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 applicant's application with application number 202080060051.7 and the invention title "Cleaning Agent Composition". The parent application of this application was filed on July 8, 2020, and the priority date is August 23, 2019. Technical Field

[0002] This invention relates to a cleaning agent composition. In particular, it relates to a cleaning agent composition that is preferably used in the manufacture of semiconductor devices. Background Technology

[0003] Semiconductor devices such as CCDs (Charge-Coupled Devices) and memory are manufactured using photolithography to form fine electronic circuit patterns on a substrate. Specifically, semiconductor devices are manufactured by forming a resist film on a stack of layers containing a metal film that serves as wiring material, an etch stop layer, and an interlayer insulating layer on a substrate, and then performing photolithography and dry etching processes (e.g., plasma etching).

[0004] For substrates that have undergone dry etching, a resist stripping process is performed as needed, using a stripping method such as a dry ashing process (e.g., plasma ashing treatment) to remove the resist film, which is mainly composed of organic matter.

[0005] In substrates that have undergone dry etching and resist stripping processes, there are often residues containing a large amount of organic components derived from the resist film adhering to their wiring films and / or interlayer insulating films. Therefore, it is common to remove these residues using a cleaning agent composition to avoid hindering the next process.

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

[0007] Previous technical documents

[0008] Patent documents

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

[0010] The technical problem to be solved by the invention

[0011] Based on the description in Patent Document 1, the inventors studied the cleaning agent composition used in the manufacturing process of semiconductor devices and found that there is room for further improvement in the removal performance of organic residues after the cleaning agent composition has been stored for a period of time.

[0012] Furthermore, the cleaning agent composition is required to suppress corrosion (corrosion resistance) of the wiring metal (e.g., one or more metals selected from Cu, W and Co) of the metal layer formed on the semiconductor device to be cleaned.

[0013] Therefore, the objective of this invention is to provide a cleaning agent composition for use in semiconductor devices that exhibits excellent long-term stability in removing organic residues and excellent corrosion resistance to metal layers.

[0014] means for solving technical problems

[0015] As a result of in-depth research in order to achieve the above-mentioned problem, the inventors discovered that the above-mentioned problem can be solved by the following configuration.

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

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

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

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

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

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

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

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

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

[0025]

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

[0026]

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

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

[0027]

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

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

[0028] Invention Effects

[0029] According to the present invention, a cleaning agent composition for use as a semiconductor device can be provided, which exhibits excellent long-term stability in removing organic residues and excellent corrosion resistance to metal layers. Attached Figure Description

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

[0031] The present invention will now be described in detail.

[0032] The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0033] In addition, in this specification, the numerical range indicated by “~” refers to the range included by taking the values ​​recorded before and after “~” as the lower limit and upper limit values.

[0034] Furthermore, when referred to as “preparation” in this specification, it means not only preparation by synthesizing or blending specific materials, but also preparation by purchasing prescribed materials.

[0035] Furthermore, in this specification, "ppm" refers to "parts-per-million" (10... -6 "ppb" refers to "parts-per-billion" (10...). -9 "ppt" refers to "parts-per-trillion (1 trillion parts) (10 -12 )".

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

[0037] Furthermore, in the designation of groups (atoms) in this specification, the absence of markings indicating substituted and unsubstituted groups, without impairing the effects of the invention, includes both unsubstituted and substituted groups. For example, "hydrocarbon group" includes not only unsubstituted hydrocarbon groups (unsubstituted hydrocarbon groups) but also substituted hydrocarbon groups (substituted hydrocarbon groups). This meaning is the same for all compounds.

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

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

[0040] [Cleaning agent composition]

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

[0042] The inventors have surprisingly obtained the following insight: by comprising hydroxylamine compounds, specific chelating agents and benzotriazole compounds, a cleaning agent composition can be obtained that exhibits excellent long-term stability in removing organic residues and excellent corrosion resistance to metal layers.

[0043] Furthermore, in this specification, "organic residue" refers to residue generated during the manufacturing process of semiconductor devices that is primarily composed of organic matter. In this case, "primarily composed of organic matter" means that the content of organic matter relative to the total amount of residue is 50% by mass or more. Moreover, in this specification, the removal performance of organic residue is simply described as "removal performance."

[0044] The following describes the components contained in the cleaning agent composition.

[0045] 〔Element〕

[0046] <Hydramine compounds>

[0047] The cleaning agent composition of the present invention contains one or more hydroxylamine compounds selected from hydroxylamine and hydroxylamine salts. Hydroxylamine compounds have the function of promoting the decomposition and solubility of organic residues.

[0048] Here, the term "hydroxylamine" as used in hydroxylamine compounds refers to hydroxylamine in a broad sense, including substituted or unsubstituted alkyl hydroxylamines, which, regardless of their composition, provide excellent removal performance, long-term stability, and excellent corrosion resistance.

[0049] There are no particular limitations on hydroxylamine compounds; preferred examples include unsubstituted hydroxylamines and hydroxylamine derivatives, as well as their salts.

[0050] There are no particular limitations on what constitutes a hydroxylamine derivative, and examples include O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,O-dimethylhydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, N,O-diethylhydroxylamine, O,N,N-trimethylhydroxylamine, N,N-dicarboxyethylhydroxylamine, and N,N-disulfoethylhydroxylamine.

[0051] Salts of unsubstituted hydroxylamine or hydroxylamine derivatives are preferred, preferably inorganic or organic acid salts of the aforementioned unsubstituted hydroxylamine or hydroxylamine derivatives; more preferably, salts of inorganic acids bonded to nonmetallic atoms such as Cl, S, N, or P and hydrogen atoms; and even more preferably, salts of any one of hydrochloric acid, sulfuric acid, and nitric acid. Among these, hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine phosphate, N,N-diethylhydroxylamine sulfate, N,N-diethylhydroxylamine nitrate, or mixtures thereof are preferred.

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

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

[0054] Hydroxylamine compounds can be used alone or in combination. From the viewpoint of superior corrosion resistance, it is preferable to use two or more hydroxylamine compounds.

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

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

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

[0058] Hydroxylamine compounds can be used alone or in combination with two or more. When two or more are used, their total content is preferably within the range described above.

[0059] <Specific chelating agents>

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

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

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

[0063] The number of ligands in a particular chelating agent is not particularly limited, but is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0064] (Phosonic acid chelating agents)

[0065] Phosphonic acid chelating agents are compounds that have one or more phosphonic acid groups and are chelated with metals.

[0066] Examples of phosphonic acid chelating agents include hydroxyphosphonic acid compounds, polyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonoacylcarboxylic acid compounds.

[0067] Preferably, hydroxyphosphonic acid compounds, aminophosphonic acid compounds, or phosphonocarboxylic acid compounds are used, with aminophosphonic acid compounds being more preferred.

[0068] Hydroxyphosphonic acid compounds are compounds that have one or more phosphonic acid groups and one or more hydroxyl groups in their molecules.

[0069] Furthermore, polyphosphonic acid compounds are compounds having two or more phosphonic acid groups within their molecules. Additionally, compounds having any one of hydroxyl, amino, or carboxyl groups within their molecules are excluded from the definition of polyphosphonic acid compounds.

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

[0071] [Chemical Formula 1]

[0072]

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

[0074] R in equation (1) 1 The alkyl group represented can be any of the following: straight-chain, branched, and cyclic, preferably straight-chain or branched.

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

[0076] Furthermore, in the specific examples of alkyl groups described in this specification, n- denotes the normal form (positive type).

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

[0078] Furthermore, examples of hydroxyphosphonic acid compounds other than those represented by formula (1) include 2-hydroxyethane-1,1-bisphosphonic acid, 3-hydroxypropane-1,1-bisphosphonic acid, glycerol-3-phosphate, and ethane-hydroxy-1,1,2-triphosphonic acid.

[0079] As the hydroxyphosphonic acid compound, 1-hydroxyethane-1,1-bisphosphonic acid or glycerol-3-phosphonic acid are preferred. Among these, 1-hydroxyethane-1,1-bisphosphonic acid is more preferred from the viewpoint of superior removal performance and corrosion resistance, and glycerol-3-phosphonic acid is more preferred from the viewpoint of superior removal performance and long-term stability.

[0080] Aminophosphonic acid compounds are compounds having one or more phosphonic acid groups and one or more amino groups within their molecules. Compounds having a carboxyl group within their molecules are excluded from the category of aminophosphonic acid compounds.

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

[0082] [Chemical Formula 2]

[0083]

[0084] In the formula, Q represents a hydrogen atom or -R 3 -PO3H2,R 2 and R 3 Each of these can be independently represented as an alkylene group, where Y represents a hydrogen atom, -PO3H2, or a group represented by formula (4) below.

[0085] [Chemical Formula 3]

[0086]

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

[0088] In equation (2), R 2 The alkylene group represented can be either straight-chain or branched. As R 2 The alkylene group represented is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably methylene or ethylene.

[0089] As Y in formula (2), it is preferably -PO3H2 or the group represented by formula (4), more preferably -PO3H2.

[0090] Furthermore, R in equation (2) 2 The combination of R and Y is preferred. 2 A combination of methylene and Y being -PO3H2 or R 2 Y is a combination of ethylene and the group represented by formula (4).

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

[0092] In equations (2) and (4), R 3 The alkylene group represented can be either straight-chain or branched. As R 3 The alkylene group represented is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and even more preferably methylene or ethylene, especially methylene.

[0093] Examples of aminophosphonic acid compounds represented by formula (2) include ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrosotris(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), 1,3-propylidenediaminebis(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) (EDTPO), ethylenediaminetetra(ethylenephosphonic acid), 1,3-propanediaminetetra(methylenephosphonic acid) (PDTMP), 1,2-diaminopropanetetra(methylenephosphonic acid), and 1,6-hexamethylenediaminetetra(methylenephosphonic acid).

[0094] [Chemical Formula 4]

[0095]

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

[0097] In equation (3), R 4 and R 5 The alkylene groups representing 1 to 4 carbon atoms can be either straight-chain or branched. As R 4 and R 5 The alkylene group represented has 1 to 4 carbon atoms, preferably an ethylene group.

[0098] In equation (3), n is preferably 1 or 2.

[0099] Z in equation (3) 1 ~Z 5 The alkyl group represented and the alkyl group having a phosphonic acid group can be any of straight-chain alkyl and branched alkyl, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably methyl.

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

[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) (EDTPO), 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 may have a linking group containing one or more heteroatoms selected from oxygen, nitrogen and sulfur atoms. Preferably, it has an oxygen or nitrogen linking group or does not have a linking group containing heteroatoms. From the viewpoint of better removal performance and stability over time, it is more preferable to not have a linking group containing heteroatoms.

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

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

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

[0114] In equation (5), the sum of i and j (i+j) is preferably an integer from 2 to 6, and more preferably an integer from 2 to 4.

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

[0116] From the viewpoint of superior removal performance and stability over time, 2-phosphonobutane-1,2,4-tricarboxylic acid or 4-phosphonobutyric acid is preferred. From the viewpoint of superior residue removal performance and corrosion resistance, 2-phosphonobutane-1,2,4-tricarboxylic acid or glycine-N,N-bis(methylenephosphonic acid) is preferred. As a hydroxyphosphonic acid compound, 2-phosphonobutane-1,2,4-tricarboxylic acid is further preferred.

[0117] Polyphosphonic acid compounds are compounds having two or more phosphonic acid groups within their molecules. However, hydroxyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonoacylcarboxylic acid compounds are not included in polyphosphonic acid compounds.

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

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

[0120] In equation (6), R 7 This represents an aliphatic hydrocarbon group with a valence of k, where k represents an integer from 2 to 6.

[0121] R 7The aliphatic hydrocarbon group represented can be any of the following: straight-chain, branched, and cyclic, preferably straight-chain or branched. Furthermore, R... 7 The aliphatic hydrocarbon group represented can be either saturated or unsaturated hydrocarbons, but saturated hydrocarbons are preferred.

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

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

[0124] Examples of polyphosphonic acid compounds include ethylidene bisphosphonic acid, propylene bisphosphonic acid, butylidene bisphosphonic acid, and isopropylene bisphosphonic acid.

[0125] Furthermore, as a polyphosphonic acid compound, the compound (copolymer) described in paragraphs

[0031] to

[0046] of International Publication No. 2018 / 030006 can also be cited, which is incorporated into this specification.

[0126] (Carboxylic acid chelating agents)

[0127] Carboxylic acid chelating agents are compounds having one or more carboxyl groups that chelate with a metal. Hereinafter, unless otherwise specified, carboxylic acid chelating agents other than polyaminocarboxylic acids will be simply referred to as "carboxylic acid chelating agents". Furthermore, compounds having both a carboxyl group and a phosphonic acid group are excluded from the category of carboxylic acid chelating agents, but are included in the category of phosphonic acid chelating agents.

[0128] Examples of carboxylic acid chelating agents include polycarboxylic acid compounds, hydroxy acid compounds, aromatic carboxylic acid compounds, and amino acid compounds.

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

[0130] Polycarboxylic acid compounds are compounds having two or more carboxyl groups within their molecules. However, hydroxy acid compounds, aromatic carboxylic acid compounds, and amino acid compounds, which are mentioned later, are not included in polycarboxylic acid compounds.

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

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

[0133] In equation (7), R 8 This represents an aliphatic hydrocarbon group with a p valence, where p represents an integer from 2 to 6.

[0134] R8 The aliphatic hydrocarbon group represented can be any of the following: straight-chain, branched, and cyclic, preferably straight-chain or branched. Furthermore, R... 8 The aliphatic hydrocarbon group represented can be either saturated or unsaturated hydrocarbons, but saturated hydrocarbons are preferred.

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

[0136] R 8 The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but 1 to 10 is preferred, more preferably 2 to 6, and from the viewpoint of better stability over time in terms of removal performance, 2 to 4 is even more preferred.

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

[0138] Examples of polycarboxylic acid compounds include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 3-methyladipic acid, sebacic acid, maleic acid, and 1,3,5-pentanetricarboxylic acid. Succinic acid, glutaric acid, adipic acid, pimelic acid, 3-methyladipic acid, or 1,3,5-pentanetricarboxylic acid are preferred. From the viewpoint of superior long-term stability in removal performance, succinic acid, glutaric acid, or adipic acid are more preferred. Furthermore, from the viewpoint of removal performance, 1,3,5-pentanetricarboxylic acid is more preferred.

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

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

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

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

[0143] R 9 The aliphatic hydrocarbon group represented can be any of straight-chain, branched, or cyclic, but straight-chain or branched is preferred. Furthermore, R... 9 The aliphatic hydrocarbon group represented can be either saturated or unsaturated hydrocarbons, but saturated hydrocarbons are preferred.

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

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

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

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

[0148] In equation (8), the sum of m and n (m+n) is preferably an integer from 2 to 4, more preferably 2 or 3.

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

[0150] Aromatic carboxylic acid compounds are compounds that have one or more carboxyl groups and aromatic rings within their molecules.

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

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

[0153] In formula (9), Ar represents an aromatic hydrocarbon group with a valence of q that can have substituents, and q represents an integer from 1 to 6. When q represents 1, the aromatic hydrocarbon group represented by Ar further has ligands other than carboxyl and phosphonic acid groups.

[0154] Substituents that can be present in the aromatic hydrocarbon group represented by Ar include, for example, one or more ligands selected from hydroxyl, amino, and sulfonyl groups, as well as aliphatic hydrocarbon groups (preferably alkyl groups having 1 to 4 carbon atoms) that can have the above-mentioned ligands. In addition, the aliphatic hydrocarbon group present in Ar can have a carboxyl group in formula (9).

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

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

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

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

[0159] Amino acid compounds are compounds that have one or more carboxyl groups and one or more amino groups as ligands within their molecules. However, hydroxy acid compounds and aromatic carboxylic acid compounds are not included in amino acid compounds.

[0160] Examples of amino acid compounds include glycine, serine, α-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), leucine, isoleucine, cysteine, ethionine, threonine, aspartic acid, glutamic acid, proline, methionine, and phenylalanine, as well as their salts.

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

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

[0163] A specific chelating agent can be used alone or in combination with two or more.

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

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

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

[0167] Furthermore, from the viewpoint of superior removal performance and stability over time, the aforementioned mass ratio is preferably 100 or less, and more preferably 10 or less.

[0168] <Benzotriazole compounds>

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

[0170] As a benzotriazole compound, there are no particular restrictions as long as it has a benzotriazole structure, for example, the compound represented by the following formula (A) can be cited.

[0171] [Chemical Formula 5]

[0172]

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

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

[0175] n represents an integer from 0 to 4. When n is 2 or more, there are n R's. 11 They can be the same or different.

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

[0177] Furthermore, R 11 The substituents may further have one or more substituents selected from hydroxyl and carboxyl groups.

[0178] [Chemical Formula 6]

[0179]

[0180] In equation (B), R 13 and R 14 Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 6 carbon atoms that may have a hydroxyl group.

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

[0182] * indicates the bonding site.

[0183] R in equation (B) 13 and R 14 Preferably, it contains hydrogen atoms or alkyl groups with 1 to 3 carbon atoms having hydroxyl groups, more preferably hydrogen atoms or 2-hydroxyethyl groups.

[0184] R in equation (B) 15Preferably, it is a single bond or an alkylene group having 1 to 3 carbon atoms, more preferably a single bond or an ethylene group.

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

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

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

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

[0189] Furthermore, R 12 The substituents may further have one or more substituents selected from hydroxyl and carboxyl groups.

[0190] As R in equation (A) 12 Preferably, hydrogen atoms, hydroxyl groups, groups represented by the above formula (B), or alkyl groups having 1 to 6 carbon atoms and a carboxyl group are used, and hydrogen atoms or hydroxyl groups are more preferred.

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

[0192] Benzotriazole compounds can be used alone or in combination with two or more.

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

[0194] Furthermore, the upper limit is not particularly limited, but from the viewpoint of superior residue removal performance, it is preferably 10% by mass or less, more preferably 3% by mass or less, and even more preferably 0.5% by mass or less relative to the total mass of the cleaning agent composition.

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

[0196] Furthermore, from the viewpoint of superior corrosion resistance, the above-mentioned mass ratio is preferably 1000 or less, and more preferably 100 or less.

[0197] Solvent

[0198] The liquid medicine may contain a solvent.

[0199] Examples of solvents include water and organic solvents, with water being the preferred choice.

[0200] (water)

[0201] The cleaning agent composition preferably contains water.

[0202] There are no particular restrictions on the type of water used in the cleaning agent composition, as long as it does not adversely affect the semiconductor substrate. Examples include distilled water, deionized water (DI), and pure water (ultrapure water). From the viewpoint that it contains almost no impurities and has less impact on the semiconductor substrate during the semiconductor device manufacturing process, pure water is preferred.

[0203] The water content in the cleaning agent composition is not particularly limited, but is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 85% by mass or more, relative to the total mass of the cleaning agent composition. Furthermore, there is no particular upper limit, but it is preferably 99% by mass or less, more preferably 95% by mass or less.

[0204] (Organic solvents)

[0205] Cleaning agent compositions may contain organic solvents.

[0206] As an organic solvent, water-soluble organic solvents are preferred, alcohol-based solvents, ketone-based solvents, or amide-based solvents are more preferred, and alcohol-based solvents are even more preferred.

[0207] Examples of alcohol solvents include alkyl glycols, alkylene glycols, alkoxy alcohols, saturated or unsaturated aliphatic alcohols, and alcohols with three or more hydroxyl groups.

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

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

[0210] Examples of alkoxy alcohols include monoalkylene glycol ethers and dialkylene glycol ethers.

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

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

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

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

[0215] Examples of alcohols that are trivalent or higher include glycerol.

[0216] Alkoxy alcohols are preferred as alcohol solvents. Among the alkoxy groups mentioned above, alkoxy groups with 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy, are preferred.

[0217] As ketone solvents, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone can be cited.

[0218] As amide solvents, for example, formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone can be cited.

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

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

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

[0222] <pH adjuster>

[0223] To adjust the pH of the cleaning agent composition, the cleaning agent composition may contain a pH adjuster.

[0224] As pH adjusters, for example, inorganic acids, organic acids (excluding specific chelating agents), organic bases, and inorganic bases can be cited.

[0225] As inorganic acids, sulfuric acid, acetic acid, nitric acid, phosphoric acid, and hydrofluoric acid can be cited. As organic acids, lower (carbon number 1 to 4) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid can be cited. And the above carboxylic acid-based chelating agents can be used to also serve as pH adjusters for reducing the pH of the cleaning agent composition.

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

[0227] As quaternary ammonium salt compounds, quaternary ammonium hydroxides are preferred, and the 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] Examples of water-soluble amines with pKa values ​​of 7.5 to 13.0 include diethylene glycolamine (DGA) (pKa = 9.80), methylamine (pKa = 10.6), ethylamine (pKa = 10.6), propylamine (pKa = 10.6), butylamine (pKa = 10.6), pentylamine (pKa = 10.0), monoethanolamine (pKa = 9.3), monopropanolamine (pKa = 9.3), monobutanolamine (pKa = 9.3), methoxyethylamine (pKa = 10.0), methoxypropylamine (pKa = 10.0), dimethylamine (pKa = 10.8), diethylamine (pKa = 10.9), dipropylamine (pKa = 10.8), trimethylamine (pKa = 9.80), and triethylamine (pKa = 10.72).

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

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

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

[0241] pH adjusters can be used alone or in combination with two or more.

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

[0243] <Additives>

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

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

[0246] Cleaning agent compositions may contain surfactants.

[0247] There are no particular restrictions on the types of surfactants; examples include ionic surfactants (anionic surfactants, cationic surfactants, and amphoteric surfactants) and nonionic surfactants.

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

[0249] The cleaning agent composition may contain other components besides those mentioned above, provided that it does not impair the effectiveness of the invention or the function of each component.

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

[0251] [pH]

[0252] The pH of the cleaning agent composition is not particularly limited, but from the viewpoint of superior removal performance stability over time and superior corrosion resistance, it is preferred to be above 7, and more preferably above 8.

[0253] The upper limit of pH is not particularly limited, but it is preferred to be below 14, and more preferably below 12.

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

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

[0256] [Manufacturing Method]

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

[0258] For example, a cleaning agent composition can be manufactured by sequentially adding a hydroxylamine compound, a specific chelating agent, a benzotriazole compound, and any other component to a mixer containing purified pure water and then thoroughly mixing the components.

[0259] In the preparation of the cleaning agent composition, the raw materials used are preferably classified as semiconductor grade or as high purity grade based on semiconductor grade.

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

[0261] The purification method is not particularly limited and can include methods such as using ion exchange resins or RO membranes (Reverse Osmosis Membrane), distillation, and filtration. More specifically, a method can be described as follows: after a first purification by a reverse osmosis membrane, a second purification is performed using a purification device composed of cation exchange resins, anion exchange resins, or mixed-bed ion exchange resins.

[0262] <Reagent Kit and Concentrate>

[0263] The cleaning agent composition can be formulated into a kit by separating its raw materials into multiple parts.

[0264] While not particularly restricted, a specific method for preparing a kit from a cleaning agent composition may be exemplified as follows: preparing a solution composition containing a hydroxylamine compound, a specific chelating agent, and a benzotriazole compound as a first solution, and preparing a solution composition containing other ingredients as a second solution.

[0265] Furthermore, the cleaning agent composition can also be prepared using a concentrate. When preparing a concentrate of the cleaning agent composition, its concentration ratio can be appropriately determined according to the composition, but is preferably 5 to 2000 times. That is, the cleaning agent composition is used after diluting the concentrate by 5 to 2000 times. Moreover, from the viewpoint of further improving the long-term stability of the removal performance, it is preferable to prepare a composition containing a large amount of alcohol solvent by minimizing the amount of water that contributes to the decomposition of hydroxylamine compounds.

[0266] <Container (Containment Container)>

[0267] As long as no corrosion or other problems occur (whether in the reagent kit or the concentrate), the cleaning agent composition can be filled into any container for storage, transportation, and use. As a container, containers with high cleanliness and minimal leaching of impurities are preferred for semiconductor applications. Examples of usable containers include, for example, the "Cleag Bottle" series manufactured by AICELLO CHEMICAL CO.,LTD. and the "Pure Bottle" manufactured by KODAMA PLASTICS CO.,LTD., but are not limited to these.

[0268] As a container, it is preferable to have an interior that has been cleaned before filling with the cleaning agent composition. Regarding the liquid used in cleaning, it is preferable to reduce the amount of metallic impurities in the solution. The cleaning agent composition can also be transported and stored in containers such as gallon bottles or coated bottles after manufacturing.

[0269] Cleanroom

[0270] Operations, processing analysis, and determinations, including the manufacture of the cleaning agent composition, the opening and / or cleaning of the containment container, and the filling of the cleaning agent composition, are preferably performed in a cleanroom. The cleanroom preferably meets the 14644-1 cleanroom standard, more preferably meets any one of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, further preferably meets ISO Class 1 or ISO Class 2, and especially preferably meets ISO Class 1.

[0271] [Cleaning Method]

[0272] As a cleaning method using a cleaning agent composition, an example example is a cleaning step (hereinafter also referred to as "cleaning step B") that involves cleaning a semiconductor substrate with a metal layer using the aforementioned cleaning agent composition. Furthermore, the cleaning method may include a cleaning agent composition preparation step (hereinafter also referred to as "cleaning agent composition preparation step A") prior to cleaning step B.

[0273] In the following description of the cleaning method, the case in which the cleaning agent composition preparation step A is performed before the cleaning step B is shown as an example, but it is not limited to this. The cleaning method can also be performed using the cleaning agent composition prepared in advance.

[0274] <Objects to be cleaned>

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

[0276] As a more specific object to be cleaned, an example is a stack of layers having at least the aforementioned metal layer, interlayer insulating layer, and metal hard mask sequentially on a substrate. The stack is further subjected to a dry etching process to form holes from the surface (opening) of the metal hard mask toward the substrate, thereby exposing the surface of the metal layer.

[0277] The manufacturing method of the stacked material with holes as described above is not particularly limited. For example, the following method can be used: for a pre-processing stacked material having a substrate, a metal layer, an interlayer insulating layer and a metal hard mask in sequence, a dry etching process is performed using the metal hard mask as a mask to etch the interlayer insulating layer so that the surface of the metal layer is exposed, thereby forming a hole through the metal hard mask and the interlayer insulating layer.

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

[0279] After manufacturing the metal hard mask, the resist stripping process is carried out by dry ashing treatment such as plasma ashing.

[0280] In substrates that have undergone dry etching and resist stripping processes, residues containing organic components derived from the resist film adhere to their metal layers and / or interlayer insulating layers. These adhered residues are removed from the laminate using the aforementioned cleaning agent composition.

[0281] The laminate may have layers other than those mentioned above, such as an etch stop layer and an anti-reflective layer.

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

[0283] Figure 1 The laminate 10 shown has a metal layer 2, an etch stop layer 3, an interlayer insulating layer 4, and a metal hard mask 5 sequentially formed on a substrate 1. Holes 6 are formed at predetermined locations through a dry etching process to expose the metal layer 2. That is, Figure 1 The stack 10 shown is a stack comprising, in sequence, a substrate 1, a metal layer 2, an etch stop layer 3, an interlayer insulating layer 4, and a metal hard mask 5, wherein an opening 6 is provided in the metal hard mask 5, extending from its surface to the surface of the metal layer 2. Furthermore, Figure 1 The resist film of the laminate 10 shown is removed by a resist stripping process.

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

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

[0286] The following describes the materials that make up each layer of the above-mentioned laminated material.

[0287] (Metal hard mask)

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

[0289] Materials that can be used as the aforementioned metal hard mask include, for example, TiN, WO2 and ZrO2.

[0290] (Interlayer insulation layer)

[0291] The material of the interlayer insulation layer is not particularly limited, for example, preferably with a dielectric constant k of 3.0 or less, more preferably 2.6 or less.

[0292] Materials used as specific interlayer insulating layers include, for example, SiO2, SiOC-based materials, and organic polymers such as polyimide.

[0293] (Etching stop layer)

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

[0295] (Metal layer)

[0296] The wiring material forming the metal layer is not particularly limited; for example, it can contain one or more metals selected from Cu (copper), W (tungsten), and Co (cobalt). The wiring material can be a metal composed solely of Cu, W, or Co, or an alloy of Cu, W, or Co with other metals. Preferably, it contains a metal of W or Co, and more preferably, it contains a metal of Co.

[0297] Furthermore, the wiring material may further include metals other than Cu, W and Co, metal nitrides or alloys, such as one or more selected from titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxide and aluminum.

[0298] (Substrate)

[0299] The term "substrate" as used herein includes, for example, a semiconductor substrate consisting of a single layer and a semiconductor substrate consisting of multiple layers.

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

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

[0302] <Processing Steps>

[0303] The following sections describe in detail the preparation process A of the cleaning agent composition and the cleaning process B.

[0304] (Step A in the preparation of the cleaning agent composition)

[0305] Step A, the preparation step of the cleaning agent composition, is the step of preparing the above-mentioned cleaning agent composition. The components used in this step are as described above.

[0306] The steps in this process are not particularly limited. For example, a method can be given to prepare a cleaning agent composition by adding hydroxylamine compounds, specific chelating agents, benzotriazole compounds, and other arbitrary ingredients and mixing them. Furthermore, the ingredients can be added together or in multiple stages.

[0307] Furthermore, the components included in the cleaning agent composition preferably use components classified as semiconductor grade or high purity grade based on these standards, and preferably use components that have undergone foreign matter removal based on filtration and / or ion content reduction based on ion exchange resins. Moreover, after mixing the raw material components, it is further preferable to perform foreign matter removal based on filtration and / or ion content reduction based on ion exchange resins.

[0308] Furthermore, when preparing a concentrated solution of the cleaning agent composition, before performing cleaning step B, the concentrated solution is diluted to obtain a diluted solution, and then cleaning step B is performed using the diluted solution. In this case, it is preferable to use a diluted solution containing water for the above dilution.

[0309] (Cleaning process B)

[0310] As an example of the object to be cleaned in cleaning step B, the aforementioned laminate can be cited. As described above, a porous laminate 10 formed by performing a dry etching process and a dry ashing process can be illustrated (see reference). Figure 1 Additionally, residue 12 adheres to the layer 10 within the hole 6.

[0311] <Cleaning Method>

[0312] The method of bringing the cleaning agent composition into contact with the object to be cleaned is not particularly limited. Examples include immersing the object to be cleaned in the cleaning agent composition placed in a container, spraying the cleaning agent composition onto the object to be cleaned, allowing the cleaning agent composition to flow onto the object to be cleaned, and combinations thereof. From the viewpoint of removal performance, the method of immersing the object to be cleaned in the cleaning agent composition is preferred.

[0313] The temperature of the cleaning agent composition is preferably below 90°C, more preferably 25-80°C, even more preferably 30-75°C, and particularly preferably 40-70°C.

[0314] During cleaning, the temperature of c can be adjusted according to the cleaning method and the cleaning agent composition used.

[0315] When cleaning by batch immersion (a batch method of immersing and treating multiple sheets of objects to be cleaned 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 even more preferably 4 to 15 minutes.

[0316] When cleaning in a single-sheet manner, the cleaning time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, and even more preferably 20 seconds to 2 minutes.

[0317] In addition, mechanical stirring can be used to further enhance the cleaning ability of the cleaning agent composition.

[0318] Examples of mechanical stirring methods include circulating the cleaning agent composition over the object to be cleaned, flowing or spraying the cleaning agent composition over the object to be cleaned, and stirring the cleaning agent composition by ultrasonic or megasononic methods.

[0319] (Rinsing process B2)

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

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

[0322] There are no particular limitations on the rinsing solvents used; examples include deionized water, methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Furthermore, aqueous rinsing solutions with a pH greater than 8 (such as diluted aqueous ammonium hydroxide) can also be used.

[0323] As a rinsing solvent, aqueous solution of ammonium hydroxide, DI water, methanol, ethanol or isopropanol are preferred, aqueous solution of ammonium hydroxide, DI water or isopropanol are more preferred, and aqueous solution of ammonium hydroxide or DI water are even more preferred.

[0324] The method described above for contacting the cleaning agent composition with the object being cleaned can also be used as a method for bringing the rinsing solvent into contact with the object being cleaned.

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

[0326] (Drying process B3)

[0327] The cleaning method for substrates using a cleaning agent composition may include a drying step after the rinsing step to dry the object being cleaned.

[0328] There are no particular limitations on the drying method. Examples include rotary drying, methods of passing dry gas over the surface of the object to be cleaned, methods of heating the substrate by means of a heating mechanism such as a heating plate or infrared lamp, Marangoni drying, Rotagoni drying, IPA (isopropyl alcohol) drying, and combinations thereof.

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

[0330] The cleaning target of the substrate cleaning method 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 sequentially on the substrate as described above. For example, it can also be used to remove residues originating from the resist film that adhere to the laminate having at least a metal layer, an interlayer insulating layer, and a resist film sequentially on the substrate.

[0331] Example

[0332] The present invention will now be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below. Furthermore, unless otherwise specified, "%" refers to "mass %".

[0333] [Preparation of Cleaning Agent Composition]

[0334] The cleaning agent compositions were prepared according to the following steps. Furthermore, the amounts (all by weight) of the various components used in each cleaning agent composition are shown in the table.

[0335] 〔raw material〕

[0336] The following shows the raw materials used in the preparation of the cleaning agent composition. Furthermore, all compounds used in the preparation of the cleaning agent composition are classified as semiconductor grade or as high-purity grades based on these classifications.

[0337] <Hydramine compounds (or redox agents)>

[0338] HA: Hydroxylamine

[0339] HAS: Hydroxylamine sulfate

[0340] DEHA: N,N-Diethylhydroxylamine

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

[0342] <Specific chelating agents>

[0343] (Aminophosphonic acid compounds)

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

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

[0346] (hydroxy acid compounds)

[0347] 2-a: Diethanolglycine

[0348] 2-b: Citric acid

[0349] 2-c: malic acid

[0350] (phosphonoacylcarboxylic acid compounds)

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

[0352] 3-b:4-phosphonobutyric acid

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

[0354] (Aromatic carboxylic acid compounds)

[0355] 4-a: Isophthalic acid

[0356] 4-b: Salicylic acid

[0357] (Polycarboxylic acid compounds)

[0358] 5-a: Glutaric acid

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

[0360] 5-C: 3-Methyladipic acid

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

[0362] (Hydroxyphosphonic acid compound)

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

[0364] 6-b: Glycerol 3-phosphate

[0365] <pH regulator>

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

[0367] MEA: Monoethanolamine

[0368] TMAH: Tetramethylammonium hydroxide

[0369] <Organic solvent>

[0370] EGBE: Ethylene glycol monobutyl ether

[0371] EGME: Ethylene glycol monomethyl ether

[0372] <Water>

[0373] Water: DI water

[0374] 〔Evaluation〕

[0375] The following various evaluations were performed on each cleaning agent composition prepared above.

[0376] <Removal performance of organic residues>

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

[0378] 200 mL of the cleaning agent composition was filled into a 500 mL glass beaker. While stirring, the temperature of the cleaning agent composition was raised to 65°C. Then, while stirring, the prepared test piece was immersed in the cleaning agent composition at 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 in place using 4-inch plastic locking pinsets with the side of the test piece with the light-resist removed facing the stir bar.

[0379] After the cleaning time has elapsed, the test piece was immediately removed from the cleaning agent composition, filled into a 500 mL plastic beaker, and placed in 400 mL of DI water (17°C) under slow stirring. After immersing the test piece in the DI water for 30 seconds, it was immediately removed and rinsed for 30 seconds under a 17°C DI water stream.

[0380] Next, the surface of the test piece was dried by exposing it to a nitrogen gas stream, which blew away the droplets adhering to the surface of the test piece.

[0381] After the nitrogen drying process, the test piece was removed from the holding part of the plastic tweezers and placed in a covered plastic storage box with the component side facing up.

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

[0383] 5: Removal rate is over 95%

[0384] 4. The removal rate is above 80% but less than 95%.

[0385] 3: The removal rate is above 75% and less than 80%.

[0386] 2: The removal rate is above 50% and less than 75%.

[0387] 1: Removal rate less than 50%

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

[0389] Next, the cleaning agent compositions of each embodiment and each comparative example were used as test solutions for storage tests, and the time-dependent stability of the removal performance of each cleaning agent composition was evaluated.

[0390] Each test solution, prepared using the above method, was filled into a 250 mL high-density polyethylene container and sealed. The containers filled with the test solutions were then stored at 60°C for 24 hours.

[0391] In addition to using the cleaning agent compositions after the storage test, the removal performance was evaluated according to the above-described method for evaluating removal performance, and the stability of each cleaning agent composition over time was evaluated.

[0392] Corrosion Resistance

[0393] A substrate (substrate with a metal layer) was prepared in which a layer composed of Co (Co layer) was formed on one surface of a substrate (silicon wafer (diameter: 12 inches)) by chemical vapor deposition (CVD). The substrate with the Co layer was then immersed in the cleaning agent composition (65°C) of the examples and comparative examples for 5 minutes.

[0394] The etching rate of the Co layer by the cleaning agent composition is calculated based on the difference in the thickness of the Co layer before and after immersion in the cleaning agent composition. / minute). The lower the etching rate (FR) of the Co layer measured in this experiment, the better the corrosion resistance of the Co layer.

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

[0396] A:

[0397] B:

[0398] C:

[0399] D:

[0400] E:

[0401] 〔result〕

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

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

[0404] The "pH Adjuster" label indicates that each cleaning agent composition contains a pH adjuster. The amount of pH adjuster in each cleaning agent composition is the amount by which the pH of the final cleaning agent composition is equal to the value shown in the "pH" column of the table.

[0405] The description of "remaining portion" as the water content indicates that the final cleaning agent composition contains ingredients other than the amount of pH adjuster shown in the table and the amount of pH adjuster that makes up the pH shown in the table, and the remaining component is water.

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

[0407] In the table, the "Removal Performance" column indicates the evaluation results of the removal performance of organic residues using the cleaning agent compositions of each example and each comparative example. The "After Preparation" column of "Removal Performance" indicates the evaluation results of the removal performance immediately after the preparation of each cleaning agent composition, and the "After Storage" column of "Removal Performance" indicates the evaluation results of the removal performance of each cleaning agent composition after storage tests.

[0408] [Table 1]

[0409] [Table 1]

[0410]

[0411] [Table 2]

[0412] [Continued from Table 1]

[0413]

[0414] [Table 3]

[0415] [Table 2]

[0416]

[0417] [Table 4]

[0418] [(Continued from Table 2)]

[0419]

[0420] [Table 5]

[0421] [Table 3]

[0422]

[0423] [Table 6]

[0424] [Table 4]

[0425]

[0426] [Table 7]

[0427] [Table 5]

[0428]

[0429] [Table 8]

[0430] [Table 6]

[0431]

[0432] [Table 9]

[0433] [Table 7]

[0434]

[0435] The results shown in the table confirm that the problem of the present invention can be solved by using the cleaning agent composition of the present invention.

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

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

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

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

[0440] It was confirmed that when the ratio 1 (mass ratio of the content of hydroxylamine compound to the content of a specific chelating agent) in the cleaning agent composition is 100 or less, the removal performance has better stability over time, and when the ratio 1 is 10 or less, the removal performance has even better stability over time (comparison of Examples 1-3, comparison of Examples 24, 25 and 27).

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

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

[0443] It was confirmed that when the ratio 2 (mass ratio of hydroxylamine compound content to benzotriazole compound content) in the cleaning agent composition is below 1000, the corrosion resistance is superior (comparison of Examples 7 and 12).

[0444] Furthermore, it was confirmed that when the ratio 2 is 10 or higher, the residue removal performance is superior (comparison of Examples 2 and 8).

[0445] The results in Table 2 confirm that the removal performance is superior when hydroxylamine or hydroxylamine sulfate is used in hydroxylamine compounds (comparison of Examples 24, 39 and 40).

[0446] Furthermore, it was confirmed that when two or more hydroxylamine compounds were used, the corrosion resistance was superior compared to the use of a single hydroxylamine compound (comparison of Examples 24, 39 and 41).

[0447] Based on the results in Tables 1 to 6, it was confirmed that when using aminophosphonic acid compounds or hydroxy acid compounds in specific chelating agents, the removal performance and the stability of the removal performance over time are superior (comparison of Examples 2, 16, 24, 35, 36, 45, 47, 48, 50, 52, 54, 56, 57, 59 and 61).

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

[0449] The results in Table 5 confirm that the removal performance exhibits superior stability over time when glutaric acid from polycarboxylic acid compounds is used (comparison of Examples 54, 56, and 57), and the removal performance is even better when 1,3,5-pentanetricarboxylic acid is used (comparison of Examples 54, 56, and 57).

[0450] The results in Table 6 confirm that when 1-hydroxyethane-1,1-diphosphonic acid from the hydroxyphosphonic acid compound is used, the removal performance and corrosion resistance are superior (comparison of Examples 59 and 61), and when glycerol-3-phosphoric acid is used, the removal performance has superior stability over time (comparison of Examples 59 and 61).

[0451] Symbol Explanation

[0452] 1-Substrate, 2-Metal layer, 3-Etching stop layer, 4-Interlayer insulating layer, 5-Metal hard mask, 6-Hole, 10-Laminated material, 11-Inner wall, 11a-Section wall, 11b-Bottom wall, 12-Residue.

Claims

1. A cleaning agent composition, which is a cleaning agent composition for semiconductor devices, said cleaning agent composition comprising: One or more hydroxylamine compounds selected from hydroxylamine and hydroxylamine salts; Chelating agents selected from one or more of carboxylic acid chelating agents (excluding polyaminocarboxylic acids) and phosphonic acid chelating agents; and benzotriazole compounds, The mass ratio of the hydroxylamine compound content to the chelating agent content is 0.1 to 100.

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 chelating agent comprises one or more compounds selected from hydroxyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonoacylcarboxylic acid compounds.

4. The cleaning agent composition according to claim 2 or 3, wherein, The phosphonic acid chelating agent contains 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 chelating agent comprises one or more compounds selected from hydroxy acid compounds, polycarboxylic acid compounds, and aromatic polycarboxylic acid compounds.

7. The cleaning agent composition according to claim 5 or 6, wherein, The carboxylic acid chelating agent contains hydroxy acid compounds.

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). In formula (A), R 11 Indicates a carboxyl group, an amino group, or an alkyl group having 1 to 6 carbon atoms. n represents an integer from 0 to 2. R 12 It represents a hydrogen atom or a hydroxyl group.

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

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

12. The cleaning agent composition according to claim 1 or 2, wherein, The pH of the cleaning agent composition is above 7.0 and below 10.

0. The cleaning agent composition also contains an organic solvent. The content of the organic solvent is 0.001% to 10% by mass relative to the total mass of the cleaning agent composition.

13. The cleaning agent composition according to claim 1 or 2, wherein, The cleaning agent composition also includes a pH adjuster.

14. The cleaning agent composition according to claim 12, wherein, The organic solvent includes alcohol-based solvents.

15. The cleaning agent composition according to claim 12, wherein, The organic solvent contains alkoxy alcohols.

16. The cleaning agent composition according to claim 9, wherein, R in equation (A) 11 It is a methyl group.

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

18. The cleaning agent composition according to claim 9, wherein, R in equation (A) 12 It is 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 pKa of the water-soluble amine is 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% by mass or more and 15% by mass or less relative 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% by mass or more and 15% by mass or less relative to the total mass of the cleaning agent composition.

24. The cleaning agent composition according to claim 12, wherein, The content of the organic solvent is 0.1% to 5% by mass relative 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 more than 0.001% by mass and less than 3% by mass relative 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 more than 0.001% by mass and less than 0.5% by mass relative 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 more than 0.1% by mass and less than 0.3% by mass relative 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 hydroxylamine compound content to the benzotriazole compound content is more than 1 and less than 100.

29. The cleaning agent composition according to claim 1 or 2, wherein, The mass ratio of the hydroxylamine compound content to the benzotriazole compound content is 30 or more and 120 or less.

30. The cleaning agent composition according to claim 5, wherein, The content of the carboxylic acid chelating agent is more than 0.02% by mass and less than 1.0% by mass relative 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 above 7.0 and below 9.

0.

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 more than 0.1% by mass and less than 30% by mass relative 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 more than 0.5% by mass and less than 6.0% by mass relative to the total mass of the cleaning agent composition.

36. The cleaning agent composition according to claim 12, wherein, The organic solvent contains alkylene glycol monoalkyl ethers.

37. The cleaning agent composition according to claim 1 or 2, wherein, The cleaning agent composition also contains an organic solvent. The content of the organic solvent is 0.001% to 10% by mass relative to the total mass of the cleaning agent composition.

38. The cleaning agent composition according to claim 37, wherein, The content of the organic solvent is 0.001% to 5% by mass relative to the total mass of the cleaning agent composition.

39. The cleaning agent composition according to claim 37, wherein, The content of the organic solvent is 0.1% to 2.0% by mass relative to the total mass of the cleaning agent composition.

40. The cleaning agent composition according to claim 37, wherein, The content of the organic solvent is 2.0% to 5% by mass relative to the total mass of the cleaning agent composition.

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

42. The cleaning agent composition according to claim 1 or 2, wherein, The content of the benzotriazole compound is more than 0.1% by mass and less than 1.0% by mass relative to the total mass of the cleaning agent composition.

43. The cleaning agent composition according to claim 1 or 2, wherein, The content of the benzotriazole compound is more than 0.3% by mass and less than 1.0% by mass relative to the total mass of the cleaning agent composition.

44. The cleaning agent composition according to claim 1 or 2, wherein, The carboxylic acid chelating agent contains amino acid compounds.

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

46. ​​The cleaning agent composition according to claim 1 or 2, wherein, The content of the chelating agent is 0.05% by mass or more and 5% by mass or less relative 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 also contains water. The water content is 70% by mass or more and 99% by mass or less relative to the total mass of the cleaning agent composition.

48. The cleaning agent composition according to claim 1 or 2, wherein, The cleaning agent composition also contains water. The water content is 70% by mass or more and 95% by mass or less relative to the total mass of the cleaning agent composition.

49. The cleaning agent composition according to claim 1 or 2, wherein, The mass ratio of the hydroxylamine compound content to the benzotriazole compound content is 0.6 or more and 60 or less.

50. The cleaning agent composition according to claim 1 or 2, wherein, The mass ratio of the hydroxylamine compound content to the chelating agent content is 0.3 or more and 30 or less.

51. The cleaning agent composition according to claim 1 or 2, wherein, The mass ratio of the hydroxylamine compound content to the chelating agent content is 6 or more and 60 or less.

52. The cleaning agent composition according to claim 1 or 2, wherein, The pH of the cleaning agent composition is above 7.0 and below 10.0.

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