Post-CMP cleaning composition

Abstract

To provide a composition of post cleaning agent for the CMP process that excels in removing and inhibiting the adhesion of metal and organic residues that remain on the planarized polished surface, and also excels in inhibiting corrosion.SOLUTION: A composition post cleaning agent for the CMP process in semiconductor manufacturing processes, contains (A) a nonionic surfactant containing an alkylene oxide adduct of an alcohol having a carbon number of 6 or more, (B) aliphatic amines, and (C) at least one corrosion inhibitor selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cleaning composition for use after a CMP step in a semiconductor manufacturing process, more particularly to a cleaning composition for use after a CMP step that is excellent in removing metal residues and organic residues, inhibiting adhesion of the residues, and inhibiting corrosion. [Background technology]

[0002] CMP (Chemical-Mechanical-Planarization / Polishing) is a type of wafer surface planarization technology used in the semiconductor manufacturing process. It uses chemical abrasives and polishing pads to remove unevenness on the wafer surface and flatten it with a combined chemical and mechanical polishing action. Metal residues from abrasive grains and polishing debris remain on the flattened wafer surface after polishing. In addition, because the wafer surface has high metal activity and is prone to corrosion (oxidation), a protective film is formed using an anticorrosive agent, and the components of this protective film may remain as organic residues after polishing. These residues have a negative effect on the electrical properties of semiconductors, so post-CMP cleaning is performed to remove the residues.

[0003] Post-CMP cleaning is usually performed by combining chemical cleaning using a cleaning agent with physical cleaning using a brush, etc. As the above-mentioned cleaning agent, a cleaning agent composition containing a main component, a chelating agent, a surfactant, etc. is usually used.

[0004] Post-CMP cleaning compositions have been widely studied (Patent Documents 1 to 6). For example, Patent Document 1 describes a working fluid that contains water, a pH buffer containing a basic pH adjuster and an acidic complexing agent, and a surfactant, and has a pH of 7 to 12, which is useful for modifying a wafer surface. Patent Document 2 describes a cleaning agent for substrates having metal wiring, which contains a carboxylic acid having a nitrogen-containing heterocycle and an alkylhydroxylamine, and comprises an aqueous solution having a pH of 10 or higher. Furthermore, for example, Patent Document 3 describes a cleaning composition that contains one or more basic compounds and one or more nitrogen-containing heterocyclic monocyclic aromatic compounds and has a hydrogen ion concentration (pH) of 8 to 11, and Patent Document 4 describes a cleaning solution for semiconductor device substrates that contains a compound having an amine group and a carboxyl group, adenine, purine, uric acid, derivatives thereof, a pH adjuster, and water. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2010-537404 [Patent Document 2] International Publication No. 2014 / 168166 [Patent Document 3] JP 2014-212262 A [Patent Document 4] JP 2016-86094 A [Patent Document 5] JP 2012-216690 A [Patent Document 6] JP 2018-107353 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, conventional post-CMP cleaning compositions are still insufficient in removing or preventing adhesion of metal residues, such as abrasive grains or polishing debris derived from abrasives, and organic residues derived from anticorrosives, present on the wafer surface after the CMP process, leaving room for improvement. In addition, semiconductor wafers have deposited layers, such as metal films and insulating films, which serve as wiring, formed on the substrate, and various metal materials are used for these, and it is necessary for the composition to exhibit excellent corrosion inhibition function for all of these materials.

[0007] In particular, in recent years, as semiconductor logic devices have become increasingly highly integrated due to the advancement of miniaturization, the metal deposition layer formed on the wafer surface is expected to use cobalt as well as conventional aluminum and copper. Since a higher degree of planarity is required in the CMP process, polishing abrasives with smaller particle size and higher sphericality than conventional ones are adopted, and the influence of the Vanderwaals force and electrostatic interaction on the polishing substrate becomes greater, making it difficult to completely wash off the abrasives with conventional cleaning solutions. In addition, since the polishing residue generated after the CMP process becomes a complex of an organic rust inhibitor present as a protective layer on the outermost surface of the metal deposition layer and transition metal ions such as cobalt ions, a new cleaning mechanism is required. In addition, the adoption of new metal films has created a new problem that metal corrosion is caused when conventional post-CMP cleaning solutions are used at the metal multilayer film interface. Thus, there has been a demand for a post-CMP cleaning agent composition that can solve not only the CMP processing characteristics but also these problems at the same time.

[0008] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a cleaning composition for use after a CMP process that is excellent in removing metal residues and organic residues remaining on a planarized polished surface, inhibiting their adhesion, and also inhibiting corrosion. [Means for solving the problem]

[0009] In order to solve the above problems, the present inventors have conducted extensive research into post-CMP cleaning compositions and have found that a combination of a specific nonionic surfactant, an aliphatic amine, and a specific corrosion inhibitor significantly improves the removal of metal and organic residues and inhibits adhesion, and also provides excellent corrosion inhibition, thereby completing the present invention.

[0010] That is, the present invention provides a cleaning agent composition for use after a CMP step in a semiconductor manufacturing process, comprising: (A) a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms; (B) an aliphatic amine; and (C) at least one corrosion inhibitor selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds.

[0011] The aliphatic amines preferably have a molecular weight of 2000 or less.

[0012] The aliphatic amines preferably include an amine compound represented by the following general formula (1) and / or a polyalkyleneimine.

[0013] [ka]

[0014] (In formula (1), R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom, an alkyl group, or -R 4 -(NH-R 5 ) n -NH2. R 4 and R 5 are the same or different and represent an alkylene group having 1 to 6 carbon atoms. n represents an integer of 0 to 100.

[0015] The nitrogen-containing heterocyclic compound preferably contains at least one selected from the group consisting of pyrrole, pyridine, triazole, triazine, purine, and derivatives thereof.

[0016] The carboxylate compound preferably includes a fatty acid salt.

[0017] The post-CMP cleaning composition is preferably used for cleaning a wafer surface on which a cobalt-containing compound is exposed. Effect of the Invention

[0018] The post-CMP cleaning composition of the present invention has the above-mentioned constitution, and therefore is excellent in removing metal residues and organic residues from the wafer surface and inhibiting their adhesion, and is also excellent in inhibiting corrosion. The post-CMP cleaning composition of the present invention can be suitably used as a post-CMP cleaning composition in the semiconductor manufacturing process.

Brief Description of the Drawings

[0019] [Figure 1] It is an AFM observation image of the surface of the substrate for cleaning evaluation when evaluating the cleaning performance of the cleaning composition.

Modes for Carrying Out the Invention

[0020] The present invention will be described in detail below. In addition, a combination of two or more of the individual preferred forms of the present invention described below is also a preferred form of the present invention.

[0021] <Post-Cleaning Agent Composition for CMP Process> The present invention relates to a post-cleaning agent composition for a CMP process in a semiconductor manufacturing process, which comprises (A) a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms, (B) aliphatic amines, and (C) at least one corrosion inhibitor selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds. The post-cleaning agent composition for the CMP process of the present invention contains three specific components, and thus is excellent in removing and suppressing the adhesion of metal residues and organic residues, and is also excellent in corrosion inhibition. The reason why the post-cleaning agent composition for the CMP process of the present invention is excellent in removing and suppressing the adhesion of metal residues and organic residues and is also excellent in corrosion inhibition is that the nonionic surfactant contained in the post-cleaning agent composition for the CMP process of the present invention penetrates into the surface of the substrate and the interface of abrasive grain residues and dirt and floats up in the water which is the main component of the cleaning liquid, and the high coordination ability of the aliphatic amines to heavy metal ions reduces the adsorption force of the polishing residues to the fresh metal surface exposed in the CMP process. In addition, it is presumed that the nitrogen-containing heterocyclic compound and the carboxylate compound adsorb on the surface of the metal deposition film, so that the electrochemical interaction between the chemical components coexisting in the cleaning agent composition is in an equilibrium state, and the corrosion potential and corrosion current value of the metal species constituting the metal deposition film can be reduced.

[0022] The components contained in the post-cleaning agent composition for the CMP process of the present invention will be described. (A) Nonionic surfactant The post-CMP cleaning composition of the present invention contains a nonionic surfactant (hereinafter also referred to as "component (A)") that contains an alkylene oxide adduct of an alcohol having 6 or more carbon atoms. By containing the nonionic surfactant, the composition can penetrate into the interface between the substrate surface and the abrasive grain residue or dirt, and can stably maintain the state in which the residue, etc. is floated in the water, which is the main component of the cleaning solution. Ionic surfactants such as cationic or anionic surfactants are ionic and have a significant tendency to adsorb to the cleaned substrate due to electrostatic interaction, and therefore tend to remain on the surface of the substrate cleaned after the CMP process and may become contaminants in the final product. On the other hand, nonionic surfactants have a small electrostatic interaction due to their lack of ionicity, and therefore can be easily removed by rinsing with pure water even if they are adsorbed to the surface of the substrate cleaned after the CMP process. For this reason, nonionic surfactants are used in the present invention.

[0023] Examples of nonionic surfactants include known nonionic surfactants such as polyhydric alcohol type surfactants in which a polyhydric alcohol and a fatty acid are ester-bonded, and ether type surfactants in which an alkylene oxide is added to a compound having a hydroxyl group, such as a higher alcohol, an alkylphenol, or propylene glycol. The present invention includes at least a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms. The alkylene oxide adduct of an alcohol having 6 or more carbon atoms is a compound in which an alkylene oxide is added to an alcohol having 6 or more carbon atoms.

[0024] Examples of the alcohol having 6 or more carbon atoms include alkyl alcohols such as hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, 1,2-hexanediol, 1,6-hexanediol, and 1,10-decanediol; cycloalkyl alcohols such as cyclohexyl alcohol, cycloheptyl alcohol, 1,4-cyclohexanedimethanol, and 1,4-cyclohexanediol; allyl alcohol; and alkylphenyl alcohols such as octylphenol and nonylphenol. Among these, alkyl alcohols are preferred from the viewpoint of ease of adjusting the hydrophobicity by the structure or the addition position and from the viewpoint of environmental hazards. The alkyl alcohol may be either linear or branched.

[0025] The alcohol preferably has 10 or more carbon atoms, preferably 20 or less, and more preferably 18 or less carbon atoms. Moreover, the alcohol having 6 or more carbon atoms is preferably a secondary or tertiary alcohol, more preferably a secondary alcohol, in that it can achieve both high penetration into the solid residue interface and metal corrosion inhibition performance. The alcohol having 6 or more carbon atoms may be monohydric, dihydric or polyhydric, but from the standpoint of ease of production and cost, monohydric alcohols are preferred.

[0026] Examples of the alkylene oxide to be added to the alcohol having 6 or more carbon atoms include ethylene oxide, propylene oxide, butylene oxide, etc., and among these, at least one selected from the group consisting of ethylene oxide and propylene oxide is preferred, and a mixture of ethylene oxide and propylene oxide is more preferred.

[0027] Examples of the alkylene oxide adducts of alcohols having 6 or more carbon atoms include primary alcohol ethoxylates, secondary alcohol ethoxylates, tertiary alcohol ethoxylates, octylphenyl ethoxylate, nonylphenyl ethoxylate, benzylphenyl ethoxylate, acetylenic primary alcohol ethoxylates, acetylenic primary dialcohol ethoxylates, acetylenic secondary alcohol ethoxylates, acetylenic secondary dialcohol ethoxylates, acetylenic tertiary alcohol ethoxylates, and acetylenic tertiary dialcohol ethoxylates. The ethoxylates include those having at least ethylene oxide (EO) added thereto, and also those having ethylene oxide (EO) and other alkylene oxides (eg, propylene oxide (PO)) added thereto.

[0028] The alkylene oxide adduct of the alcohol having 6 or more carbon atoms preferably has a cloud point of 25° C. or higher, and more preferably has a cloud point of 40° C. or higher, in that it can form a homogeneous solution without separation in the cleaning composition. The cloud point can be determined by a method in which a 1% aqueous solution of the nonionic surfactant is cooled while stirring and temperature monitoring, and the temperature at which the solution becomes transparent is observed with the naked eye.

[0029] Specific examples of the nonionic surfactant include polyalkylene oxide alkyl ether surfactants, block polymers consisting of polyethylene oxide and polypropylene oxide, polyalkylene oxide alkyl phenyl ether surfactants, polyoxyalkylene distyrene-type phenyl ether surfactants, polyalkylene tribenzyl phenyl ether surfactants, and acetylene polyalkylene oxide surfactants. Among these, polyalkylene oxide alkyl ether surfactants and block polymer surfactants consisting of polyethylene oxide and polypropylene oxide are preferred from the viewpoint of being able to inhibit corrosion of metal laminate films caused by the cleaning composition.

[0030] Specifically, the nonionic surfactant is preferably a compound represented by the following general formula (2) or (3).

[0031] [ka]

[0032] (In formula (2), R 6 , R 7 and R 8 R may be the same or different and represents a hydrogen atom or an alkyl group. 9 and R 10 are the same or different and represent an alkylene group. x and y are the same or different and represent an integer of 0 to 50. (x+y) is an integer of 1 or greater. In formula (3), R 11 , R 12 , R 13 and R 14 R may be the same or different and represents a hydrogen atom or an alkyl group. 15 , R 16 , R 17 , R 18 and R 19 are the same or different and each represents an alkylene group or an alkynylene group. x and y are the same or different and each represents an integer of 0 to 50. (x+y) is an integer of 1 or more.)

[0033] In the above general formula (2), R 6 , R 7 and R 8 The alkyl group represented by the formula (I) may be linear or branched. The alkyl group preferably has 1-20 carbon atoms, more preferably 1-18 carbon atoms, and further preferably 1-16 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a heptyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 3-ethylpentyl group, and straight-chain or branched alkyl groups such as a 2,2,3-trimethylbutyl group, octyl group, methylheptyl group, dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-tetramethylbutyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group.

[0034] In the above general formula (2), R 6 , R 7 and R 8 It is preferred that two or more of the groups are alkyl groups.

[0035] In the above general formula (2), R 6 , R 7 and R 8 The total number of carbon atoms is preferably 5 to 19, more preferably 7 to 17, further preferably 9 to 15, and most preferably 11 to 13.

[0036] In the above general formula (2), R 9 and R 10 The alkylene group represented by the formula (I) may be linear or branched. Examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, a 2-propylene group, an n-butylene group, a pentamethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1,4-dimethylbutylene group, etc. Among these, an alkylene group having 2 or 3 carbon atoms is preferred in terms of ease of production and ability to control hydrophilicity and hydrophobicity.

[0037] In the above general formula (2), -(R 9 O) x (R 10 O) y H is favored because it is easy to manufacture and its hydrophilicity and hydrophobicity can be controlled. x H, -(CH2CH2O) x (CH2CH(CH3)O) y H is preferred, -(CH2CH2O) x (CH2CH(CH3)O) y H is more preferred.

[0038] In the above general formula (2), x and y are the same or different and are an integer of 0 to 50, preferably an integer of 0 to 30, more preferably an integer of 0 to 24, and even more preferably an integer of 0 to 16. x is an alkylene oxide (R 9 represents the average number of moles of alkylene oxide (R 10 O). x and y may be the same or different in any alkylene oxide. x is preferably an integer of 1 to 20, more preferably an integer of 3 to 18, and further preferably an integer of 5 to 16. y is preferably an integer of 0 to 20, more preferably an integer of 0 to 15, and further preferably an integer of 1 to 10. (x+y) is an integer greater than or equal to 1. That is, at least one of x and y is an integer greater than or equal to 1. (x+y) is preferably an integer of 1-50, and more preferably an integer of 3-30.

[0039] In the above general formula (3), R 11 , R 12 , R 13 and R 14 The alkyl group represented by the above formula is 6 , R 7 and R 8 The alkyl group may be the same as the alkyl group represented by the following formula: Among these, the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, or an iso-butyl group, since this results in a compact molecular structure and allows for high permeability to be exhibited.

[0040] In the above general formula (3), R 15 , R 16 , R 17 and R 18 is preferably an alkylene group, and the alkylene group is preferably an alkylene group such as those described above for R 9 and R 10 Among them, the alkylene group represented by R 15 , R 16 , R 17 and R 18 is more preferably an alkylene group having 2 or 3 carbon atoms. Also, R 19 is preferably an alkynylene group, more preferably an ethynylene group (-C≡C-), a propynylene group (-C≡C-CH2-), a 1-butynylene group (-C≡C-CH2-CH2-), or a 2-butynylene group (-CH2-C≡C-CH2-), further preferably an alkynylene group having 2 or 3 carbon atoms, and most preferably an alkynylene group having 2 carbon atoms.

[0041] In the above general formula (3), -(R 15 O) x (R 16 O) y -H and -(R 17 O)x (R 18 O) y -H is the above-mentioned -(R 9 O) x (R 10 O) y Preferred examples of the groups are the same as those of H.

[0042] In the above general formula (3), x and y are the same or different and are an integer of 0 to 50, preferably an integer of 0 to 20, more preferably an integer of 0 to 15, and even more preferably an integer of 0 to 10. x is an alkylene oxide (R 15 O), (R 17 represents the average number of moles of alkylene oxide (R 16 O), (R 18 O). x and y may be the same or different in any alkylene oxide. x is preferably an integer of 1-20, more preferably an integer of 1-12, and further preferably an integer of 2-8. y is preferably an integer of 0 to 20, more preferably an integer of 0 to 10, and further preferably an integer of 0 to 5. (x+y) is an integer greater than or equal to 1. That is, at least one of x and y is an integer greater than or equal to 1. (x+y) is preferably an integer of 1-50, and more preferably an integer of 3-30.

[0043] The nonionic surfactants may be used alone or in combination of two or more kinds.

[0044] The content of the nonionic surfactant (component (A)) is preferably 0.5 to 65 mass%, more preferably 1 to 60 mass%, and even more preferably 2 to 55 mass%, relative to 100 mass% of the active ingredients in the post-CMP process cleaning composition. In this specification, the term "active ingredient" refers to all ingredients in the post-CMP cleaning composition other than the solvent.

[0045] The content of the nonionic surfactant (component (A)) is preferably 0.001 to 5 mass%, more preferably 0.005 to 2 mass%, and even more preferably 0.01 to 1 mass%, relative to 100 mass% of the post-CMP process cleaning agent composition.

[0046] (B) Aliphatic amines The post-CMP cleaning composition contains an aliphatic amine (hereinafter also referred to as "component (B)"). By containing an aliphatic amine, the aliphatic amine has a high coordination ability with heavy metal ions, and therefore the adsorptivity of polishing residues to fresh metal surfaces exposed in the CMP process can be reduced.

[0047] The aliphatic amines include primary aliphatic amines, secondary aliphatic amines, and tertiary aliphatic amines.

[0048] The aliphatic amines preferably include an amine compound represented by the following general formula (1) and / or a polyalkyleneimine.

[0049] [ka]

[0050] (In formula (1), R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom, an alkyl group, or -R 4 -(NH-R 5 ) n -NH2. R 4 and R 5 are the same or different and represent an alkylene group having 1 to 6 carbon atoms. n represents an integer of 0 to 100.

[0051] In the above general formula (1), R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom, an alkyl group, or -R 4 -(NH-R5 ) n -NH2. R 1 , R 2 and R 3 The number of carbon atoms in the alkyl group represented by the following formula (I) is preferably 1 to 6, more preferably 1 to 5, and even more preferably 1 to 4, in terms of water solubility.

[0052] R 1 , R 2 and R 3 Represented by -R 4 -(NH-R 5 ) n In -NH2, R 4 and R 5 are the same or different and represent an alkylene group having 1 to 6 carbon atoms. In addition, n represents an integer of 0 to 100. n is -(NH-R 5 )-, preferably an integer of 0 to 50, more preferably an integer of 0 to 30, further preferably an integer of 0 to 20, and particularly preferably an integer of 0 to 10.

[0053] Specific examples of the compound represented by the general formula (1) include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, diethylenetriamine, N-ethylbutylamine, 1,2-bis-(3-aminopropylamino)ethane, tributylamine, 3-(diethylamino)propylamine, triethylenetetramine, tetraethylenepentamine, etc. Among these, at least one selected from the group consisting of ethylenediamine, diethylenetriamine, N-ethylbutylamine, 3-(diethylamino)propylamine, and 1,2-bis-(3-aminopropylamino)ethane is preferred in terms of low toxicity.

[0054] Examples of the polyalkyleneimine include polyethyleneimine, polypropyleneimine, polybutyleneimine, and polypentyleneimine. The polyalkyleneimine may be linear or branched, with the branched one being preferred from the viewpoint of ease of production.

[0055] The molecular weight of the aliphatic amines is preferably 2000 or less. When the molecular weight is 2000 or less, the viscosity of the post-CMP cleaning composition becomes suitable. The molecular weight of the aliphatic amines is more preferably 300 or less, further preferably 250 or less, and further more preferably 220 or less. The molecular weight of the above aliphatic amines is preferably 50 or more in view of their low boiling point.

[0056] The above aliphatic amines may be used alone or in combination of two or more kinds.

[0057] The content of the aliphatic amines (component (B)) is preferably 30 to 95 mass%, more preferably 35 to 93 mass%, and even more preferably 40 to 90 mass%, relative to 100 mass% of the active ingredients in the post-CMP process cleaning composition.

[0058] The content of the aliphatic amines (component (B)) is preferably 0.01 to 5 mass %, more preferably 0.05 to 2 mass %, and even more preferably 0.1 to 1 mass %, relative to 100 mass % of the post-CMP process cleaning agent composition.

[0059] (C) Corrosion inhibitors The post-CMP cleaning composition contains a corrosion inhibitor (hereinafter also referred to as "component (C)"), and the corrosion inhibitor contains at least one selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds.

[0060] (C1) Nitrogen-containing heterocyclic compound The nitrogen-containing heterocyclic compound is not particularly limited as long as it is a compound having a heterocycle having at least one nitrogen atom, and may contain a heteroatom other than a nitrogen atom, such as an oxygen atom, a sulfur atom, etc. The nitrogen-containing heterocycle may be saturated or unsaturated, but is preferably a nitrogen-containing unsaturated heterocycle in terms of its high adsorption performance to a transition metal film. The nitrogen-containing heterocyclic compound may be a heteromonocyclic compound or a condensed heterocyclic compound.

[0061] Examples of the heteromonocyclic compound include five-membered ring compounds such as pyrrole, pyrazoline, pyrazole, imidazole, triazole, imidazoline, oxazoline, oxazole, and isoxazole; six-membered ring compounds such as piperidine, pyridine, pyrazine, piperazine, pyrimidine, pyridazine, triazine, and morpholine; and derivatives thereof. Examples of the derivative include compounds in which at least one atom in the nitrogen-containing heterocycle is substituted with an alkyl group, an aryl group, an amino group, a carboxyl group, a hydroxyl group, a ketone group, or a combination of these groups.

[0062] Specific examples of the heteromonocyclic compound include 1H-pyrrole, 1-pyrroline, 2-pyrroline, 3-pyrroline, pyrrolidine, pyrrolidone, γ-butyrolactam, γ-valerolactam, proline, prolyl, 1H-pyrazole, 1-pyrazoline, 2-pyrazoline, pyrazolidine, pyrarizolidone, 3-pyrazolone, 4-pyrazolone, 5-pyrazolone, 1H-pyrazole-4-carboxylic acid, ethyl pyrazole-4-carboxylate, 1-methyl-1H-pyrazole-5-carboxylic acid, 5-methyl-1H-pyrazole- 3-Carboxylic acid, 3,5-pyrazoledicarboxylic acid, 3-amino-5-hydroxypyrazole, 1H-imidazole, 2-imidazoline, 3-imidazoline, 4-imidazoline, imidazolidine, imidazolidone, ethyleneurea, hydantoin, allantoin, histidine, histidyl, histamine, 1,2,3-triazole, 1,2,4-triazole, 1-hydroxybenzotriazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3,5-diamino-1,2,4 -Triazole, piperidine, piperidyl, piperidylidene, piperidylene, piperidone, pipecolic acid, pipecoloyl, pipecolamide, nipecotic acid, isonipecotoyl, isonipecotamide, pelletierine, isopelletierine, piperine, isopiperine, chavicine, isochavicin, pyridine, pyridyl, pyridylidene, pyridylene, pyridylene, 2-pyridone, 4-pyridone, picoline, α-collidine, β-collidine, γ-collidine, picoline, nicotinic acid, nicotinamide, isonicotinic acid, isoni Examples of such compounds include cocinoyl, citrazinic acid, quinolinic acid, lutidic acid, isocinchomeronic acid, dipicolinic acid, cinchomeronic acid, dinicotinic acid, berberonic acid, fusaric acid, ethionamide, nicotine, cotinine, anabasine, anatabine, homarine, aminohydroxypyrazole, dihydroxypyridine, pyrazine, pyrazinoyl, pyrazinamide, piperazine, pyrimidine, cytosine, uracil, thymine, orotic acid, uramyl, thiamine, pyritazine, maleic hydrazide, melamine, and cyanuric acid.

[0063] Examples of the condensed heterocyclic compound include indole, isoindole, benzimidazole, benzotriazole, triazine, quinoline, isoquinoline, quinazoline, purine, cinnoline, phthalazine, quinoxaline, acridine, phenanthridine, and derivatives thereof.

[0064] Specific examples of the condensed heterocyclic compound include benzotriazole and uric acid.

[0065] Among these, the nitrogen-containing heterocyclic compound preferably contains at least one selected from the group consisting of pyrrole, pyridine, triazole, triazine, purine, and derivatives thereof, in terms of high adsorption performance for transition metal films, more preferably uric acid, nicotinic acid, triazole, or melamine, and even more preferably uric acid. The nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.

[0066] (C2) Carboxylate compounds The carboxylate compound is not particularly limited as long as it is a salt of a compound having a carboxy group, but is preferably a fatty acid salt. The fatty acid salt may be a salt of either a saturated fatty acid or an unsaturated fatty acid. The number of carbon atoms in the fatty acid salt is preferably 6 to 50, more preferably 8 to 40, even more preferably 10 to 30, and most preferably 14 to 24, from the viewpoint of improving the corrosion resistance of the adsorbed metal film.

[0067] Specific examples of the fatty acid salt include salts of saturated fatty acids such as butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, and arachidic acid; and salts of unsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, eicosenoic acid, linoleic acid, and linolenic acid. Among them, the fatty acid salt is preferably a salt of at least one fatty acid selected from the group consisting of capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, myristoleic acid, palmitoleic acid, oleic acid, eicosenoic acid, linoleic acid, and linolenic acid, in terms of improving the corrosion resistance of the adsorbed metal film.

[0068] Examples of the salt include alkali metal salts such as potassium salts and cesium salts, alkaline earth metal salts such as magnesium salts, calcium salts, strontium salts and barium salts, ammonium salts, quaternary ammonium salts, and organic amine salts such as alkylamine salts and alkanolamine salts. Among these, the salts are preferably alkali metal salts, ammonium salts, quaternary ammonium salts and organic amine salts, more preferably alkali metal salts and ammonium salts, and further preferably potassium salts and ammonium salts.

[0069] Among these, from the viewpoint of improving corrosion resistance by a balance between polar groups and hydrophobic groups, the above-mentioned carboxylate compound is preferably a palmitate, a stearate, an arachidate, a palmitoleate, an oleate, or an eicosenoate, more preferably an alkali metal salt or ammonium salt of palmitic acid, stearic acid, arachidic acid, palmitoleic acid, oleic acid, or eicosenoic acid, even more preferably an alkali metal salt of oleic acid, and particularly preferably potassium oleate.

[0070] The above carboxylate compounds may be used alone or in combination of two or more.

[0071] The post-CMP cleaning composition of the present invention may further contain other corrosion inhibitors in addition to the nitrogen-containing heterocyclic compound and the carboxylate compound. Examples of the other corrosion inhibitors include known corrosion inhibitors such as rust inhibitors and anticorrosive agents. Specific examples of the corrosion inhibitor include oxidation coating type corrosion inhibitors such as chromates, molybdates, tungstates, and nitrites; precipitation coating type corrosion inhibitors such as polymerized phosphates, zinc salts, and sulfur-containing organic compounds; and adsorption coating type corrosion inhibitors such as alkanolamines, alkyleneamine ethylene oxide adducts, alkyl phosphate ester salts, and various surfactants.

[0072] The total content of the nitrogen-containing heterocyclic compound (C1) and the carboxylate compound (C2) in the corrosion inhibitor is preferably 50 mass% or more, more preferably 55 mass% or more, even more preferably 60 mass% or more, and particularly preferably 100 mass%, based on 100 mass% of the total amount of the corrosion inhibitor.

[0073] The content ratio of the nitrogen-containing heterocyclic compound (C1) to the carboxylate compound (C2) [(C1) / (C2)], in terms of mass ratio, is preferably 0 / 100 to 100 / 0, and either compound may be used alone or they may be mixed in any ratio.

[0074] The content of the corrosion inhibitor (component (C)) is preferably 0.2 to 35 mass%, more preferably 0.5 to 30 mass%, and even more preferably 1 to 25 mass%, relative to 100 mass% of the active ingredients in the post-CMP process cleaning composition.

[0075] The content of the corrosion inhibitor (component (C)) is preferably 0.001 to 3 mass %, more preferably 0.003 to 2 mass %, and even more preferably 0.005 to 1 mass %, relative to 100 mass % of the post-CMP process cleaning agent composition.

[0076] (D) Other ingredients The post-CMP cleaning composition of the present invention may contain an optional component (D) in addition to the above-mentioned components (A), (B), and (C). Examples of the component (D) include a pH adjuster, a chelating agent, a solvent, a surfactant, and the like.

[0077] The pH adjuster is not particularly limited as long as it is a component capable of adjusting the pH to the desired level, and examples thereof include acid compounds and alkaline compounds. Examples of the acid compound include inorganic acids such as sulfuric acid and nitric acid and their salts, and organic acids such as acetic acid and lactic acid and their salts. Examples of the alkaline compound include alkali metal hydroxides such as potassium hydroxide and cesium hydroxide; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and monoisopropanolamine; and quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethyl-2-hydroxyethylammonium (choline) hydroxide, and triethyl(hydroxyethyl)ammonium hydroxide.

[0078] Examples of the chelating agent include oxalic acid, citric acid, tartaric acid, malic acid, picolinic acid, glycine, etc. Also included are phosphonic acid-based chelating agents such as N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid), glycine-N,N-bis(methylenephosphonic acid), and nitrilotris(methylenephosphonic acid).

[0079] Examples of the solvent include water, aprotic polar organic solvents such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, and dimethylsulfoxide, and protic organic solvents such as lower alcohols, aromatic alcohols, and glycols. Of these, the solvent preferably contains water. The solvent may be a mixture containing two or more kinds of solvents.

[0080] The surfactant may be anionic surfactants or cationic surfactants other than the nonionic surfactants mentioned above. Examples of the anionic surfactant include carboxylate-type anionic surfactants such as aliphatic monocarboxylates, polyoxyethylene alkyl ether carboxylates, N-acylsarcosine salts, and N-acylglutamates; sulfonate-type anionic surfactants such as dialkyl sulfosuccinates, alkanesulfonates, alpha-olefin sulfonates, alkylbenzene sulfonates, naphthalene sulfonate-formaldehyde condensates, alkylnaphthalene sulfonates, and N-methyl-N-acyltaurate salts; sulfate ester-type anionic surfactants such as alkyl sulfates, polyoxyethylene alkyl ether sulfates, and fat sulfate esters; and phosphate ester-type anionic surfactants such as alkyl phosphates, polyoxyethylene alkyl ether phosphates, and polyoxyethylene alkyl phenyl ether phosphates.

[0081] Examples of the cationic surfactant include alkylamine salt-type cationic surfactants such as monoalkylamine salts, dialkylamine salts, and trialkylamine salts; and quaternary ammonium salt-type cationic surfactants such as dialkyldimethylammonium chloride, dialkyldimethylammonium bromide, dialkyldimethylammonium iodide, alkyltrimethylammonium chloride, alkyltrimethylammonium bromide, alkyltrimethylammonium iodide, and alkylbenzyldimethylammonium chloride.

[0082] The post-CMP cleaning composition is preferably an aqueous solution having a pH (hydrogen ion concentration) of 7.5 or more at 25° C. When the pH of the post-CMP cleaning composition is within the above-mentioned range, the corrosion rate of the metal film can be suppressed even if the cleaning solution does not contain a predetermined amount of an active ingredient. The pH (25° C.) of the post-CMP cleaning composition is more preferably 8.0 or higher, and even more preferably 8.5 or higher. The pH of the post-CMP cleaning composition can be adjusted by adjusting the content of the alkaline compound. The pH can be determined using a pH meter (for example, F71S, manufactured by Horiba, Ltd.).

[0083] The post-CMP cleaning composition has a corrosion current value of 10 μA / cm 2 It is preferable that the corrosion current value and the corrosion potential difference of the dissimilar metal interface are not more than 40 mV. When the corrosion current value and the corrosion potential difference are within the above ranges, corrosion of the substrate to be cleaned can be suppressed. The post-CMP cleaning composition has a corrosion current value of 5 μA / cm 2 More preferably, the corrosion potential difference at the interface between different metals is 30 mV or less, and the corrosion current value is 3 μA / cm 2 It is more preferable that the corrosion potential difference at the interface between different metals is 25 mV or less, and the corrosion current value is 1 μA / cm 2 It is particularly preferable that the corrosion potential difference at the interface between the different metals is 20 mV or less. In this specification, the above-mentioned corrosion current value and corrosion potential difference can be determined by measurement according to the method described in the examples described later.

[0084] <Preparation method> The post-CMP cleaning composition can be prepared by mixing the above-mentioned components (A), (B), (C), and, if necessary, the component (D). The mixing can be carried out by any known mixing / dispersing means, such as a stirrer, mixer, or disperser, without particular limitation.

[0085] <How to use> The post-CMP cleaning composition of the present invention is used in a post-CMP cleaning step in a semiconductor manufacturing process. More specifically, the post-CMP cleaning composition of the present invention is preferably used in a step of cleaning a semiconductor substrate (wafer) after a CMP step in a semiconductor manufacturing process. The post-CMP cleaning method using the post-CMP cleaning composition of the present invention preferably includes a step of cleaning the surface of a semiconductor substrate after CMP with the post-CMP cleaning composition.

[0086] Examples of the semiconductor substrate include substrates made of silicon, silicon carbide, silicon nitride, gallium arsenide, gallium nitride, gallium phosphide, indium phosphide, or the like.

[0087] The semiconductor substrate may be provided with metal wiring, and examples of the metal wiring include copper wiring, tungsten wiring, aluminum wiring, cobalt wiring, and alloy wiring of these metals with other metals, etc. Examples of the other metals include metals such as tungsten, titanium, tantalum, and chromium.

[0088] The semiconductor substrate may be anticorrosive. Examples of the anticorrosive treatment include a method of treating the surface of the semiconductor substrate with an anticorrosive agent. Examples of the anticorrosive agent include compounds known as anticorrosive agents, such as benzotriazoles, imidazoles, quinaldines, and quinolines. Examples of the treatment method include a known method of applying an anticorrosive agent to the surface of the semiconductor substrate and drying or heating the applied agent to form a coating (protective film).

[0089] The semiconductor substrate may include an insulating film, such as a p-TEOS thermal oxide film, silicon nitride (SiN), silicon carbide nitride (SiCN), a low-k dielectric film (SiOC, SiC), or cobalt silicide (CoSi2). The semiconductor substrate may include a barrier metal (Ta, TaN, TiN, etc.).

[0090] After the CMP process, polishing debris and organic residues from the metal wiring, protective film, insulating film, and the like remain on the surface of the semiconductor substrate.

[0091] Furthermore, the chemical polishing agent used in the CMP process may remain on the semiconductor substrate after the CMP process. The chemical polishing agent is a slurry of abrasive grains, and the abrasive grains include metal oxides such as CeO2, Fe2O3, SnO2, MnO, and SiO2. Therefore, the residue of these metal oxides may remain on the surface of the semiconductor substrate after the CMP process. The CMP step can be carried out by a known method.

[0092] The post-CMP cleaning composition of the present invention is preferably used for cleaning the surface of a semiconductor substrate (wafer) after the CMP process on which the above-mentioned metal residues and organic residues exist. By cleaning the surface of a semiconductor substrate on which such residues exist using the post-CMP cleaning composition of the present invention, the above residues can be removed. In addition, the above residues can be prevented from reattaching to the surface of the semiconductor substrate. Furthermore, the surface of the semiconductor substrate can be inhibited from corroding.

[0093] As described above, the post-CMP cleaning composition of the present invention can be suitably used for cleaning semiconductor substrates after the CMP process in which the above-mentioned metal residues and organic residues are present, and in particular, can be suitably used for cleaning a wafer surface on which a compound containing cobalt is exposed, and can be more suitably used for cleaning a wafer surface on which a compound containing cobalt alone, or cobalt and at least one metal selected from the group consisting of titanium, tantalum, and silicon, is exposed.

[0094] The method for cleaning the wafer surface after CMP using the post-CMP cleaning composition of the present invention is not particularly limited and may be a known method, for example, a method of immersing the wafer after the CMP process in the post-CMP cleaning composition for cleaning, a spin-type or spray-type cleaning method, etc. Also, a batch-type method in which a plurality of substrates are treated at once, or a single-wafer method in which substrates are treated one by one may be used.

[0095] In the method for cleaning a wafer surface using the post-CMP cleaning composition of the present invention, the cleaning time is not particularly limited and may be a usual one. From the viewpoint of efficiency, the cleaning time is, for example, 10 to 300 seconds, and preferably 15 to 250 seconds. The temperature of the post-CMP cleaning composition is not particularly limited, but is, for example, 5 to 80°C, and preferably 10 to 70°C. EXAMPLES

[0096] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0097] Examples 1 to 5, Comparative Examples 1 to 3 <Preparation of cleaning composition> A nonionic surfactant, an aliphatic amine, a nitrogen-containing heterocyclic compound, a carboxylate compound, and other additives were mixed into water according to the formulation shown in Table 1, and then potassium hydroxide was added to adjust the pH (25°C) to 11, thereby preparing the cleaning compositions of the Examples and Comparative Examples. In addition, the "ratio" in the table indicates the mass proportion of each component in the active ingredients (all components other than water).

[0098] [Table 1]

[0099] The specific compounds in Table 1 are as follows: DEAP: 3-(diethylamino)propylamine EN: Ethylenediamine TEP: Tetraethylenepentamine PO: Potassium oleate EDTA: Ethylenediaminetetraacetic acid Nonionic surfactant A-1:

[0100] [ka] (In the formula, R 6 :H,R 7 and R 8 are each a linear alkyl group having 1 to 12 carbon atoms, and R 7 and R 8 The total number of carbon atoms is 11 to 13, R 9 :-C2H4-, R 10 :-CH2CH(CH3)-, x = 12, y = 3, x and y represent the average number of moles added.) A mixture of multiple compounds that satisfies the following conditions.

[0101] Nonionic surfactant A-2:

[0102] [ka] R 11 and R 12 : Methyl group, R 13 and R 14 : isobutyl group, R 19 :-C≡C-, R 15 and R 17 :-C2H4-, x=4, y=0

[0103] Nonionic surfactant A-3:

[0104] [ka] R 20 =-C2H4-, R 21 =-CH2CH(CH3)-, x=23, y=0, n=11

[0105] <Cleaning performance evaluation> (Preparation of Co-BTA particle dispersion) 1 L of a solution in which 200 μmol / L of cobalt (II) nitrate was dissolved in 0.01 mol / L pure aqueous nitric acid solution, and 1 L of a solution in which 200 μmol / L of benzotriazole was dissolved in 0.01 mol / L pure aqueous nitric acid solution were prepared, and the two were mixed at room temperature to obtain 2 L of an aqueous solution in which insoluble associations of cobalt (II) ions and benzotriazole (hereinafter abbreviated as "Co-BTA particles") were dispersed. Potassium hydroxide powder was added to the obtained aqueous solution to adjust the pH of the aqueous solution to 8.0, and a Co-BTA particle dispersion was obtained.

[0106] (Preparation of cleaning evaluation substrate) A 1 cm square test piece was prepared by depositing Co, TiN, SiN, or SiO2 to a thickness of about 5 to 200 nm on a silicon wafer. 100 mL of the Co-BTA particle dispersion obtained above was placed in a beaker, and the test piece was immersed in the dispersion for 1 minute while stirring at 300 rpm using a magnetic rotor. After immersion, the test piece was taken out and rinsed with pure water, and then air-dried to remove moisture, obtaining a substrate for cleaning evaluation.

[0107] (Microscopic Observation) The surface state of the cleaning evaluation substrate obtained above was observed using an atomic force microscope (AFM) XE-300P (manufactured by Park Systems) using a PPP-NCHR AFM probe in non-contact mode (observation conditions: scan rate 0.5 Hz, observation area 5 μm × 5 μm).

[0108] (Cleaning process) The cleaning evaluation substrate was immersed in 100 mL of the cleaning composition of the Example or Comparative Example obtained above, and a cleaning treatment was performed by ultrasonic irradiation for 1 minute (treatment conditions: output 115 W, 40 KHz, temperature inside the beaker: 25° C.) using an ultrasonic cleaning device (8895, manufactured by Cole-Parmer). After ultrasonic irradiation, the cleaning evaluation substrate was taken out and rinsed with pure water, and the surface condition of the cleaning evaluation substrate was observed in the same manner as above. An AFM observation image of the surface of the obtained cleaning evaluation substrate is shown in FIG. 1.

[0109] From Fig. 1, it was confirmed that white foreign matter was attached to the Co film, TiN film, SiN film, and SiO2 film in the AFM observation before the cleaning treatment, and contamination with Co-BTA particles of various particle sizes occurred. When the cleaning treatment was performed using the cleaning agent compositions of Examples 1 to 3, the Co-BTA particles could be completely removed from the Co film, TiN film, SiN film, and SiO2 film, and it was found that the cleaning power was excellent. On the other hand, when the cleaning agent compositions of Comparative Examples 1 and 2 were used, significant white foreign matter was confirmed to remain on the Co film, and it was found that the cleaning power was insufficient.

[0110] <Electrochemical evaluation> The substrate for cleaning evaluation obtained by the same method as above was immersed in a beaker containing 100 mL of a pure aqueous solution of 10 mmol / L benzotriazole adjusted to pH = 10.0, and the substrate was left for 1 minute while being stirred at 300 rpm with a magnetic rotor, and then removed and washed with pure water to obtain a test piece for electrochemical evaluation. The electrochemical evaluation test piece was attached as the working electrode in a three-electrode glass cell equipped with a platinum counter electrode and an SCE standard electrode, and after connecting to a potentiostat, the glass cell was filled with the cleaning composition of the Example or Comparative Example, and swept at a scan rate of 5 mV / s to obtain a dynamic polarization curve with a potential width at an open circuit potential of ±0.5 V. Furthermore, the corrosion potential and corrosion current values ​​were calculated by the Tafel extrapolation method. The results are shown in Table 2. In addition, "ND" in the table indicates that the current value was below the lower limit of measurement.

[0111] [Table 2]

[0112] The descriptions in Table 2 represent the following: CoE CORR : Corrosion potential of Co film Co I CORR : Corrosion current value of Co film TINE CORR : Corrosion potential of TiN film TiN I CORR :Corrosion current value of TiN film ΔE CORR Corrosion potential difference at the Co / TiN interface

[0113] A cleaning agent composition that does not cause corrosion has a corrosion current value of 10 μA / cm 2 It is necessary that the corrosion potential difference at the interface between different metals is 40 mV or less, and that the corrosion potential difference at the interface between different metals is 40 mV or less. When the cleaning compositions of Examples 1 to 5 were used, both of these evaluation criteria were satisfied, and it can be determined that the occurrence of corrosion can be suppressed. In contrast, when the cleaning compositions of Comparative Examples 1 to 3 were used, at least one of the evaluation criteria was not satisfied.

Claims

1. (A) a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms; (B) aliphatic amines; (C) at least one corrosion inhibitor selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds, The alkylene oxide adduct of an alcohol having 6 or more carbon atoms is a compound represented by the following general formula (2) or a compound represented by the following general formula (3): A post-CMP cleaning composition for use in a semiconductor manufacturing process. 【Chemistry 1】 In formula (2), R 6 , R 7 and R 8 are the same or different and represent a hydrogen atom or an alkyl group. Two or more of R 6 , R 7 and R 8 are alkyl groups. R 9 and R 10 are the same or different and represent an alkylene group. x and y are the same or different and represent an integer of 0 to 50. (x+y) is an integer of 1 or greater. In formula (3), R 11 , R 12 , R 13 and R 14 are the same or different and each represents a hydrogen atom or an alkyl group. R 15 , R 16 , R 17 , R 18 and R 19 are the same or different and each represents an alkylene group or an alkynylene group. x and y are the same or different and each represents an integer of 0 to 50. (x+y) is an integer of 1 or more.)

2. 2. The post-CMP cleaning composition according to claim 1, wherein the aliphatic amine has a molecular weight of 2,000 or less.

3. 3. The post-CMP cleaning composition according to claim 1, wherein the aliphatic amines include an amine compound represented by the following general formula (1) and / or a polyalkyleneimine: 【Chemistry 2】 (In formula (1), R １ , R ２ and R ３ are the same or different and each represents a hydrogen atom, an alkyl group, or -R ４ -(NH-R ５ ) ｎ -NH ２ Represents ４ and R ５ are the same or different and represent an alkylene group having 1 to 6 carbon atoms; and n represents an integer of 0 to 100.

4. The post-CMP cleaning agent composition according to any one of claims 1 to 3, wherein the nitrogen-containing heterocyclic compound comprises at least one selected from the group consisting of pyrrole, pyridine, triazole, triazine, purine, and derivatives thereof.

5. The post-CMP process cleaning agent composition according to any one of claims 1 to 4, wherein the carboxylate compound contains a fatty acid salt.

6. The post-CMP cleaning composition according to any one of claims 1 to 5, wherein the post-CMP cleaning composition is used for cleaning a wafer surface on which a cobalt-containing compound is exposed.

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