resistance, the content of the hydroxylamine compound is preferably 20% by mass or less, more preferably 15% by mass or less, relative to the total mass of the cleaning agent composition.

[0058] The hydroxylamine compound can be used singly or two or more kinds thereof can be used. When two or more kinds are used, the total content of these is preferably within the above range.

[0059] <Specific Chelating Agent>

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

[0061] In the present specification, the polyaminocarboxylic acid means a compound having a plurality of amino groups and one or more carboxyl groups.

[0062] The specific chelating agent contained in the cleaning agent composition has a function of chelating with metals in the cleaning step included in the manufacturing process of semiconductor devices. Among them, a compound having two or more functional groups (coordination bases) which coordinate with metal ions in one molecule is preferred.

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

[0064] (Phosphonic Acid-Based Chelating Agent)

[0065] The phosphonic acid-based chelating agent is a compound having one or more phosphonic acid groups and chelating with metals.

[0066] As the phosphonic acid-based chelating agent, for example, a hydroxyphosphonic acid compound, a polyphosphonic acid compound, an aminophosphonic acid compound, and a phosphonocarboxylic acid compound can be mentioned.

[0067] Among them, a hydroxyphosphonic acid compound, an aminophosphonic acid compound, or a phosphonocarboxylic acid compound is preferred, and an aminophosphonic acid compound is 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] Further, the polyphosphonic acid compound is a compound having two or more phosphonic acid groups in the molecule. In addition, a compound having any one of a hydroxyl group, an amino group, and a carboxyl group in the molecule is excluded from the polyphosphonic acid compound.

[0070] As the hydroxyphosphonic acid compound and the polyphosphonic acid compound, for example, a compound represented by the following formula (1) can be mentioned.

[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] The alkyl group represented by R 1 in the formula (1) can be any one of a linear shape, a branched shape, and a cyclic shape, and is preferably a linear shape or a branched shape.

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

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

[0077] As the compound represented by the formula (1), 1-hydroxyethane-1, 1-diphosphonic acid, 1-hydroxypropane-1, 1-diphosphonic acid, and 1-hydroxybutane-1, 1-diphosphonic acid can be mentioned.

[0078] Further, as the hydroxyphosphonic acid compound other than the compound represented by the formula (1), 2-hydroxyethane-1, 1-diphosphonic acid, 3-hydroxypropane-1, 1-diphosphonic acid, glycerol 3-phosphate, and ethanehydroxy-1, 1, 2-triphosphonic acid can be mentioned.

[0079] As the hydroxyphosphonic acid compound, 1-hydroxyethane-1,1-diphosphonic acid or glycerol 3-phosphate is preferable. Among them, 1-hydroxyethane-1,1-diphosphonic acid is more preferable from the viewpoint of more excellent removal performance and corrosion resistance, and glycerol 3-phosphate is more preferable from the viewpoint of more excellent time stability of the removal performance.

[0080] The amino phosphonic acid compound is a compound having one or more phosphonic acid groups and one or more amino groups in a molecule. In addition, a compound having a carboxyl group in a molecule is excluded from the amino phosphonic acid compound.

[0081] As the amino phosphonic acid compound, for example, a compound represented by the following formula (2) and a compound represented by formula (3) can be given.

[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 are the same as Q and R 3 in formula (2).

[0088] In formula (2), R 2 represents an alkylene group can be either of a linear shape and a branched shape. As the alkylene group represented by R 2 , an alkylene group having 1 to 12 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and a methylene group or an ethylene group is further preferable.

[0089] As Y in formula (2), -PO3H2or a group represented by formula (4) is preferable, and -PO3H2is more preferable.

[0090] Further, as the combination of R 2 and Y in formula (2), the combination in which R 2 is a methylene group and Y is -PO3H2or the combination in which R 2 is an ethylene group and Y is a group represented by formula (4) is preferable.

[0091] As Q in formulae (2) and (4), -R 3 -PO3H2is preferable.

[0092] In formulae (2) and (4), R 3 The alkylene group represented by R 3 The alkylene group represented by R

[0093] As the aminophosphonic acid compound represented by formula (2), for example, ethylaminobis(methylene phosphonic acid), dodecylaminobis(methylene phosphonic acid), nitroso tris(methylene phosphonic acid) (NTPO), ethylenediamine bis(methylene phosphonic acid) (EDDPO), 1,3-propanediyl diamine bis(methylene phosphonic acid), ethylenediamine tetra(methylene phosphonic acid) (EDTPO), ethylenediamine tetra(ethyl phosphonic acid), 1,3-propanediamine tetra(methylene phosphonic acid) (PDTMP), 1,2-diaminopropane tetra(methylene phosphonic acid), and 1,6-hexamethylenediamine tetra(methylene phosphonic acid) can be given.

[0094] [Chemical Formula 4]

[0095]

[0096] In formula (1), R 4 and R 5 independently represent an alkylene group having 1 to 4 carbon atoms, n represents an integer of 1 to 4, and Z 1 to Z 4 represent an alkyl group having a phosphonic acid group. 5 At least 4 of Z

[0097] In formula (3), R 4 and R 5 The alkylene group having 1 to 4 carbon atoms represented by R 4 and R 5 The alkylene group having 1 to 4 carbon atoms represented by R

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

[0099] Z 1 to Z 5 The alkyl group and the alkyl group having a phosphonic acid group represented by Z

[0100] As the number of the phosphonic acid group in the alkyl group having a phosphonic acid group represented by Z 1 to Z 5 is 1 or 2, and more preferably 1.

[0101] As Z 1 ~Z 5 The alkyl group represented is preferably monophosphonomethyl or monophosphonoethyl, more preferably monophosphonomethyl.

[0102] Z in equation (3) 1 ~Z 5 Z is preferred 1 ~Z 4 and n Z 5 All of them are alkyl groups with phosphonic acid groups as described above.

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

[0104] As aminophosphonic acid compounds, ethylaminobis(methylenephosphonic acid), nitrosotris(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), ethylenediaminetetra(methylenephosphonic acid) (EDTP0), ethylenediaminetetra(ethylenephosphonic acid), 1,3-propanediaminetetra(methylenephosphonic acid) (PDTMP) or diethylenetriaminepenta(methylenephosphonic acid) (DEPPO) are preferred, and NTPO or EDDPO are more preferred.

[0105] Phosphonocarboxylic acid compounds are compounds that have one or more carboxyl groups and one or more phosphonic acid groups in their molecules.

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

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

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

[0109] R 6 The aliphatic hydrocarbon group represented can be any of straight-chain, branched, or cyclic, but straight-chain or branched is preferred. Furthermore, R... 6 The aliphatic hydrocarbon group represented can be either saturated or unsaturated hydrocarbons, but saturated hydrocarbons are preferred.

[0110] R 6The aliphatic hydrocarbon group represented can have a linking group containing one or more heteroatoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom, preferably an oxygen atom or a nitrogen atom linking group, or no linking group containing a heteroatom, more preferably no linking group containing a heteroatom, from the viewpoint of more excellent time stability of the removal performance.

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

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

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

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

[0115] As the hydroxyphosphonic acid compound, for example, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 4-phosphonobutyric acid, and glycine-N, N-bis (methylene phosphonic acid) can be given, and 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 4-phosphonobutyric acid, or glycine-N, N-bis (methylene phosphonic acid) is preferable.

[0116] Among them, 2-phosphonobutane-1, 2, 4-tricarboxylic acid or 4-phosphonobutyric acid is more preferable from the viewpoint of more excellent time stability of the removal performance, and 2-phosphonobutane-1, 2, 4-tricarboxylic acid or glycine-N, N-bis (methylene phosphonic acid) is more preferable from the viewpoint of excellent residue removal performance and corrosion resistance. As the hydroxyphosphonic acid compound, 2-phosphonobutane-1, 2, 4-tricarboxylic acid is further preferable.

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

[0118] As the polyphosphonic acid compound, for example, a compound represented by the following formula (6) can be given.

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

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

[0121] R 7The aliphatic hydrocarbon group represented can be any of a straight chain, a branched chain, and a cyclic, and is preferably a straight chain or a branched chain. Also, R 7 The aliphatic hydrocarbon group represented can be any of a saturated hydrocarbon and an unsaturated hydrocarbon, but is preferably a saturated hydrocarbon.

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

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

[0124] As the polyphosphonic acid compound, for example, ethylene bisphosphonic acid, propylene bisphosphonic acid, butylene bisphosphonic acid, and isopropylene bisphosphonic acid can be given.

[0125] Also, as the polyphosphonic acid compound, the compounds ((co)polymers) described in

[0031] to

[0046] of International Publication No. 2018 / 030006 can also be given, which are incorporated into the present specification.

[0126] (Carboxylic acid-based chelating agent)

[0127] The carboxylic acid-based chelating agent is a compound having one or more carboxyl groups and chelating with a metal. Hereinafter, the carboxylic acid-based chelating agent other than the polyaminocarboxylic acid is simply described as "carboxylic acid-based chelating agent" unless otherwise specified. Also, the compound having both a carboxyl group and a phosphonic acid group is not included in the carboxylic acid-based chelating agent, but is included in the phosphonic acid-based chelating agent.

[0128] As the carboxylic acid-based chelating agent, for example, a polycarboxylic acid compound, a hydroxy acid compound, an aromatic carboxylic acid compound, and an amino acid compound can be given.

[0129] Among them, the polycarboxylic acid compound, the hydroxy acid compound, or the aromatic carboxylic acid compound is preferred, and the hydroxy acid compound is more preferred.

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

[0131] As the polycarboxylic acid compound, for example, a compound represented by the following formula (7) can be given.

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

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

[0134] R8 The aliphatic hydrocarbon group represented can be any of linear, branched, and cyclic, and is preferably linear or branched. Also, R 8 The aliphatic hydrocarbon group represented can be any of saturated hydrocarbons and unsaturated hydrocarbons, but is preferably a saturated hydrocarbon.

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

[0136] R 8 The number of carbon atoms of the aliphatic hydrocarbon group represented 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 more excellent stability over time of the removal performance.

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

[0138] As the polycarboxylic acid compound, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 3-methyl adipic acid, sebacic acid, maleic acid, and 1,3,5-pentane tricarboxylic acid can be given, and succinic acid, glutaric acid, adipic acid, pimelic acid, 3-methyl adipic acid, or 1,3,5-pentane tricarboxylic acid is preferred, and from the viewpoint of more excellent stability over time of the removal performance, succinic acid, glutaric acid, or adipic acid is more preferred. Also, from the viewpoint of the removal performance, 1,3,5-pentane tricarboxylic acid is more preferred.

[0139] The hydroxy acid compound is a compound having one or more carboxyl groups and one or more hydroxyl groups in the molecule. However, a compound having an aromatic ring in the molecule is not included in the hydroxy acid compound.

[0140] As the hydroxy acid compound, for example, a compound represented by the following formula (8) can be given.

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

[0142] In formula (8), R 9 represents an aliphatic hydrocarbon group of (m+n) valence, 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 can be any of linear, branched, and cyclic, and is preferably linear or branched. Also, R 9 The aliphatic hydrocarbon group represented can be any of saturated hydrocarbons and unsaturated hydrocarbons, but is preferably a saturated hydrocarbon.

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

[0145] R 9 The number of carbon atoms of the aliphatic hydrocarbon group represented 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] m in formula (8) is preferably 1 or 2, and more preferably 1.

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

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

[0149] As the hydroxy acid compound, for example, malic acid, citric acid, glycolic acid, tartaric acid, lactic acid, and diethanolglycine can be given, and preferably malic acid, citric acid, or diethanolglycine, and more preferably citric acid or diethanolglycine from the viewpoint of excellent corrosion resistance.

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

[0151] As the aromatic carboxylic acid compound, for example, a compound represented by the following formula (9) can be given.

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

[0153] In formula (9), Ar represents a q-valent aromatic hydrocarbon group which can 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 coordination site other than a carboxyl group and a phosphonic acid group.

[0154] As the substituent which the aromatic hydrocarbon group represented by Ar can have, for example, one or more coordination sites selected from 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) which can have the above coordination sites can be given. In addition, the aliphatic hydrocarbon group possessed by Ar can have a carboxyl group in formula (9).

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

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

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

[0158] As the aromatic carboxylic acid compound, for example, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and gallic acid can be given, and isophthalic acid or salicylic acid is preferable from the viewpoint of excellent corrosion resistance, and isophthalic acid is more preferable.

[0159] The amino acid compound is a compound having one or more carboxyl groups and one or more amino groups as the ligating group in the molecule. However, the above-mentioned hydroxy acid compound and the aromatic carboxylic acid compound are not included in the amino acid compound.

[0160] As the amino acid compound, for example, glycine, serine, α-alanine (2-amino propionic acid), β-alanine (3-amino propionic acid), leucine, isoleucine, cysteine, ethionine, threonine, aspartic acid, glutamic acid, proline, methionine, and phenylalanine, and salts of these can be given.

[0161] As the salt, alkali metal salts such as sodium salt and potassium salt, ammonium salt, carbonate, and acetate can be given.

[0162] As the specific chelating agent, a hydroxy phosphonic acid compound, an amino phosphonic acid compound, a phosphonocarboxylic acid compound, a polycarboxylic acid compound, a hydroxy acid compound, or an aromatic carboxylic acid compound is preferable from the viewpoint of more excellent removal performance and more excellent time stability of the removal performance, and an amino phosphonic acid compound or a hydroxy acid compound is more preferable.

[0163] The specific chelating agent can be used singly or two or more kinds can be used.

[0164] From the viewpoint of more excellent time 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 further preferably 0.5% by mass or more, relative to the total mass of the cleaning agent composition.

[0165] Further, the upper limit is not particularly limited, but from the viewpoint of more excellent corrosion resistance, the content is preferably 30% by mass or less, more preferably 10% by mass or less, and further preferably less than 2% by mass, relative to the total mass of the cleaning agent composition.

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

[0167] Further, from the viewpoint of more excellent time stability of the removal performance, the above-mentioned mass ratio is preferably 100 or less, and more preferably 10 or less.

[0168] <benzotriazole compound>

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

[0170] As the benzotriazole compound, as long as it is a compound having a benzotriazole structure, it is not particularly limited, and for example, a compound represented by the following formula (A) can be mentioned.

[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, and when n is 2 or more, n number of R 11 may be the same or different.

[0176] As the substituent represented by R 11 in formula (A), for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, a group represented by the following formula (B), a hydroxyl group, a mercapto group, a carboxyl group, and an alkoxycarbonyl group having 1 to 12 carbon atoms can be mentioned.

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

[0178] [Chemical Formula 6]

[0179]

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

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

[0182] * represents a bonding site.

[0183] In formula (B), R 13 and R 14 preferably represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which has a hydroxyl group, and more preferably a hydrogen atom or a 2-hydroxyethyl group.

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

[0185] Amino or N,N-bis(hydroxyethyl)aminoethyl is preferred as the group represented by formula (B).

[0186] R 11 Carboxyl, amino or an alkyl group having 1 to 6 carbon atoms is preferred as R

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

[0188] R 12 As the substituent represented by R

[0189] Further, the substituent represented by R 12 may further have one or more substituents selected from the group consisting of hydroxy and carboxyl.

[0190] R 12 Hydrogen atom, hydroxy, the group represented by formula (B) described above or an alkyl group having 1 to 6 carbon atoms which can have carboxyl is preferred as R

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

[0192] The benzotriazole compound can be used singly or two or more kinds can be used.

[0193] From the viewpoint of more excellent corrosion resistance, the content of the benzotriazole compound is preferably 0.0001 mass% or more, and more preferably 0.001 mass% or more, relative to the total mass of the cleaning agent composition.

[0194] Further, the upper limit is not particularly limited, but from the viewpoint of more excellent residue removal performance, the content of the hydroxylamine compound is preferably 10% by mass or less, more preferably 3% by mass or less, and further preferably 0.5% by mass or less, relative to the total mass of the cleaning agent composition.

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

[0196] Further, from the viewpoint of more excellent corrosion resistance, the above mass ratio is preferably 1000 or less, and more preferably 100 or less.

[0197] <solvent>

[0198] The liquid medicine can include a solvent.

[0199] As the solvent, water and organic solvents can be given, and water is preferred.

[0200] (water)

[0201] The cleaning agent composition preferably includes water.

[0202] The kind of water used in the cleaning agent composition is not particularly limited as long as it does not adversely affect the semiconductor substrate, and distilled water, deionized water (DI water), and pure water (ultra-pure water) can be given. From the viewpoint of containing almost no impurities and having less influence on the semiconductor substrate in the manufacturing process of semiconductor devices, pure water is preferred.

[0203] The content of water in the cleaning agent composition is not particularly limited, and is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 85% by mass or more, relative to the total mass of the cleaning agent composition. Further, 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 agent composition can include an organic solvent.

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

[0207] As the alcohol-based solvent, for example, alkanediols, alkylene glycols, alkoxy alcohols, saturated or unsaturated aliphatic alcohols, and alcohols of three or more carbons can be given.

[0208] As the alkanediol, for example, diol, 2-methyl-l,3-propanediol, 1,2-propanediol, 1,3-propanediol (1,3-dihydroxypropane), 2-methyl-2,4-pentanediol, 2,2-dimethyl-l,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 can be mentioned.

[0209] As the alkylene glycol, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol and tetraethylene glycol can be mentioned.

[0210] As the alkoxy alcohol, for example, alkylene glycol monoalkyl ether and alkylene glycol dialkyl ether can be mentioned.

[0211] As the alkylene glycol monoalkyl ether, for example, 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-l-propanol, 1-ethoxy-2-propanol, 2-ethoxy-l-propanol, 3-methoxy-3-methyl-l-butanol, 3-methoxy-l-butanol, 3-methoxy-3-methylbutanol and 1-methoxy-2-butanol can be mentioned.

[0212] As the alkylene glycol dialkyl ether, for example, 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 can be mentioned.

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

[0214] As the saturated or unsaturated aliphatic alcohol, for example, methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, tert-amyl alcohol, 1-hexanol, allyl alcohol, propargyl alcohol, 2-butenol, 3-butenol and 4-penten-2-ol can be mentioned.

[0215] As the alcohol having three or more valences, for example, glycerol can be mentioned.

[0216] As the alcohol-based solvent, an alkoxy alcohol is preferred. As the above alkoxy group, for example, an alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group is preferred.

[0217] As the ketone-based solvent, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone can be given.

[0218] As the amide-based solvent, for example, formamide, monomethyl formamide, dimethyl formamide, acetamide, monomethyl acetamide, dimethyl acetamide, monoethyl acetamide, diethyl acetamide, and N-methyl pyrrolidone can be given.

[0219] As the organic solvent, an alkylene glycol monoalkyl ether is preferred, and 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 can be used singly or two or more kinds can be used.

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

[0222] <PH Adjusting Agent>

[0223] In order to adjust the pH of the detergent composition, the detergent composition can contain a pH adjusting agent.

[0224] As the pH adjusting agent, for example, inorganic acids, organic acids (except for specific chelating agents), organic bases, and inorganic bases can be given.

[0225] As the inorganic acid, sulfuric acid, acetic acid, nitric acid, phosphoric acid, and hydrofluoric acid can be given. As the organic acid, lower (carbon number 1 to 4) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid can be given. Also, the above-described carboxylic acid-based chelating agent can be used to serve as a pH adjusting agent for lowering the pH of the detergent composition.

[0226] As the organic base, for example, quaternary ammonium salt compounds, nitrogen-containing heterocyclic compounds, and water-soluble amines can be given.

[0227] As the quaternary ammonium salt compound, a 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 of the following groups independently represents an alkyl group (preferably methyl, ethyl, propyl, or butyl) having 1 to 6 carbon atoms, a hydroxyalkyl group (preferably hydroxymethyl, hydroxyethyl, or hydroxybutyl) having 1 to 6 carbon atoms, a benzyl group, or an aryl group (preferably phenyl, naphthyl group, or naphthalene group). Among these, alkyl groups having 1 to 6 carbon atoms, hydroxyethyl groups having 1 to 6 carbon atoms, or benzyl groups are preferred.

[0231] Examples of compounds represented by formula (10) include tetramethylammonium hydroxide (TMAH), ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), dimethyldipropylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methyltris(hydroxyethyl)ammonium hydroxide, tetra(hydroxyethyl)ammonium hydroxide, trimethylbenzylammonium hydroxide, dihydroxyethyldimethylammonium hydroxide, and choline. TMAH, ETMAH, TEAH, or TBAH are preferred.

[0232] In this specification, a nitrogen-containing heterocyclic compound is a compound having a heterocycle in which at least one of the atoms constituting the ring is a nitrogen atom, and refers to compounds not included in the above-mentioned benzotriazole compounds.

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

[0234] Cyclic amidine compounds are compounds that have a heterocycle containing an amidine structure (>NC=N-) within the ring.

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

[0236] In this specification, water-soluble amines are defined as amines that can dissolve more than 50 g in 1 L of water. The pKa of water-soluble amines is not particularly limited, but is preferably 7.5 to 13.0. Furthermore, water-soluble amines do not include the aforementioned hydroxylamine compounds and ammonia.

[0237] As the water-soluble amine having a pKa of 7.5 to 13.0, for example, diethanolamine (DGA) (pKa = 9.80), methylamine (pKa = 10.6), ethylamine (pKa = 10.6), propylamine (pKa = 10.6), butylamine (pKa = 10.6), amylamine (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) can be given.

[0238] As the inorganic base, for example, alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia can be given.

[0239] As the alkali metal hydroxides, for example, lithium hydroxide, sodium hydroxide, and potassium hydroxide can be given. As the alkaline earth metal hydroxides, for example, calcium hydroxide, strontium hydroxide, and barium hydroxide can be given.

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

[0241] The pH adjuster can be used singly or two or more kinds can be used.

[0242] As for the kind and content of the pH adjuster, the kind of the pH adjuster used and the content are appropriately selected so that the pH of the detergent composition is within the preferable range described later. 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 detergent composition.

[0243] <Additives>

[0244] The detergent composition can contain additives other than the above-described components as necessary.

[0245] As such additives, for example, surfactants, reducing agents, antifoaming agents, rust preventives, and preservatives can be given.

[0246] The detergent composition can contain a surfactant.

[0247] The kind of the surfactant is not particularly limited, and for example, ionic surfactants (anionic surfactants, cationic surfactants, and amphoteric surfactants) and nonionic surfactants can be given.

[0248] When the cleaning agent composition contains the interfacial active agent, the content of the interfacial active agent is preferably 1 ppm by mass or more and 3% by mass or less with respect to the total mass of the cleaning agent composition.

[0249] The cleaning agent composition can contain other components than the above components, as long as the effects of the present application and the functions of the components are not hindered.

[0250] The content of the above components contained in the cleaning agent composition can be determined by a publicly known method 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 agent composition is not particularly limited, but from the viewpoint of more excellent time-dependent stability of the removal performance and more excellent corrosion resistance, it is preferably more than 7, and more preferably 8 or more.

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

[0254] The pH of the cleaning agent composition can be adjusted using the above-described pH adjustor.

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

[0256] 〔Manufacturing method〕

[0257] The manufacturing method of the cleaning agent composition is not particularly limited, and the composition can be manufactured, for example, by mixing the above-described components. The order and / or timing of mixing the above-described components are not particularly limited.

[0258] For example, the following method can be mentioned: the cleaning agent composition is manufactured by adding a hydroxylamine compound, a specific chelating agent, a benzotriazole compound, and optional components in this order into a mixing stirrer or the like into which purified pure water is put, and sufficiently stirring to mix the components.

[0259] Each raw material used in the preparation of the cleaning agent composition preferably uses a raw material classified as a semiconductor grade or a raw material classified as a high-purity grade or the like.

[0260] Also, any one or more of the raw materials used to manufacture the cleaning agent composition can be purified in advance by distillation, ion exchange, or filtration.

[0261] As the purification method, there are no particular limitations, and methods such as those using ion exchange resins or RO membranes (Reverse Osmosis Membrane), distillation, and filtration can be given. More specifically, a method in which one purification is performed by an RO membrane, and two purifications are performed by a purification device composed of a cation exchange resin, an anion exchange resin, or a mixed bed ion exchange resin can be given.

[0262] <Kit and Concentrate>

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

[0264] Although there are no particular limitations, as a specific method for manufacturing the cleaning agent composition as a kit, a method in which a solution composition containing the hydroxylamine compound, the specific chelating agent, and the benzotriazole compound is prepared as a first solution, and a solution composition containing the other components is prepared as a second solution can be given.

[0265] Also, the cleaning agent composition can be prepared using a concentrate. When a concentrate of the cleaning agent composition is prepared, the concentration ratio thereof can be appropriately determined according to the composition to be formed, but is preferably 5 to 2000 times. That is, the cleaning agent composition is used after the concentrate is diluted 5 to 2000 times. Also, from the viewpoint of further improving the stability of the removal performance over time, it is preferable to manufacture a composition containing a large amount of an alcohol-based solvent in advance in order to reduce water, which is a cause of decomposition of the hydroxylamine compound, as much as possible.

[0266] <Container (Storage Container)>

[0267] The cleaning agent composition can be stored, transported, and used in any container as long as problems such as corrosion do not occur (regardless of whether it is a kit or a concentrate). As the container, a container for semiconductor use in which the cleanliness is high and the elution of impurities is small is preferable. As the container that can be used, "Cleag Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and "Pure Bottle" manufactured by KODAMA PLASTICS CO., LTD. can be given, but are not limited thereto.

[0268] As the container, a container in which the inside is cleaned before the cleaning agent composition is filled is preferable. As the liquid used in the cleaning, it is preferable to reduce the amount of metal impurities in the solution. The cleaning agent composition can be transported and stored in a container such as a gallon bottle or a coated bottle after being manufactured.

[0269] <clean room>

[0270] The operations including the production of the cleaning agent composition, the opening of the storage container and / or the cleaning, the filling of the cleaning agent composition, the analysis and the measurement of the treatment are preferably performed in a clean room. The clean room preferably satisfies the 14644-1 clean room standard, more preferably satisfies any one of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, ISO Class 4, further preferably satisfies ISO Class 1 or ISO Class 2, and particularly preferably satisfies ISO Class 1.

[0271] 〔cleaning method〕

[0272] As the cleaning method using the cleaning agent composition, for example, a method having a cleaning step (hereinafter, also referred to as "cleaning step B") of cleaning a semiconductor substrate having a metal layer using the above-described cleaning agent composition can be given. Also, the cleaning method can have a cleaning agent composition preparation step (hereinafter, also referred to as "cleaning agent composition preparation step A") of preparing the above-described cleaning agent composition before the cleaning step B.

[0273] In the following description of the cleaning method, a case where the cleaning agent composition preparation step A is performed before the cleaning step B is exemplified, but is not limited thereto, and the cleaning method can also be performed using the above-described cleaning agent composition prepared in advance.

[0274] <cleaning target>

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

[0276] As a more specific cleaning target, for example, a laminate having at least the above-described metal layer, an interlayer insulating layer, and a metal hard mask provided in this order on a substrate can be given. The laminate has a hole formed from the surface (opening portion) of the metal hard mask toward the substrate by further subjecting to a dry etching step so as to expose the surface of the metal layer.

[0277] The manufacturing method of the laminate having the hole as described above is not particularly limited, and for example, a method in which a pre-treatment laminate having a substrate, a metal layer, an interlayer insulating layer, and a metal hard mask in this order is subjected to a dry etching step using the metal hard mask as a mask to etch the interlayer insulating layer so as to expose the surface of the metal layer, thereby providing a hole penetrating through the metal hard mask and the interlayer insulating layer can be given.

[0278] The method for manufacturing the metal hard mask is not particularly limited, and for example, a method in which a metal film containing prescribed components is first formed on an interlayer insulating layer, a resist film having a prescribed pattern is formed thereon, and then the metal film is etched using the resist film as a mask, thereby manufacturing a metal hard mask (i.e., a film in which the metal film is patterned) can be given.

[0279] After the metal hard mask is manufactured, an resist peeling process in which the resist film is peeled off by a dry ashing process such as a plasma ashing process is performed.

[0280] In the substrate subjected to the dry etching process and the resist peeling process, a residue containing an organic component derived from the resist film is attached to the metal layer and / or the interlayer insulating layer thereof. The attached residue is removed from the laminate using the cleaning agent composition described above.

[0281] The laminate can have layers other than the layers described above, and for example, an etching stop layer and an anti-reflection layer can be given.

[0282] Figure 1 is a schematic cross-sectional view showing an example of a laminate, which is a cleaning target of a cleaning method using the cleaning agent composition described above.

[0283] Figure 1 The laminate 10 shown is provided with 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, and a hole 6 exposing the metal layer 2 is formed at a prescribed position by a dry etching process. That is, Figure 1 The laminate 10 shown is a laminate provided with 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. Also, Figure 1 The laminate 10 shown has the resist film removed by a resist peeling process.

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

[0285] The cleaning method can be preferably used for cleaning aimed at removing the residues 12. That is, the cleaning agent composition has excellent residue 12 removal performance, and excellent corrosion resistance to the inner wall 11 (e.g., the metal layer 2, etc.) of the cleaning target.

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

[0287] (Metal Hard Mask)

[0288] The metal hard mask preferably contains at least one component selected from the group consisting of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx. Here, x and y each represent a number indicated by x = 1 to 3 and y = 1 to 2.

[0289] As the material of the metal hard mask, for example, TiN, WO2, and ZrO2 can be given.

[0290] (interlayer insulating layer)

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

[0292] As a specific material of the interlayer insulating layer, for example, SiO2, SiOC-based materials, and organic polymers such as polyimide can be given.

[0293] (etching stopper layer)

[0294] The material of the etching stopper layer is not particularly limited. As a specific material of the etching stopper layer, SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx can be given.

[0295] (metal layer)

[0296] The wiring material forming the metal layer is not particularly limited, and for example, a metal containing one or more selected from the group consisting of Cu (copper), W (tungsten), and Co (cobalt) can be given. The wiring material can be a metal composed of only Cu, W, or Co, or an alloy of Cu, W, or Co and another metal. Among them, a metal containing W or Co is preferable, and a metal containing Co is more preferable.

[0297] Further, the wiring material can further contain a metal other than Cu, W, and Co, a nitride metal, or an alloy, and for example, one or more selected from the group consisting of titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxides, and aluminum can be further contained.

[0298] (substrate)

[0299] The "substrate" described herein 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, and it is preferable to be composed of, for example, a Group III-V compound such as silicon, silicon germanium, GaAs, or an arbitrary combination of these.

[0301] When the semiconductor substrate is composed of a plurality of layers, the composition is not particularly limited, and for example, it can have an integrated circuit structure in which interconnect features such as metal lines and dielectric materials are exposed on the semiconductor substrate such as silicon. As the metal and alloy used in the interconnect features, there can be mentioned aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten, but the list is not limited to these. Further, the semiconductor substrate can have thereon an interlayer dielectric layer, a silicon oxide layer, a silicon nitride layer, a silicon carbide layer, and a carbon-doped silicon oxide layer.

[0302] <Processing steps>

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

[0304] (Cleaning agent composition preparation step A)

[0305] The cleaning agent composition preparation step A is a step for preparing the above-described cleaning agent composition. Each component used in this step is as described above.

[0306] The steps of this step are not particularly limited, and for example, there can be mentioned a method of preparing the cleaning agent composition by adding a hydroxylamine compound, a specific chelating agent, a benzotriazole compound, and other arbitrary components and stirring and mixing. In addition, when each component is added, it can be added all at once or in multiple times.

[0307] Further, each component included in the cleaning agent composition preferably uses a component classified as a semiconductor grade or a component classified as a high-purity grade based thereon, and a component subjected to foreign matter removal based on filtration and / or ion component reduction based on ion exchange resin is preferably used. Further, after the raw material components are mixed, foreign matter removal based on filtration and / or ion component reduction based on ion exchange resin is further preferably performed.

[0308] Further, when a concentrated solution of the cleaning agent composition is prepared, after diluting the concentrated solution to obtain a diluted solution, the cleaning step B is performed using the diluted solution before the cleaning step B is performed. At this time, the above-described dilution is preferably performed using a diluted solution including water.

[0309] (Cleaning step B)

[0310] As the cleaning target in the cleaning step B, there can be mentioned the above-described laminate, and as described above, there can be exemplified a laminate 10 in which a hole is formed by performing a dry etching step and a dry ashing step (refer to FIG. 1). Figure 1 In addition, the laminate 10 has attached thereto a residue 12 in the hole 6.

[0311] <Cleaning method>

[0312] The method of contacting the cleaning agent composition with the cleaning target is not particularly limited, and for example, a method in which the cleaning target is immersed in the cleaning agent composition placed in a container, a method in which the cleaning agent composition is sprayed on the cleaning target, a method in which the cleaning agent composition is flowed on the cleaning target, and a combination of these can be given. From the viewpoint of the removal performance, the method in which the cleaning target is immersed in the cleaning agent composition is preferred.

[0313] The temperature of the cleaning agent 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 depending on the cleaning method used and the temperature of the cleaning agent composition.

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

[0316] When cleaning in a single piece method, 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 improve the cleaning ability of the cleaning agent composition, a mechanical agitation method can be used.

[0318] As the mechanical agitation method, for example, a method in which the cleaning agent composition is circulated on the cleaning target, a method in which the cleaning agent composition is flowed or sprayed on the cleaning target, and a method in which the cleaning agent composition is agitated by ultrasonic waves or megasonic waves can be given.

[0319] (Rinse Process B2)

[0320] The cleaning method of the substrate using the cleaning agent composition can further have a process in which the cleaning target is rinsed with a solvent (hereinafter, referred to as "rinse process B2") after the cleaning process.

[0321] The rinse process B2 is preferably performed after the cleaning process, and a process in which the cleaning target is rinsed with a rinse solvent (rinse liquid) for 5 seconds to 5 minutes is preferred. The rinse process B2 can be performed using the above-described mechanical agitation method.

[0322] The rinse solvent is not particularly limited, and for example, deionized (DI) water, methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate can be given. Furthermore, an aqueous rinse liquid (diluted aqueous ammonium hydroxide or the like) having a pH of 8 or more can also be used.

[0323] As the rinsing solvent, an aqueous ammonium hydroxide solution, DI water, methanol, ethanol or isopropanol is preferred, an aqueous ammonium hydroxide solution, DI water or isopropanol is more preferred, and an aqueous ammonium hydroxide solution or DI water is further preferred.

[0324] As the method of contacting the rinsing solvent with the cleaning target, the above-described method of contacting the cleaning agent composition with the cleaning target can be applied as it is.

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

[0326] (Drying step B3)

[0327] The cleaning method of the substrate using the cleaning agent composition can have a drying step of drying the cleaning target after the rinsing step.

[0328] The drying method is not particularly limited, and for example, a spin-drying method, a method of flowing a dry gas over the surface of the cleaning target, 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 a combination of these can be mentioned.

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

[0330] The cleaning target of the cleaning method of the substrate using the cleaning agent composition is not limited to the laminate having at least a metal layer, an interlayer insulating layer and a metal hard mask in this order on the substrate as described above. For example, it can be used for removal of a residue derived from a resist film attached to a laminate having at least a metal layer, an interlayer insulating layer and a resist film in this order on the substrate.

[0331] Examples

[0332] Hereinafter, the present application will be further explained in detail according to examples. The materials, amounts, proportions, contents of treatment and steps of treatment shown in the following examples can be appropriately changed as long as the gist of the present application is not deviated. Therefore, the scope of the present application should not be limitatively interpreted by the examples shown below. In addition, " % " means " mass % " unless otherwise specified.

[0333] [Preparation of cleaning agent composition]

[0334] The cleaning agent composition was prepared according to the following procedure. In addition, the content (all on a mass basis) of each component used in each cleaning agent composition is as described in the table.

[0335] [Raw materials]

[0336] The following shows each raw material used in the preparation of the cleaning agent composition. In addition, the compounds used in the preparation of the cleaning agent composition all use compounds classified as semiconductor grade or compounds classified as high purity grade or the like.

[0337] <Hydroxylamine 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 agent>

[0343] (Aminophosphonic acid compound)

[0344] 1-a: Nitroso tris(methylene phosphonic acid)

[0345] 1-b: Ethylenediamine tetra(methylene phosphonic 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(methylene phosphonic 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-Pentane tricarboxylic acid

[0360] 5-c: 3-Methyl adipic acid

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

[0362] (Hydroxyphosphonic acid compound)

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

[0364] 6-b: Glycerol 3-phosphate

[0365] <PH adjuster>

[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] Each of the cleaning agent compositions prepared in the above was subjected to various evaluations shown below.

[0376] [Removal performance of organic matter residue]

[0377] A multilayer substrate in which an antireflection film, a metal hard mask (TiN layer), an etching stopper layer (Al2O3 layer), a Co layer, and an interlayer dielectric layer (ILD) were sequentially stacked on the surface of a substrate was prepared. The multilayer substrate was subjected to a lithography-based patterning process, an etching process using a metal plasma etching device, and an antireflection film removal process based on oxygen plasma ashing, and an evaluation test multilayer substrate (hereinafter, also referred to as "test piece") was produced. The obtained test piece was cleaned using each of the cleaning agent compositions of the examples and the comparative examples.

[0378] A glass beaker with a volume of 500 mL was filled with 200 mL of the cleaning agent composition. While stirring with a stirrer, the temperature of the cleaning agent composition was raised to 65°C. Next, while stirring, the test piece prepared in the above was immersed in the cleaning agent composition at a liquid temperature of 65°C for 5 minutes, thereby cleaning the test piece. During the immersion of the test piece in the cleaning agent composition, the test piece was held using a 4-inch length plastic locking pin set in such a manner that the side from which the resist of the test piece was removed faced the stirrer.

[0379] After the elapse of the cleaning time, the test piece was immediately taken out of the cleaning agent composition, filled in a plastic beaker with a volume of 500 mL, and put in 400 mL of DI water (water temperature 17°C) under slow stirring. After the test piece was immersed in the DI water for 30 seconds, the test piece was immediately taken out and rinsed under a stream of DI water at 17°C for 30 seconds.

[0380] Next, the surface of the test piece was dried by blowing off the droplets adhering to the surface of the test piece by exposing the test piece to a nitrogen gas stream.

[0381] After this nitrogen drying process, the test piece was released from the holding portion of the plastic tweezers, and the test piece was put in a plastic storage box with a lid attached in such a manner that the element face faced upward, and stored.

[0382] The surface of the obtained test piece was subjected to composition analysis by X-ray photoelectron spectroscopy (XPS). The surface of the obtained test piece was measured using an XPS device (manufactured by Ulvac-PHI, Inc., trade name Quantera SXM). As to the amount of fluorine atoms contained in the organic residue of the measured test piece, the reduction rate before and after the treatment was calculated, and this was taken as the residue removal rate. The removal performance of the organic residue was evaluated in accordance with the following evaluation criteria.

[0383] 5: removal rate of 95% or more

[0384] 4: removal rate of 80% or more and less than 95%

[0385] 3: removal rate of 75% or more and less than 80%

[0386] 2: removal rate of 50% or more and less than 75%

[0387] 1: removal rate of less than 50%

[0388] <Time-dependent stability of removal performance>

[0389] Next, the cleaning agent compositions of each of the examples and each of the comparative examples were used as test solutions to perform a storage test, and the time-dependent stability of the removal performance of each of the cleaning agent compositions was evaluated.

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

[0391] The evaluation test of the removal performance was performed in accordance with the above evaluation method of the removal performance, except that the cleaning agent composition after the storage test was used, and the time-dependent stability of each of the cleaning agent compositions was evaluated.

[0392] <Corrosion Resistance>

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

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

[0395] The corrosion resistance to the Co layer was evaluated in accordance with the following criteria based on the measured ER.

[0396] A:

[0397] B:

[0398] C:

[0399] D:

[0400] E:

[0401] [Results]

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

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

[0404] The notation "yes" in the column of "pH adjuster" indicates that each of the cleaning agent compositions contains a pH adjuster. The content of the pH adjuster in each of the cleaning agent compositions is an amount in which the pH of the finally obtained cleaning agent composition becomes the value shown in the column of "pH" in the table.

[0405] The notation "remainder" shown as the content of water indicates that the finally obtained cleaning agent composition contains components other than the pH adjuster in the content shown in the table and the pH adjuster in an amount in which the pH shown in the table, and the remaining components are water.

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

[0407] In the table, the column of "removal performance" indicates the evaluation results of the removal performance of organic matter residues using the cleaning agent compositions of each of the examples and each of the comparative examples. The column of "after preparation" of "removal performance" indicates the evaluation results of the removal performance after each of the cleaning agent compositions is just prepared, and the column of "after storage" of "removal performance" indicates the evaluation results of the removal performance of each of the cleaning agent compositions after the storage test.

[0408] [Table 1] [Table 1]

[0409]

[0410] [Table 2] [(Continued) Table 11

[0411]

[0412] [Table 3] [Table 2]

[0413]

[0414] [Table 4] [(Continued) Table 2]

[0415]

[0416] [Table 5] [Table 3]

[0417]

[0418] [Table 6] [Table 4]

[0419]

[0420] [Table 7] [Table 5]

[0421]

[0422] [Table 8] [Table 6]

[0423]

[0424] [Table 9]

[0425] [Table 7]

[0426]

[0427] It was confirmed from the results shown in the table that the problem of the present application could be solved by using the detergent composition of the present application.

[0428] It was confirmed from the results shown in the table that when the content of the specific chelating agent was 0.1% by mass or more with respect to the total mass of the detergent composition, the time-dependent stability of the removal performance was more excellent, and when it was 0.5% by mass or more, the time-dependent stability of the removal performance was further excellent (comparisons of Examples 1 to 3, comparisons of Examples 24, 25, and 27).

[0429] Also, it was confirmed that when the content of the specific chelating agent was 10% by mass or less with respect to the total mass of the detergent composition, the corrosion resistance was more excellent (comparisons of Examples 4 and 5).

[0430] It was confirmed that when the content of the specific chelating agent was 0.1% by mass or more with respect to the total mass of the detergent composition, the time-dependent stability of the removal performance was more excellent, and when it was 0.5% by mass or more, the time-dependent stability of the removal performance was further excellent (comparisons of Examples 1 to 3, comparisons of Examples 24, 25, and 27).

[0431] Also, it was confirmed that when the content of the specific chelating agent was 10% by mass or less with respect to the total mass of the detergent composition, the corrosion resistance was more excellent (comparisons of Examples 4 and 5).

[0432] It was confirmed that when the ratio 1 (mass ratio of the content of the hydroxylamine compound with respect to the content of the specific chelating agent) was 100 or less in the detergent composition, the time-dependent stability of the removal performance was more excellent, and when the ratio 1 was 10 or less, the time-dependent stability of the removal performance was further excellent (comparisons of Examples 1 to 3, comparisons of Examples 24, 25, and 27).

[0433] Also, 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 (comparisons of Examples 2, 4, and 5, comparisons of Examples 28 and 35).

[0434] It was confirmed that when the content of the benzotriazole compound was 0.5% by mass or less with respect to the total mass of the detergent composition, the residue removal performance was more excellent (comparisons of Examples 2 and 8).

[0435] It was confirmed that when the ratio 2 (mass ratio of content of hydroxylamine compound to content of benzotriazole compound) in the cleaning agent composition was 1000 or less, the corrosion resistance was more excellent (comparisons of Examples 7 and 12).

[0436] Also, it was confirmed that when the ratio 2 was 10 or more, the residue removal performance was more excellent (comparisons of Examples 2 and 8).

[0437] It was confirmed from the results of Table 2 that when hydroxylamine or hydroxylamine sulfate among the hydroxylamine compounds was used, the removal performance was more excellent (comparisons of Examples 24, 39 and 40).

[0438] Also, it was confirmed that when two or more kinds of hydroxylamine compounds were used, the corrosion resistance was more excellent compared to the case where the hydroxylamine compound was used alone (comparisons of Examples 24, 39 and 41).

[0439] It was confirmed from the results of Tables 1 to 6 that when an aminophosphonic acid compound or a hydroxy acid compound among the specific chelating agents was used, the removal performance and the stability of the removal performance over time were more excellent (comparisons of Examples 2, 16, 24, 35, 36, 45, 47, 48, 50, 52, 54, 56, 57, 59 and 61).

[0440] It was confirmed from the results of Table 3 that when 2-phosphonobutane-1, 2, 4-tricarboxylic acid or 4-phosphonobutanoic acid among the phosphonocarboxylic acid compounds was used, the stability of the removal performance over time was more excellent (comparisons of Examples 45, 47 and 48), and when 2-phosphonobutane-1, 2, 4-tricarboxylic acid or glycine-N, N-bis(methylene phosphonic acid) was used, the residue removal performance was more excellent (comparisons of Examples 45, 47 and 48).

[0441] It was confirmed from the results of Table 5 that when glutaric acid among the polycarboxylic acid compounds was used, the stability of the removal performance over time was more excellent (comparisons of Examples 54, 56 and 57), and when 1, 3, 5-pentane tricarboxylic acid was used, the removal performance was more excellent (comparisons of Examples 54, 56 and 57).

[0442] It was confirmed from the results of Table 6 that when 1-hydroxyethane-1, 1-diphosphonic acid among the hydroxy phosphonic acid compounds was used, the removal performance and the corrosion resistance were more excellent (comparisons of Examples 59 and 61), and when glycerol 3-phosphate was used, the stability of the removal performance over time was more excellent (comparisons of Examples 59 and 61).

[0443] Explanation of symbols

[0444] 1 - substrate, 2 - metal layer, 3 - etching stopper layer, 4 - interlayer insulating layer, 5 - metal hard mask, 6 - hole, 10 - laminate, 11 - inner wall, 11a - cross-sectional wall, 11b - bottom wall, 12 - residue.

Claims

1. A cleaning agent composition which is a cleaning agent composition for semiconductor devices, the cleaning agent composition comprising: a hydroxylamine compound selected from one or more of hydroxylamine and hydroxylamine salts; a chelating agent selected from one or more of a carboxylic acid-based chelating agent other than a polyaminocarboxylic acid and a phosphonic acid-based chelating agent; a benzotriazole compound; and an organic solvent, the pH of the cleaning agent composition is 7.0 or greater and less than 10.0, the content of the organic solvent is 0.001 to 10 mass% with respect to the total mass of the cleaning agent composition.

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

3. The cleaning agent composition according to claim 2, wherein the phosphonic acid-based chelating agent comprises one or more compounds selected from a hydroxyphosphonic acid compound, an aminophosphonic acid compound, and a phosphonocarboxylic acid compound.

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

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

6. The cleaning agent composition according to claim 5, wherein the carboxylic acid-based chelating agent comprises one or more compounds selected from a hydroxy acid compound, a polycarboxylic acid compound, and an aromatic polycarboxylic acid compound.

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

8. The cleaning agent composition according to claim 1 or 2, 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.

9. The cleaning agent composition according to claim 1 or 2, wherein the benzotriazole compound comprises a compound represented by the following formula (A), ###0001### (A) n represents an integer of 0 to 2.

10. The cleaning agent 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 agent 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 agent composition according to claim 1 or 2, which is used for cleaning of a substrate having a metal layer comprising one or more selected from copper, tungsten, and cobalt.

13. The cleaning agent composition according to claim 1 or 2, wherein the cleaning agent composition further comprises a pH adjustor.

14. The cleaning agent composition according to claim 1 or 2, wherein the organic solvent comprises an alcohol-based solvent.

15. The cleaning agent composition according to claim 1 or 2, wherein the organic solvent comprises an alkoxy alcohol.

16. The cleaning agent composition according to claim 9, wherein n in the formula (A) is 1.

17. The cleaning agent composition according to claim 9, wherein n in the formula (A) is 1.

18. The cleaning agent composition according to claim 9, wherein n in the formula (A) is 1. ​ ​ ​ ​ ​ In formula (A), R 11 represents a carboxyl group, an amino group, or an alkyl group having 1 to 6 carbon atoms, ​ R 12 represents a hydrogen atom or a hydroxyl group. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ R in the formula (A) is methyl. 11 is methyl. ​ ​ ​ R in the formula (A) is a hydrogen atom. 12 a hydrogen atom.

19. The cleaning agent composition according to claim 13, wherein the pH adjuster is an organic base.

20. The cleaning agent composition according to claim 13, wherein the pH adjuster is a water-soluble amine.

21. The cleaning agent composition according to claim 20, wherein the water-soluble amine has a pKa of 7.5 to 13.

0.

22. The cleaning agent composition according to claim 1 or 2, wherein the content of the hydroxylamine compound is 0.5 mass% or more and 15 mass% or less with respect to the total mass of the cleaning agent composition.

23. The cleaning agent composition according to claim 1 or 2, wherein the content of the hydroxylamine compound is 6 mass% or more and 15 mass% or less with respect to the total mass of the cleaning agent composition.

24. The cleaning agent composition according to claim 1 or 2, wherein the content of the organic solvent is 0.1 mass% to 5 mass% with respect to the total mass of the cleaning agent composition.

25. The cleaning agent composition according to claim 1 or 2, wherein the content of the benzotriazole compound is 0.001 mass% or more and 3 mass% or less with respect to the total mass of the cleaning agent composition.

26. The cleaning agent composition according to claim 1 or 2, wherein the content of the benzotriazole compound is 0.001 mass% or more and 0.5 mass% or less with respect to the total mass of the cleaning agent composition.

27. The cleaning agent composition according to claim 1 or 2, wherein the content of the benzotriazole compound is 0.1 mass% or more and 0.3 mass% or less with respect to the total mass of the cleaning agent composition.

28. The cleaning agent 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 or more and 100 or less.

29. The cleaning agent 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 30 or more and 120 or less.

30. The cleaning agent composition according to claim 5, wherein the content of the carboxylic acid-based chelating agent is 0.02 mass% or more and 1.0 mass% or less with respect to the total mass of the cleaning agent composition.

31. The cleaning agent composition according to claim 1 or 2, wherein the pH of the cleaning agent composition is 7.0 or more and 9.0 or less.

32. The cleaning agent composition according to claim 1 or 2, wherein the hydroxylamine compound is a hydroxylamine derivative.

33. The cleaning agent composition according to claim 1 or 2, wherein the hydroxylamine compound is N,N-dimethylhydroxylamine.

34. The cleaning agent composition according to claim 1 or 2, wherein the content of the hydroxylamine compound is 0.1 mass% or more and 30 mass% or less with respect to the total mass of the cleaning agent composition.

35. The cleaning agent composition according to claim 1 or 2, wherein the content of the hydroxylamine compound is 0.5 mass% or more and 6.0 mass% or less with respect to the total mass of the cleaning agent composition.

36. The cleaning agent composition according to claim 1 or 2, wherein the organic solvent comprises an alkylene glycol monoalkyl ether.

37. The cleaning agent composition according to claim 1 or 2, wherein the content of the organic solvent is 0.001 to 5 mass% with respect to the total mass of the cleaning agent composition.

38. The cleaning agent composition according to claim 1 or 2, wherein the content of the organic solvent is 0.1 to 2.0 mass% with respect to the total mass of the cleaning agent composition.

39. The cleaning agent composition according to claim 1 or 2, wherein the content of the organic solvent is 2.0 to 5 mass% with respect to the total mass of the cleaning agent composition.

40. The cleaning agent composition according to claim 1 or 2, wherein the benzotriazole compound is benzotriazole.

41. The cleaning agent composition according to claim 1 or 2, wherein the content of the benzotriazole compound is 0.1 mass% or more and 1.0 mass% or less with respect to the total mass of the cleaning agent composition.

42. The cleaning agent composition according to claim 1 or 2, wherein the content of the benzotriazole compound is 0.3 mass% or more and 1.0 mass% or less with respect to the total mass of the cleaning agent composition.

43. The cleaning agent composition according to claim 1 or 2, wherein the carboxylic acid-based chelating agent comprises an amino acid compound.

44. The cleaning agent composition according to claim 1 or 2, wherein the content of the chelating agent is 0.02 mass% or more and 10 mass% or less with respect to the total mass of the cleaning agent composition.

45. The cleaning agent composition according to claim 1 or 2, wherein the content of the chelating agent is 0.05 mass% or more and 5 mass% or less with respect to the total mass of the cleaning agent composition.

46. The cleaning agent composition according to claim 1 or 2, wherein the cleaning agent composition further comprises water, the content of the water is 70 mass% or more and 99 mass% or less with respect to the total mass of the cleaning agent composition.

47. The cleaning agent composition according to claim 1 or 2, wherein the cleaning agent composition further comprises water, the content of the water is 70 mass% or more and 95 mass% or less with respect to the total mass of the cleaning agent composition.

48. The cleaning agent 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 0.6 or more and 60 or less.

49. The cleaning agent 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 0.3 or more and 30 or less.

50. The cleaning agent 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 6 or more and 60 or less.

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