Composition, method for manufacturing cleaned workpiece, and method for manufacturing electronic device

Abstract

The present invention provides a composition which exhibits excellent particle removability and organic matter removability at a time when applied to a workpiece including a hydrophilic surface derived from an insulating film such as an oxide film and a nitride film that have undergone CMP treatment. Furthermore, provided are a method for manufacturing a cleaned workpiece, and a method for manufacturing an electronic device. A composition according to the present invention is used for cleaning a workpiece having undergone chemical mechanical polishing treatment, and contains: a nonionic surfactant having a polyoxyalkylene chain and a hydrophilic-lipophilic balance value of 14-20; and a specific compound (excluding zwitterionic compounds) selected from the group consisting of an inorganic acid, an amino alcohol, an organic acid, a quaternary ammonium compound, and an aliphatic polyamine. The organic acid has at least one group selected from the group consisting of a carboxylic acid group, a phosphonic acid group, and a sulfonic acid group, and the mass ratio of the content of the nonionic surfactant to the total content of the specific compound is 0.1-10,000.

Description

Composition, method for manufacturing a cleaned workpiece, method for manufacturing an electronic device

[0001] The present invention relates to a composition, a method for manufacturing a cleaned workpiece, and a method for manufacturing an electronic device.

[0002] In the semiconductor field, with the remarkable increase in integration and performance, even minute amounts of impurities (contaminations) and / or attached substances (particles) can significantly affect the performance of equipment and, consequently, the yield of products. Various types of contaminations and particles (hereinafter also referred to as residues) can be generated in each manufacturing process of semiconductor devices. In semiconductor manufacturing, substrate processing processes are appropriately carried out to remove such residues.

[0003] For example, in the manufacturing of semiconductor devices, chemical mechanical polishing (CMP) is sometimes performed to planarize the surface of a semiconductor substrate having metal wiring films, barrier metals, and insulating films using a polishing slurry containing polishing particles (e.g., silica and alumina). In CMP processing, metal components derived from the polishing particles used in the CMP process, the polished wiring metal films, and / or barrier metals tend to remain on the semiconductor substrate surface and the polishing components (e.g., polishing pads) after polishing. Therefore, a process to remove these residues using a composition is generally performed after CMP processing.

[0004] As described above, in the semiconductor manufacturing process, the composition is used for processes such as removing unwanted metal components, resists, and residues from various materials used in semiconductor manufacturing. As an example of a composition, Patent Document 1 discloses a "polishing cleaning liquid composition characterized by containing a nonionic surfactant and water" as a polishing cleaning liquid that can efficiently remove particles from the surface of a semiconductor substrate after chemical mechanical polishing.

[0005] Japanese Patent Publication No. 2004-323840

[0006] The present inventors investigated the removal of residue after CMP treatment using the polishing and cleaning liquid composition specifically disclosed in Patent Document 1, and found that the desired effect could not be obtained. Specifically, when performing the step of CMP treatment on a workpiece containing a hydrophilic surface derived from an insulating film such as an oxide film or a nitride film (hereinafter also referred to as the "CMP step"), and the step of cleaning the workpiece after the CMP treatment with the above composition (hereinafter also referred to as the "cleaning step"), particles and organic residues were found to be present on the workpiece, and it was confirmed that the removal of these was insufficient. Here, particles refer to polishing particles used in the CMP treatment, metal components derived from polished wiring metal films and / or barrier metals, etc., and organic matter refers to organic components derived from the polishing slurry and the cleaning liquid composition.

[0007] Therefore, the present invention aims to provide a composition that exhibits excellent particle removal and organic matter removal properties when applied to a workpiece containing a hydrophilic surface derived from an insulating film such as an oxide film or nitride film that has undergone CMP treatment. Furthermore, the present invention also aims to provide a method for manufacturing a cleaned workpiece and a method for manufacturing an electronic device.

[0008] As a result of diligent research to solve the above problems, the inventors have found that the problems can be solved by the following configuration.

[0009] [1] A composition used for cleaning a workpiece that has undergone chemical mechanical polishing, comprising: a nonionic surfactant having a polyoxyalkylene chain and a hydrophilic-lipophilic balance value of 14 to 20; and a specific compound selected from the group consisting of inorganic acids, amino alcohols, organic acids, quaternary ammonium compounds, and aliphatic polyamines (excluding zwitterionic compounds), wherein the organic acid has at least one group selected from the group consisting of carboxylic acid groups, phosphonic acid groups, and sulfonic acid groups, and the mass ratio of the content of the nonionic surfactant to the total content of the specific compound is 0.1 to 10000. [2] The composition according to [1], wherein the specific compound comprises nitric acid, phosphoric acid, or sulfuric acid. [3] The composition according to [1] or [2], wherein the pH is 6 or less. [4] The composition according to any one of [1] to [3], wherein the pH is 1 to 6. [5] The composition according to any one of [1] to [4], wherein the specific compound is an amino alcohol. [6] The composition according to [5], wherein the amino alcohol is selected from the group consisting of trishydroxymethylaminomethane, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, 1,3-bis[tris(hydroxymethyl)methylamino]propane, monoethanolamine, diethanolamine, N-methyldiethanolamine, 2-amino-2-methyl-1-propanol, triethanolamine, diethylene glycolamine, 2-(dimethylamino)-2-methyl-1-propanol, and 2-(2-aminoethylamino)ethanol. [7] The composition according to [5] or [6], wherein the pH is 7.5 or higher. [8] The composition according to any one of [5] to [7], wherein the pH is 7.5 to 9.5. [9] The composition according to any one of [1] to [8], wherein the content of the nonionic surfactant is equal to or greater than the critical micelle concentration of the nonionic surfactant at 25°C.

[10] The composition according to any one of [1] to [9], wherein the polyoxyalkylene chain has a structure consisting of a group selected from the group consisting of an oxyethylene group and an oxypropylene group.

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

[10] , further comprising an antibacterial agent.

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

[11] , which is substantially free of abrasive particles.

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

[12] , wherein the workpiece subjected to the chemical mechanical polishing treatment comprises silicon atoms and at least one of oxygen atoms and nitrogen atoms.

[14] A composition according to any one of [1] to

[13] , wherein two or more different materials are exposed on the surface of the workpiece subjected to the chemical mechanical polishing treatment.

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

[14] , wherein the workpiece subjected to the chemical mechanical polishing treatment comprises at least one selected from the group consisting of tungsten, cobalt, ruthenium, copper, aluminum, titanium, titanium nitride, tantalum, tantalum nitride, and alloys consisting of two or more of these.

[16] A method for producing a cleaned workpiece, comprising the step of bringing a composition according to any one of [1] to

[15] into contact with a workpiece subjected to chemical mechanical polishing treatment.

[17] A method for manufacturing a cleaned workpiece, comprising the step of supplying a composition according to any one of [1] to

[15] , bringing a workpiece that has undergone chemical mechanical polishing treatment into contact with a pad, moving the workpiece and the pad relative to each other to clean the workpiece, and obtaining a cleaned workpiece.

[18] A method for manufacturing a cleaned workpiece according to

[17] , wherein the pad is pressed against the workpiece and the workpiece and the pad are moved relative to each other.

[19] A method for manufacturing an electronic device, comprising the method for manufacturing a cleaned workpiece according to any one of

[16] to

[18] .

[0010] According to the present invention, a composition can be provided that exhibits excellent particle removal and organic matter removal properties when applied to a workpiece containing a hydrophilic surface derived from an insulating film such as an oxide film or nitride film that has undergone CMP treatment. Furthermore, according to the present invention, a method for manufacturing a cleaned workpiece and a method for manufacturing an electronic device can also be provided.

[0011] This is a schematic cross-sectional view of a patterned wafer.

[0012] The present invention will be described in detail below. The following descriptions of constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0013] In this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. Also, in this specification, when there are two or more kinds of a certain component, the "content" of that component means the total content of those two or more kinds of components. In the numerical ranges described step by step in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other step-by-step descriptions. Also, in the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0014] In this specification, the "total mass of the components excluding the solvent in the composition" means the total mass of all the components contained in the composition other than solvents such as water and organic solvents. In the compounds described in this specification, unless otherwise specified, structural isomers, optical isomers, and isotopes may be included. Also, structural isomers, optical isomers, and isotopes may be included alone or in combination of two or more.

[0015] In this specification, when there are a plurality of substituents and linking groups etc. (hereinafter referred to as substituents etc.) represented by specific symbols, or when a plurality of substituents etc. are defined simultaneously, it means that each of the substituents etc. may be the same as or different from each other. This also applies to the definition of the number of substituents etc. The bonding direction of the divalent groups represented in this specification is not limited unless otherwise specified. For example, in a compound represented by the formula "X - Y - Z", when Y is -COO-, Y may be -CO - O - or -O - CO -. Also, the above compound may be "X - CO - O - Z" or "X - O - CO - Z".

[0016] In this specification, "ppm" means "parts - per - million (10 －６ )", and "ppb" means "parts - per - billion (10 －９ )".

[0017] In this specification, the "weight-average molecular weight" means the weight-average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography). In this specification, the "hydrophilic-lipophilic balance" (HLB; Hydrophile-Lipophile Balance) value is defined by the following formula (Griffin method), and is a value indicating the affinity of a surfactant for water and oil. In some cases, catalog values or values calculated by other methods may be used. HLB value = 20 × [(molecular weight of hydrophilic group contained in surfactant) / (molecular weight of surfactant)] In this specification, the "critical micelle concentration" (critical micelle concentration (CMC)) means the concentration at the inflection point when the surface tension of an aqueous surfactant solution is measured by changing the concentration of the surfactant solution using a surface tension meter such as a Wilhelmy type surface tension meter at 25°C under atmospheric pressure. In some cases, catalog values or values calculated by other methods may be used. For example, a commercially available kit or the like that measures the critical micelle concentration of a surfactant by utilizing the fluorescence change of a fluorescent reagent that interacts with the surfactant can be used.

[0018] [Composition] Hereinafter, the composition of the present invention will be described in detail. The composition of the present invention (hereinafter also simply referred to as "the present composition") is a composition used for cleaning a workpiece subjected to chemical mechanical polishing treatment, and has a polyoxyalkylene chain, and a nonionic surfactant having a hydrophilic-lipophilic balance value of 14 to 20, and a specific compound selected from the group consisting of inorganic acids, amino alcohols, organic acids, quaternary ammonium compounds, and aliphatic polyamines (excluding zwitterionic compounds), wherein the organic acid has at least one group selected from the group consisting of a carboxylic acid group, a phosphonic acid group, and a sulfonic acid group, and the mass ratio of the content of the nonionic surfactant to the total content of the specific compound is 0.1 to 10000.

[0019] The reason why the composition having the above configuration can solve the problems of the present invention is not necessarily clear, but the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than those described below, it is still within the scope of the present invention. On the substrate after CMP treatment, metal components derived from polishing particles used in the CMP treatment, polished wiring metal films and / or barrier metals, and organic components derived from the polishing slurry and cleaning solution composition tend to remain. However, the nonionic surfactant effectively protects the above residues, thereby suppressing re-adhesion to the substrate, and thus the composition exhibits excellent particle removal and organic matter removal properties. Furthermore, since the nonionic surfactant does not significantly affect the dispersion and aggregation of residues, residues are less likely to remain on the substrate, and the substrate is less likely to be damaged. Also, although the detailed mechanism is unknown, certain compounds also contribute to particle removal and organic matter removal properties. Furthermore, by having a mass ratio of the nonionic surfactant content to the total content of specific compounds of 0.1 to 10000, the balance between particle removal and organic matter removal can be optimized. Thus, it is believed that the problems of the present invention have been solved by having the above-described composition. Hereinafter, when this composition is applied to a workpiece containing a hydrophilic surface derived from an insulating film such as an oxide or nitride film subjected to CMP treatment, the superiority of at least one of the particle removal and organic matter removal effects is also referred to as "the effects of the present invention being superior." The components contained in this composition and the physical properties of this composition will be described in detail below.

[0020] [Nonionic Surfactant] This composition contains a nonionic surfactant having a polyoxyalkylene chain and a hydrophilic-lipophilic balance value of 14 to 20 (hereinafter also referred to as "nonionic surfactant A"). A nonionic surfactant is a compound having a surfactant function by having a hydrophilic group and a hydrophobic group that do not exhibit ionic properties, unlike ionic surfactants such as anionic surfactants and cationic surfactants. However, within a range that does not impair the effects of the present invention, nonionic surfactant A may have an ionic group such as an amino group. In addition to the hydrophilic group and the hydrophobic group, it is also preferable that nonionic surfactant A contains at least one of an ether bond (—O—) and an ester bond (—COO— or —OCO—).

[0021] The molecular weight of nonionic surfactant A is not particularly limited and may be a high molecular compound, but the molecular weight is preferably 500 to 50,000, more preferably 500 to 30,000, and still more preferably 500 to 10,000. When nonionic surfactant A has a molecular weight distribution, the above molecular weight refers to the weight average molecular weight.

[0022] The polyoxyalkylene chain possessed by nonionic surfactant A has a structure represented by —(R ａ O) ｎ —. R ａ represents an alkylene group, and n represents an integer of 2 or more. A plurality of R ａ may be different from each other or the same. The number of carbon atoms of the above alkylene group is preferably 1 to 10, more preferably 2 to 6, and still more preferably 2 or 3. n is preferably 2 to 200, more preferably 5 to 150, and still more preferably 5 to 100. The polyoxyalkylene chain is an oxyethylene group (—CH ２ —CH ２ —O—), and a polyoxypropylene group (—CH ２ —CH(CH ３ )—O— or —(CH ２ ) ３It is preferable that the structure consists of a group selected from the group consisting of -O-). The polyoxyalkylene chain may consist of only one of the oxyethylene group and the oxypropylene group, or it may consist of both. Furthermore, it is preferable that the nonionic surfactant A has at least one of the polyoxyethylene chain and the polyoxypropylene chain, and more preferably has the polyoxyethylene chain.

[0023] The hydrophilic-lipophilic balance (HLB) value of nonionic surfactant A is not particularly limited as long as it is between 14 and 20, but is preferably between 14.5 and 20, more preferably between 15 and 19.5, and even more preferably between 15 and 19. As detailed above, the HLB value indicates the affinity of a surfactant for water and oil; a higher value indicates hydrophilicity, and a lower value indicates lipophilicity.

[0024] Examples of hydrophobic groups in nonionic surfactant A include hydrocarbon groups, more specifically, aliphatic hydrocarbon groups, aromatic ring groups which may have substituents, and groups formed by combining these. The valency of each of the above-mentioned groups is not particularly limited, for example, it can be 1 to 4-valent, and is often monovalent or divalent. In particular, nonionic surfactant A preferably has a hydrocarbon group having 3 to 30 carbon atoms as its hydrophobic group, and more preferably has a hydrocarbon group having 10 to 25 carbon atoms.

[0025] The above aliphatic hydrocarbon group may be linear, branched, or cyclic. Furthermore, the aliphatic hydrocarbon group may be monovalent or divalent or more. Examples of aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups. The number of carbon atoms in linear or branched aliphatic hydrocarbon groups is preferably 3 to 30, more preferably 8 to 25, and even more preferably 10 to 20. The cyclic aliphatic hydrocarbon group may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as adamantane. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 6 to 30, more preferably 7 to 30, and even more preferably 8 to 20.

[0026] The aromatic ring constituting the above aromatic ring group may be monocyclic or polycyclic. Examples of polycyclic rings include fused rings formed by the fusion of two or more monocyclic rings, and linked rings formed by the single bonding of two or more rings selected from monocyclic and fused rings. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but an aromatic hydrocarbon ring is preferred. The number of carbon atoms in the aromatic ring is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 15. Specific examples of aromatic rings include benzene rings and naphthalene rings. The number of substituents that the aromatic ring group may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. Examples of substituents that the aromatic ring group may have include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and halogen atoms.

[0027] Among the hydrophobic groups mentioned above, aliphatic hydrocarbon groups or polycyclic aromatic hydrocarbon groups are preferred, aliphatic hydrocarbon groups having 3 to 30 carbon atoms or distylated aromatic hydrocarbon groups are more preferred, and alkyl groups having 3 to 30 carbon atoms or distylated phenyl groups are even more preferred.

[0028] Specific examples of nonionic surfactant A include polyalkylene glycol, polyoxyalkylene alkyl ester, polyoxyalkylene polyoxyalkylene alkyl ester, polyoxyalkylene alkyl ether, polyoxyalkylene polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene polyoxyalkylene alkylphenyl ether, polyoxyalkylene polyalkylphenyl ether, polyoxyalkylene distyrene-derived phenyl ether, polyoxyalkylene glycol, polyoxyalkylene polyoxyalkylene glycol, polyoxyalkylene polyoxyalkylene block copolymer, polyoxyalkylene glycerin fatty acid ester, polyoxyalkylene polyoxyalkylene glycerin fatty acid ester, polyalkylene glycol fatty acid ester, polyoxyalkylene polyoxyalkylene glyco Examples include polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene polyoxyalkylene fatty acid esters, polyoxyalkylene castor oil, polyoxyalkylene polyoxyalkylene castor oil, polyoxyalkylene hydrogenated castor oil, polyoxyalkylene polyoxyalkylene hydrogenated castor oil, polyoxyalkylene phytosterols, polyoxyalkylene polyoxyalkylene phytosterols, polyoxyalkylene alkyl fatty acid amides, polyoxyalkylene polyoxyalkylene alkyl fatty acid amides, polyoxyalkylene alkylamines, polyoxyalkylene polyoxyalkylene alkylamines, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, and polyoxyethylene sorbitol beeswax. In the above specific examples, "polyoxyalkylene polyoxyalkylene" refers to a state in which two different polyoxyalkylene groups are bonded together. The above fatty acid ester may also be a fatty acid partial ester in which a portion has been esterified.The oxyalkylene group described above is preferably an oxyethylene group or an oxypropylene group.

[0029] Among the specific examples mentioned above, polyoxyalkylene alkyl ethers, polyoxyalkylene distyrene-phenyl ethers, polyoxyalkylene polyoxyalkylene block copolymers, polyoxyalkylene glycol fatty acid esters, polyoxyalkylene hydrogenated castor oil, or polyoxyalkylene alkylamines are particularly preferred. As the oxyalkylene group, an oxyethylene group or an oxypropylene group is preferred.

[0030] Among nonionic surfactants A, polyoxyethylene polycyclic phenyl surfactants are preferred. Polyoxyethylene polycyclic phenyl surfactants have an ether structure in which a group having at least two monocyclic aromatic hydrocarbon groups (e.g., a phenyl group and a phenylene group) or a group having at least one polycyclic aromatic hydrocarbon group (e.g., a naphthyl group) is contained within the molecular skeleton. Specific examples of polyoxyethylene polycyclic phenyl surfactants include compounds represented by formula (1) as described in paragraphs

[0022] to

[0029] of International Publication No. 2022 / 224680, the contents of which are incorporated herein by reference.

[0031] Examples of polyoxyethylene polycyclic phenyl surfactants include polyoxyethylene distylenide phenyl ether, polyoxyethylene distylenide methyl phenyl ether, polyoxyethylene tristyreneide phenyl ether, polyoxyethylene tripenzyl phenyl ether, polyoxyethylene distylenide cresyl ether, and polyoxyethylene allyl phenyl ether, with polyoxyethylene distylenide phenyl ether being preferred.

[0032] Products that can be used as polyoxyethylene polycyclic phenyl surfactants include Emulgen A-90, Emulgen A-500 (Kao Corporation), Newcol 703, Newcol 704, Newcol 706, Newcol 707, Newcol 708, Newcol 709, Newcol 710, Newcol 711, Newcol 712, Newcol 714, Newcol 719, Newcol 723, Newcol 729, Newcol 733, Newcol 740, and Newcol Examples include 747, Newcol 780, Newcol 610, Newcol 2604, Newcol 2607, Newcol 2609, Newcol 2614 (Nippon Emulsifier Co., Ltd.), Adekatol PC-13 (Adeka Co., Ltd.), Neugen EA-87, Neugen EA-137, Neugen EA-157, Neugen EA-167, Neugen EA-177, Neugen EA-197D, Neugen EA-207D (Daiichi Kogyo Seiyaku Co., Ltd.), and Brownon TSP-50 (Aoki Oil & Fat Co., Ltd.).

[0033] Nonionic surfactant A may be used alone or in combination of two or more types. The content of nonionic surfactant A is preferably 0.01 to 25.0% by mass, more preferably 0.1 to 20.0% by mass, and even more preferably 0.1 to 10.0% by mass, based on the total mass of the composition. Furthermore, the content of nonionic surfactant A is preferably 5.0 to 99.9% by mass, more preferably 50.0 to 99.8% by mass, and even more preferably 90.0 to 99.8% by mass, based on the total mass of the components in the composition excluding the solvent. In particular, for the effects of the present invention to be superior, it is preferable that the content of nonionic surfactant A relative to the total mass of the composition is equal to or greater than the critical micelle concentration (CMC) of nonionic surfactant A at 25°C. The definition and measurement method of CMC are as described above.

[0034] Furthermore, the mass ratio of the content of nonionic surfactant A to the content of the specific compound described later is 0.1 to 10000. In particular, a ratio greater than 1.0 is preferred, and a ratio less than 10000 is preferred, in terms of superior effects of the present invention. Moreover, 5.0 to 8000 is more preferred, 5.0 to 5000 is even more preferred, 10.0 to 1000 is particularly preferred, and 10.0 to 500 is most preferred. Furthermore, the mass ratio of the content of nonionic surfactant A to the content of the antibacterial agent described later is preferably 1.0 to 10000, more preferably greater than 5.0 and less than 10000, and even more preferably 10.0 to 2000. Furthermore, the mass ratio of the content of nonionic surfactant A to the content of the corrosion inhibitor described later is preferably 1.0 to 20000, more preferably 5.0 to 10000, and even more preferably 10.0 to 5000.

[0035] [Specific Compounds] This composition contains specific compounds selected from the group consisting of inorganic acids, amino alcohols, organic acids, quaternary ammonium compounds, and aliphatic polyamines (excluding zwitterionic compounds). As described above, organic acids have at least one group selected from the group consisting of carboxylic acid groups, phosphonic acid groups, and sulfonic acid groups. For superior effects of the present invention, it is more preferable that this composition contains at least one selected from the group consisting of inorganic acids and organic acids (excluding zwitterionic compounds) and at least one selected from the group consisting of amino alcohols, quaternary ammonium compounds, and aliphatic polyamines (excluding zwitterionic compounds). Also, as described above, specific compounds are compounds excluding zwitterionic compounds such as amino acids (compounds having both cationic and anionic parts). Although the detailed mechanism is unknown, it is thought that because the specific compounds are not zwitterionic compounds, competitive reactions between promoting and inhibiting the cleaning of the same compound are less likely to occur within a single compound, thus allowing for sufficient cleaning effect of the chemical solution.

[0036] The specific compound is not particularly limited, but it is preferably a low molecular weight compound. The molecular weight of the specific compound is preferably 50 to 700, more preferably 50 to 500, and even more preferably 50 to 300.

[0037] <Inorganic Acids> Examples of inorganic acids include nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, nitrite, sulfurous acid, and boric acid. Nitric acid, phosphoric acid, or sulfuric acid are preferred because they exhibit superior effects compared to the present invention. Any inorganic acid that becomes an acid or acid ion (anion) in aqueous solution may be used as a salt. The number of acid groups in the inorganic acid is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4.

[0038] <Organic Acids> As described above, organic acids have at least one group selected from the group consisting of carboxylic acid groups, phosphonic acid groups, and sulfonic acid groups. As described above, zwitterionic compounds are excluded from the specific compounds. Therefore, organic acids having at least one group selected from the group consisting of carboxylic acid groups, phosphonic acid groups, and sulfonic acid groups do not have anionic groups such as basic groups. The number of acid groups that an organic acid has is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. The number of carbon atoms in an organic acid is preferably 1 to 15, and more preferably 2 to 15. Organic acids preferably have at least one of a carboxylic acid group and a phosphonic acid group.

[0039] The effects of the present invention are considered to be even better when the composition further contains an organic acid as a specific compound. Specifically, when the CMP-treated workpiece, which is the target of cleaning with this composition, includes a metal surface, metal oxides can be removed, and furthermore, the removal of particulate residues, organic residues, and organic-metal composite residues present on the metal oxide surface can also be improved. The inventors surmise that this is due to a cleaning mechanism in which residues are lifted off by light etching of the oxide film. The residues removed by the lift-off function can be more easily removed from the surface by physical cleaning such as polishing pads and cleaning brushes, and the lift-off cleaning mechanism is considered to be particularly effective on the above-mentioned workpieces in which a thick metal oxide layer can form (for example, a tungsten surface after polishing to which a Fenton reaction-based oxidizing agent that generates highly oxidized species has been applied). In addition, by adding an organic acid, the surface potential of both the residue surface of particles and organic matter, and the surface of the above-mentioned workpiece are shifted to the negative, so an electrostatic repulsion force is acting and an improvement in cleaning performance can be expected. For example, the effects of the present invention are considered to be more pronounced when the potential shifts to below -10 mV in the acidic region (usually around 0 mV) and to around -20 mV in the weakly acidic to neutral region (usually -5 to -10 mV). In particular, the above effects are considered to be more pronounced when the residue is particulate residue, organic residue, or organo-metallic composite residue.

[0040] Furthermore, if the composition further contains an organic acid as a specific compound, it is preferable in that it can also be expected to enhance the corrosion resistance of the surface of the treated object. The inventors speculate that the reason for this effect is that the organic acid protects the surface of the treated object (for example, a metal surface) and suppresses the dissolution mechanisms of the treated object surface, such as oxidation and dissolution. In particular, if the treated object includes a metal surface such as a Cu layer, the corrosion resistance effect is considered to be even better.

[0041] The addition of multiple types of organic acids enhances the cleaning effect synergistically, and the effects of the present invention are further improved, so it is preferable for this composition to contain two or more types of organic acids. As one example of the mechanism, the inventors speculate that the first organic acid reacts kinetically quickly with residues such as particles and organic matter, and ligand exchange proceeds with the second organic acid, which reacts kinetically more slowly. After reacting with the residue, the second organic acid imparts high solubility and dispersibility to the composition, especially when the composition contains water, thereby resulting in an effective cleaning effect. The effect is often strengthened when the organic acid is a chelating agent with multiple coordination sites. In particular, the above effect is considered to be even better when the residue is particulate residue, organic matter residue, or organo-metallic composite residue.

[0042] Carboxylic acid-based organic acids are organic acids that have at least one carboxyl group in their molecule.

[0043] As for carboxylic acid-based organic acids, aliphatic carboxylic acid-based organic acids are preferred, for example.

[0044] Aliphatic carboxylic acid organic acids may further have hydroxyl groups. Examples of aliphatic carboxylic acid organic acids include citric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, sebacic acid, maleic acid, and malic acid.

[0045] Phosphonic acid-based organic acids are organic acids having at least one phosphonic acid group in their molecule. Examples of phosphonic acid-based organic acids include aliphatic phosphonic acid-based organic acids. In addition to the phosphonic acid group and the aliphatic group, aliphatic phosphonic acid-based organic acids may also have a hydroxyl group. The number of phosphonic acid groups in a phosphonic acid-based organic acid is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 to 3. The number of carbon atoms in a phosphonic acid-based organic acid is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8.

[0046] Examples of phosphonic acid-based organic acids include ethylidenediphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropylidene-1,1'-diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, and nitrilotris(methylenephosphonic acid) (NTPO), with ethylidenediphosphonic acid or HEDPO being preferred.

[0047] <Amino Alcohols> Amino alcohols are compounds of amines that further have at least one hydroxylalkyl group in their molecule. When this composition further contains amino alcohol as a specific compound, it is preferable in that it can also be expected to enhance the corrosion resistance of the surface of the CMP-treated workpiece that is the target of cleaning with this composition. The inventors speculate that the reason for obtaining the above effect is that the amino alcohol protects the surface of the workpiece (for example, a metal surface) and suppresses the dissolution mechanism of the workpiece surface, such as oxidation and dissolution. In particular, when the workpiece includes a metal surface such as a tungsten layer, the above corrosion resistance effect is considered to be even better. Amino alcohols may have any of primary to tertiary amino groups, but it is preferable that they have primary amino groups. The number of amino groups in an amino alcohol is, for example, 1 to 5, and is preferably 1 to 3. The number of hydroxyl groups in an amino alcohol is, for example, 1 to 5, and is more preferably 1 to 3.

[0048] Examples of amino alcohols include monoethanolamine (MEA), 3-amino-1-propanol, 1-amino-2-propanol, trishydroxymethylaminomethane (Tris), 2-amino-2-methyl-1-propanol (AMP), 2-dimethylamino-2-methyl-1-propanol (DMAMP), bis-trispropane, 2-amino-2-methyl-1,3-propanediol (AMPDO), 2-amino-2-ethyl-1,3-propanediol (AEPDO), 2-amino- 1,3-propanediol (2-APDO), 3-amino-1,2-propanediol (3-APDO), 3-methylamino-1,2-propanediol (MAPDO), 2-(methylamino)-2-methyl-1-propanediol (N-MAMP), 2-(aminoethoxy)ethanol (AEE), 2-(2-aminoethylamino)ethanol (AAE), diethanolamine (DEA), triethanolamine (TEA), N-methylethanolamine, N-butylethanolamine, N-cycloethanolamine Examples include xylethanolamine, 2-(ethylamino)ethanol, propylaminoethanol, diethylene glycolamine (DEGA), N,N'-bis(2-hydroxyethyl)ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, N-tert-butyldiethanolamine, N-butyldiethanolamine, N-methyldiethanolamine, bis-trispropane, 1-piperidineethanol, and 1-(2-hydroxyethyl)piperazine. In particular, it is preferable to select from the group consisting of trishydroxymethylaminomethane, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, 1,3-bis[tris(hydroxymethyl)methylamino]propane, monoethanolamine, diethanolamine, N-methyldiethanolamine, 2-amino-2-methyl-1-propanol, triethanolamine, diethylene glycolamine, 2-(dimethylamino)-2-methyl-1-propanol, and 2-(2-aminoethylamino)ethanol.

[0049] <Quaternary Ammonium Compounds> Quaternary ammonium compounds are not particularly limited as long as they are compounds or salts thereof that have at least one quaternary ammonium cationic group formed by the substitution of a nitrogen atom with four hydrocarbon groups (preferably alkyl groups). Examples of quaternary ammonium compounds include quaternary ammonium hydroxide, quaternary ammonium fluoride, quaternary ammonium bromide, quaternary ammonium iodide, quaternary ammonium acetate, and quaternary ammonium carbonate. Among these, quaternary ammonium hydroxide is preferred, and the compound represented by the following formula (a1) is more preferred.

[0050]

[0051] In the above formula (a1), R ａ１ ~R ａ４ Each of these independently represents an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or a hydroxyalkyl group having 1 to 16 carbon atoms. ａ１ ~R ａ４ At least two of these may be joined together to form a ring structure.

[0052] As the compound represented by the above formula (a1), a compound selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide (TBAH), methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, triethylmethylammonium hydroxide (MTEAH), dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide (BzTMAH), hexadecyltrimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, and spiro-(1,1')-bipyrrolidinium hydroxide is preferred from the viewpoint of availability, with TMAH, TEAH, or TBAH being more preferred.

[0053] <Aliphatic Polyamines> Aliphatic polyamines are not particularly limited as long as they are compounds having two or more amino groups. The number of amino groups in an aliphatic polyamine is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in an aliphatic polyamine is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. If an aliphatic polyamine has a hydroxyl group, it is classified as an amino alcohol. Among aliphatic polyamines, compounds represented by the following formula (A2) are particularly preferred.

[0054]

[0055] In formula (A2), R Ａ４ ~R Ａ７ Each of these independently represents a hydrogen atom or an alkyl group which may have substituents. Ａ４ ~R Ａ７ Two of these may be bonded to each other via a single bond or a divalent linking group to form a ring. Ａ４ and R Ａ７ , and R Ａ５ and R Ａ６ Both may be bonded to each other via single bonds or divalent linking groups to form a ring. Ａ８ -NR Ａｘ R represents an alkylene group which may have a linking group represented by - or -O-. Ａｘ represents a hydrogen atom or an alkyl group.

[0056] R Ａ４ ~R Ａ７ Each of these independently represents a hydrogen atom or an alkyl group which may have substituents. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, even more preferably 1 to 6, and particularly preferably 1 to 3. Examples of substituents on the alkyl group include halogen atoms such as fluorine, chlorine, and bromine atoms; alkoxy groups; acyl groups such as acetyl, propionyl, and benzoyl groups; cyano groups; and nitro groups. Among these, R Ａ４ ~R Ａ７As such, an alkyl group having 1 to 3 carbon atoms is preferred, a methyl group, an ethyl group, a propyl group, or an isopropyl group is more preferred, and a methyl group is even more preferred. Ａ４ ~R Ａ７ Preferably, at least one of them represents an alkyl group which may have substituents, R Ａ４ and R Ａ５ It is more preferable that at least two of represent alkyl groups which may have substituents, Ａ４ ~R Ａ７ It is even more preferable that represents an alkyl group which may have substituents.

[0057] R Ａ８ -NR Ａｘ R represents an alkylene group which may have a linking group represented by - or -O-. Ａｘ represents a hydrogen atom or an alkyl group. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6. The alkylene group has -NR Ａｘ The number of linking groups represented by - is preferably 0 to 3, and more preferably 0 to 1. The number of linking groups represented by -O- on the alkylene group is preferably 0 to 3, and more preferably 0 to 1. R Ａｘ The hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group is more preferred, with a methyl group being even more preferred.

[0058] R Ａ４ ~R Ａ７ Two of these may be bonded to each other via a single bond or a divalent linking group to form a ring. The resulting ring may be monocyclic or polycyclic. Examples of the divalent linking group include a divalent hydrocarbon group, -O-, and -CO-, with alkylene groups being preferred.

[0059] Examples of compounds represented by formula (A2) include N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA), tetramethyl-1,3-diaminobutane, tetramethyl-1,6-diaminohexane, N,N-diisopropylethylenediamine (DIPEN), N,N-dimethylethylenediamine (DMEN), N,N-diethylethylenediamine, tetramethyl-1,3-diaminopropane, and pentamethyldipropylenetriamine. Examples include N,N'-dimethylethylenediamine (NN'-DMEN), N-(2-hydroxypropyl)ethylenediamine (HPEN), N-ethylethylenediamine (EEN), 1,4-bis(2-hydroxyethyl)piperazine (BHEP), 1,4-bis(2-aminoethyl)piperazine (BAEP), 1,4-bis(3-aminopropyl)piperazine (BAAPP), and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0060] The specific compound may be used alone or in combination of two or more. The specific compound is preferably present in an amount of 0.0001 to 10% by mass, more preferably 0.001 to 1.0% by mass, and even more preferably 0.001 to 0.5% by mass, based on the total mass of the composition. Furthermore, the content of the specific compound is preferably 0.001 to 95.0% by mass, more preferably 0.01 to 10.0% by mass, and even more preferably 0.01 to 5.0% by mass, based on the total mass of the components in the composition excluding the solvent.

[0061] [Other Components] This composition may contain other components besides the nonionic surfactant A and the specific compound described above. Other components include anionic surfactants, cationic surfactants, nonionic surfactants other than the nonionic surfactant A described above, water, antibacterial agents, corrosion inhibitors, organic solvents, polymers, oxidizing agents, reducing agents, fluorides, and pH adjusters. In terms of achieving superior effects of the present invention, it is preferable that this composition contains a compound selected from the group consisting of water, antibacterial agents, and corrosion inhibitors. It is also believed that the effects of the present invention are superior when this composition contains the anionic surfactant or cationic surfactant described above. The inventors speculate that this is because each surfactant is adsorbed onto residues such as particles and organic matter, and in particular, when this composition contains water, it imparts solubility and dispersibility to the composition. In addition, each surfactant is adsorbed onto both the residue and the surface of the object to be treated, thereby strengthening the electrostatic repulsion between the residue and the object to be treated, and removing the residue or modifying it to a state that makes it easier to remove. Such electrostatic repulsion is thought to be more advantageous in acidic systems. In particular, the above effect is considered to be even better when the residue is particulate residue, organic residue, or organic-metal composite residue. Furthermore, when this composition contains the above anionic surfactant or cationic surfactant, it may also have the effect of enhancing the corrosion resistance of metal surfaces when the treated material includes metal surfaces such as Cu, Co, W, Mo, and Al. Here, if corrosion resistance can be imparted to Cu and Co in the acidic region, a cleaning solution can be designed for Cu and Co, which are easily corroded in the acidic region, and in this case, anionic surfactants are preferred. Note that the above compound is a different compound from other components such as antibacterial agents and corrosion inhibitors. For example, a compound of the type exemplified as a specific compound and that also has antibacterial activity is treated as a specific compound.

[0062] <Water> This composition preferably contains water. The type of water can be any water that does not adversely affect the semiconductor substrate, and distilled water, deionized (DI) water, and pure water (ultrapure water) can be used. Pure water (ultrapure water) is preferred because it contains almost no impurities and has less impact on the semiconductor substrate during the semiconductor substrate manufacturing process. The amount of water may be the remainder of the components that can be contained in this composition. The amount of water is preferably 60.0% by mass or more, more preferably 75.0% by mass or more, and even more preferably 85.0% by mass or more, based on the total mass of this composition. The upper limit is preferably 99.99% by mass or less, and more preferably 99.9% by mass or less, in terms of achieving better effects of the present invention.

[0063] <Antibacterial Agent> For the effects of the present invention to be even better, it is preferable that the composition further contains an antibacterial agent. The antibacterial agent is a compound having antibacterial activity against bacteria and / or antifungal activity against fungi, and is a compound different from each of the above components. The antibacterial agent may be in the form of a salt (for example, a known salt).

[0064] Examples of antibacterial agents include phenolic antibacterial agents, biguanide antibacterial agents, sulfamide antibacterial agents, peroxide antibacterial agents, isothiazolinone antibacterial agents, imidazole antibacterial agents, ester antibacterial agents, alcohol antibacterial agents, carbamate antibacterial agents, iodine antibacterial agents, and antibiotics.

[0065] Examples of phenolic antimicrobial agents include 3-methyl-4-chlorophenol (PCMC), 3-methyl-4-isopropylphenol (Biozol), 4-chloro-3,5-dimethylphenol (PCMX), cresol, chlorothymol, dichloroxylenol, and hexachlorophene. Cresol is preferred among these. Examples of biguanide antimicrobial agents include bis(p-chlorophenyl diguanide)hexanedigluconate (chlorhexidine gluconate) and poly(hexamethylene biguanide)hydrochloride (hexamethylene biguanidine hydrochloride). Chlorhexidine gluconate is preferred among these. Examples of sulfamide antimicrobial agents include N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide (Diclofluanide) and N-dichlorofluoromethylthio-N',N'-dimethyl-N-p-tolylsulfamide (Tolylfluanide). Among these, tolfluanide is preferred. Examples of peroxide-based antibacterial agents include hydrogen peroxide and peracetic acid. Among these, peracetic acid is preferred. Examples of isothiazolinone-based antibacterial agents include 2-methyl-4-isothiazolin-3-one (MIT), 2-octyl-4-isothiazolin-3-one (OIT), 1,2-benzoisothiazol-3(2H)-one (BIT), and 5-chloro-2-methyl-4-isothiazolin-3-one (CIT). Among these, MIT, OIT, or BIT is preferred, and MIT or OIT is more preferred. Examples of imidazole-based antibacterial agents include 2-(4-thiazolyl)-bentimidazole (TBZ) and 2-bentimidazolecarbamate methyl (Preventol BCM). Examples of ester-based antimicrobial agents include glycerol laurate (monoglyceride) and ethyl parahydroxybenzoate (ethylparaben). Examples of alcohol-based antimicrobial agents include ethyl alcohol (ethanol), 2-propanol (IPA), phenoxyethanol, 1,2-pentanediol, and 1,2-hexanediol.Examples of carbamate-based antimicrobial agents include 3-iodo-2-propynylbutylcarbamate (Glycical). Examples of iodine-based antimicrobial agents include [(4-chlorophenoxy)methyl]-3-iodo-2-propynyl ether (IF1000).

[0066] The antibacterial agent may be used alone or in combination of two or more types. The antibacterial agent content is preferably 0.00001 to 5.0% by mass, more preferably 0.0001 to 1.0% by mass, and even more preferably 0.0001 to 0.1% by mass, based on the total mass of the composition. Furthermore, the antibacterial agent content is preferably 0.001 to 20.0% by mass, more preferably 0.05 to 15.0% by mass, and even more preferably 0.1 to 2.0% by mass, based on the total mass of the components in the composition excluding the solvent.

[0067] <Corrosion Inhibitor> The composition preferably further contains a corrosion inhibitor. The corrosion inhibitor is a compound that has the function of preventing corrosion of the exposed surface of the workpiece, and is a compound different from each of the above components. The corrosion inhibitor is preferably a compound having an amino group other than a nitrogen-containing heterocyclic group (hereinafter also referred to as a "specific amino group"), selected from primary amino groups, secondary amino groups, and tertiary amino groups, and a compound having a primary amino group is more preferable. In addition, the corrosion inhibitor preferably has at least one carboxyl group in addition to the specific amino group. In other words, the corrosion inhibitor is preferably an amino acid. The amino acid may be a D-form, L-form, or DL-form. If the corrosion inhibitor has a carboxyl group, the number of carboxyl groups is preferably 1 to 5. Among these, the corrosion inhibitor is preferably a basic amino acid.

[0068] The number of specific amino groups in the corrosion inhibitor is preferably 2 to 5, more preferably 2 to 4. The number of carbon atoms in the corrosion inhibitor is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less. There is no particular lower limit, but 3 or more is preferred.

[0069] Examples of amino acids include glycine, serine, α-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), lysine, leucine, isoleucine, cystine, cysteine, ethionine, threonine, tryptophan, tyrosine, valine, histidine, histidine derivatives, ornithine, asparagine, aspartic acid, glutamine, glutamic acid, arginine, proline, methionine, phenylalanine, compounds described in paragraphs

[0021] to

[0023] of Japanese Patent Publication No. 2016-086094, and salts thereof. As histidine derivatives, compounds described in Japanese Patent Publication No. 2015-165561, Japanese Patent Publication No. 2015-165562, etc., can be used, and their contents are incorporated herein. Examples of salts include alkali metal salts such as sodium salts and potassium salts, ammonium salts, carbonates, and acetates. Preferred amino acids for use as corrosion inhibitors include arginine, histidine, lysine, ornithine, 2,4-diaminobutyric acid, tryptophan, asparagine, or glutamine; arginine, histidine, or lysine are more preferred; and L-arginine, L-histidine, or L-lysine are even more preferred.

[0070] Furthermore, heterocyclic compounds can also be used as corrosion inhibitors. Among heterocyclic compounds, nitrogen-containing heterocyclic compounds are preferred, in which at least one of the heteroatoms constituting the heterocycle is a nitrogen atom. Examples of nitrogen-containing heterocyclic compounds include azole compounds, purine compounds, pyrrole compounds, pyridine compounds, pyrazine compounds, pyrimidine compounds, indole compounds, indidine compounds, indazole compounds, quinoline compounds, and oxazole compounds, with purine compounds or azole compounds being preferred. Specifically, as corrosion inhibitors, for example, compounds described in paragraphs

[0046] to

[0050] of International Publication No. 2021 / 166571 can be referenced, and these contents are incorporated herein by reference.

[0071] The corrosion inhibitor may be used alone or in combination of two or more types. The content of the corrosion inhibitor is preferably 0.00001 to 5.0% by mass, more preferably 0.001 to 3.0% by mass, and even more preferably 0.01 to 0.5% by mass, based on the total mass of the composition. Furthermore, the content of the corrosion inhibitor is preferably 0.001 to 35.0% by mass, more preferably 0.005 to 20.0% by mass, and even more preferably 0.1 to 5.0% by mass, based on the total mass of the components in the composition excluding the solvent.

[0072] <Organic solvents> This composition may further contain organic solvents. Examples of organic solvents include known organic solvents such as alcohol-based solvents, glycol-based solvents, glycol ether-based solvents, and ketone-based solvents. The organic solvent is preferably miscible with water in any ratio. Examples of organic solvents include compounds exemplified in paragraphs

[0135] to

[0140] of International Publication No. 2022 / 044893, the contents of which are incorporated herein by reference.

[0073] [Physical Properties of the Composition] <pH> This composition may be either acidic or alkaline. When this composition is acidic, in terms of achieving superior effects of the present invention, the pH is preferably 6 or less, and more preferably 5.5 or less. As a lower limit, it is preferably 0.5 or more, more preferably 1 or more, and even more preferably 2 or more. When the CMP-treated workpiece that is the target of cleaning with this composition particularly includes a metal surface, it is preferable that the pH of this composition be in the acidic range, in order to more effectively remove particles and organic matter from the metal surface while also being able to enhance the corrosion resistance of the metal surface. The inventors speculate that the reason why the above effects are obtained is that in the acidic range, the solubility of metal oxide / solubility of metal surface (solubility ratio) can be made > 1, so an ideal system can be constructed in which metal oxide such as particles is selectively dissolved while reducing corrosion of the metal surface. In particular, when the workpiece is particularly a metal surface of Cu, Co, W, Mo, and Al, the above effects are considered to be superior. Furthermore, if the composition is alkaline, the pH is preferably 7.5 or higher, and more preferably 8.0 or higher. The upper limit is preferably 13.5 or lower, more preferably 11 or lower, even more preferably 10.5 or lower, and particularly preferably 9.5 or lower. When the object to be treated particularly includes a metal surface, the pH of the composition is preferably in the alkaline range in terms of superior effects of the present invention. The inventors speculate that the reason for obtaining the above effects is that in the alkaline range, the surface potential of both the residue such as particles and organic matter and the metal to be cleaned shifts to the negative, and an electrostatic repulsive force acts, which is expected to improve cleaning performance. The pH of the composition can be measured using a known pH meter by a method in accordance with JIS Z8802-1984. The pH measurement temperature is 25°C.

[0074] <Metal Content> The content (measured as ion concentration) of metals (for example, metal elements Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) contained as impurities in this composition is preferably 5 ppm by mass or less, and more preferably 1 ppm by mass or less, relative to the total mass of the composition. Since even higher purity compositions are expected to be required in the manufacture of state-of-the-art semiconductor devices, it is even more preferable that the content of the above metals is lower than 1 ppm by mass, i.e., on the order of ppb by mass or less, particularly preferably 100 ppb by mass or less, and most preferably less than 10 ppb by mass. A lower limit of 0 is preferred.

[0075] Methods for reducing the metal content include, for example, performing purification treatments such as distillation and filtration using ion exchange resins or filters at the stage of raw material use in manufacturing the composition, or at a stage after manufacturing the composition. Other methods for reducing the metal content include using containers that minimize the elution of impurities, as described later, as containers for holding the raw materials or the manufactured composition. Additionally, lining the inner walls of pipes with fluororesin can be applied to prevent metal components from leaching out during the manufacturing of the composition.

[0076] <Coarse Particles> This composition may contain coarse particles, but it is preferable that the content be low. Coarse particles refer to particles whose diameter (particle size) is 0.03 μm or more when the shape of the particle is considered to be a sphere. Coarse particles contained in this composition include particles such as dust, dirt, organic solids, and inorganic solids contained as impurities in the raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids introduced as contaminants into the preparation of the composition, which ultimately remain as particles in the composition without dissolving.

[0077] The coarse particle content in this composition is preferably 10,000 or less, and more preferably 5,000 or less, of particles with a particle size of 0.1 μm or larger per 1 mL of composition. The lower limit is preferably 0 or more particles per 1 mL of composition. The coarse particle content present in this composition can be measured in the liquid phase using a commercially available measuring device that uses a laser as a light source in a light scattering liquid particle measurement method. As a method for removing coarse particles, for example, purification treatment such as filtering, which will be described later, can be used.

[0078] <Abrasive Particles> Preferably, this composition contains substantially no abrasive particles. Specifically, substantially no abrasive particles means that the abrasive particle content is 1000 ppm by mass or less, preferably 500 ppm by mass or less, and more preferably 100 ppm by mass or less, relative to the total mass of the composition. The lower limit is preferably 0% by mass or more, relative to the total mass of the composition. Examples of abrasive particles include abrasive particles such as silicon dioxide contained in chemical mechanical polishing slurry and the descriptions in paragraphs

[0194] to

[0197] of International Publication No. 2021 / 131451. As a method for measuring the abrasive particle content, for example, a method of measuring in the liquid phase using a commercially available measuring device in a light scattering liquid particle measurement method with a laser as the light source is possible. As a method for adjusting the abrasive particle content, for example, known methods such as filtering treatment are possible.

[0079] [Method for Manufacturing This Composition] This composition can be manufactured by known methods. The manufacturing method is described in detail below.

[0080] [Preparation Process] This composition can be produced, for example, by mixing the above components. One method for preparing this composition is to sequentially add nonionic surfactant A, a specific compound, and any optional components to a container containing purified water, then stir to mix, and adjust the pH of the mixture by adding a pH adjuster as needed. When adding each component to the container, it may be added all at once or in multiple separate additions.

[0081] The stirring device and stirring method used to prepare the solution of this composition may be any known device as a stirrer or disperser. Examples of stirrs include industrial mixers, portable stirrers, mechanical stirrers, and magnetic stirrers. Examples of dispersers include industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.

[0082] The mixing of each component in the preparation process of this composition, the purification process described later, and the storage of the manufactured composition are preferably carried out at 40°C or below, and more preferably at 30°C or below. The lower limit is preferably 5°C or above, and more preferably 10°C or above. By preparing, processing, and / or storing the composition within the above temperature range, the performance can be maintained stably for a long period of time.

[0083] <Purification> It is preferable to perform a purification treatment on one or more of the raw materials for preparing this composition beforehand. Examples of known purification methods include distillation, ion exchange, and filtration. The degree of purification is preferably such that the purity of the raw materials is 99% by mass or higher, and more preferably such that the purity of the stock solution is 99.9% by mass or higher. The upper limit is preferably 99.9999% by mass or lower.

[0084] Methods of purification include, for example, passing the raw material through an ion exchange resin or RO membrane (Reverse Osmosis Membrane), reprecipitation, distillation of the raw material, and filtering. Multiple of the above purification methods may be combined as part of the purification process. For example, after primary purification by passing the raw material through an RO membrane, secondary purification may be performed by passing it through a purification apparatus consisting of a cation exchange resin, anion exchange resin, or mixed-bed ion exchange resin. Furthermore, the purification process may be performed multiple times.

[0085] The filters used for filtering are not particularly limited as long as they have been conventionally used for filtration purposes. For example, filters made of fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyallyl sulfone (PAS), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density or ultra-high molecular weight) are used. Among these materials, materials selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesins (including PTFE and PFA), and polyamide resins (including nylon) are preferred, and fluororesin filters are more preferred. By filtering raw materials using filters made of these materials, highly polar foreign substances that are likely to cause defects can be effectively removed.

[0086] <Container> This composition (including the form of the diluted composition described later) can be filled into any container and stored, transported, and used, as long as corrosiveness or other issues do not pose a problem.

[0087] As for the container, a container with a high degree of cleanliness inside and suppressed elution of impurities from the inner wall of the container's containment into each liquid is preferred for semiconductor applications. Examples of such containers include, but are not limited to, the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd. Furthermore, as a container, the containers exemplified in paragraphs

[0121] to

[0124] of International Publication No. 2022 / 004217 can also be referenced, and the contents of these are incorporated herein by reference.

[0088] These containers are preferably cleaned inside before being filled with the composition. The liquid used for cleaning is preferably one that has a reduced amount of metal impurities. The composition may be bottled in containers such as gallon bottles or quart bottles after production for transport and storage.

[0089] To prevent changes in the components of this composition during storage, the container may be purged with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. During transport, the temperature may be room temperature, or it may be controlled to a range of -20°C to 20°C to prevent deterioration.

[0090] <Cleanroom> It is preferable that all handling, processing, analysis, and measurement of this composition, including the manufacturing, opening and cleaning of containers, and filling of this composition, be carried out in a cleanroom. The cleanroom preferably meets the 14644-1 cleanroom standard. It is preferable that it meets any of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably ISO Class 1 or ISO Class 2, and even more preferably ISO Class 1.

[0091] [Dilution Step] This composition may be diluted using a diluent such as water, and then used as a diluted composition (diluted composition) for treating the object to be treated. The diluted composition is also a form of this composition as long as it satisfies the requirements of the present invention.

[0092] It is preferable to perform a purification treatment on the diluent used in the dilution step beforehand. Furthermore, it is even more preferable to perform a purification treatment on the diluted composition obtained in the dilution step. Examples of purification treatments for this composition include ion component reduction treatment using an ion exchange resin or RO membrane, and foreign matter removal using filtering, and it is preferable to perform either of these treatments.

[0093] The dilution ratio of the composition in the dilution step can be appropriately adjusted depending on the type and content of each component and the material to be treated. However, the ratio of the diluted composition to the original composition (dilution ratio) is preferably 1.2 to 10,000 times by mass ratio or volume ratio (volume ratio at 23°C), more preferably 2 to 3,000 times, even more preferably 2 to 1,000 times, and particularly preferably 2 to 500 times. Furthermore, the composition is preferably diluted with water (preferably ultrapure water).

[0094] The change in pH before and after dilution (the difference between the pH of the original composition before dilution and the pH of the diluted composition) is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.8 or less. The pH of the original composition before dilution and the pH of the diluted composition are preferably as described above. The pH of the diluted composition may be adjusted using the pH adjusting agent described above.

[0095] The specific method for diluting this composition may be carried out in accordance with the preparation step for this composition described above. The stirring device and stirring method used in the dilution step may also be carried out using the known stirring device mentioned in the preparation step for the processed liquid described above.

[0096] [Applications] This composition is used for cleaning workpieces that have undergone chemical mechanical polishing (hereinafter also referred to as "workpieces after CMP treatment"). The cleaning method is not particularly limited, and known methods can be used. The apparatus and conditions used in the cleaning process using this composition can be appropriately selected from known apparatus and conditions depending on the type of workpiece, the type and amount of residue to be removed. For example, the processing methods described in paragraphs

[0085] to

[0088] of International Publication No. 2017 / 169539 can be used, and these contents are incorporated herein.

[0097] This composition can be suitably used when cleaning a workpiece after CMP treatment by physically contacting the surface of the workpiece with cleaning members such as pads and brushes, and is particularly suitable for use when cleaning a workpiece after CMP treatment using a pad. The above cleaning process using a pad is generally also called rinse polishing, buff polishing, or buff cleaning, and is a process that reduces the residue present on the surface of the workpiece using a pad. Specifically, this composition is supplied to the contact area between the workpiece and the pad, and the surface of the CMP-treated workpiece is brought into contact with the pad, and the workpiece and the pad are moved relative to each other. As a result, the residue on the surface of the workpiece is removed by the frictional force of the pad and the chemical action of this composition.

[0098] [Pad] The pad described above is not particularly limited and can be appropriately selected depending on the type of material to be processed, the type of residue to be removed, and the equipment used. The pad is not particularly limited as long as it is used in the processing process of semiconductor substrates, but it is preferable that it is a pad used in CMP processing. Specific examples of pads include resin pads such as foamed polyurethane buff pads, nonwoven fabrics, suede buff pads, and sponge buff pads.

[0099] [Workpiece to be treated] After the CMP treatment, it is preferable that two or more different materials are exposed on the surface of the workpiece that has undergone chemical mechanical polishing. Examples of the two or more materials include metals and silicon compounds, and it is preferable that all of these be included. Specific examples of silicon-containing materials include silicon oxides, silicon nitrides, and silicon oxynitrides, among which silicon dioxide (SiO₂) is preferable. ２ ), tetraethyl orthosilicate (Si(OC ２ H ５ ) ４ TEOS, or silicon nitride (Si ３ N ４ ) is preferred. The workpiece is often a semiconductor substrate. If the semiconductor substrate contains materials such as metal and silicon compounds, the materials may be located anywhere on the surface, sides, or grooves of the semiconductor substrate, for example. Furthermore, if the semiconductor substrate contains metal, this includes not only cases where the metal is directly on the surface of the semiconductor substrate, but also cases where the metal is on the semiconductor substrate via other layers.

[0100] Examples of the above-mentioned metals include at least one metal M selected from the group consisting of cobalt (Co), tungsten (W), ruthenium (Ru), titanium (Ti), tantalum (Ta), molybdenum (Mo), copper (Cu), aluminum (Al), chromium (Cr), hafnium (Hf), osmium (Os), platinum (Pt), nickel (Ni), manganese (Mn), iron (Fe), zirconium (Zr), palladium (Pd), lanthanum (La), niobium (Nb), and iridium (Ir), with at least one metal selected from the group consisting of tungsten, cobalt, ruthenium, copper, aluminum, titanium, and tantalum being preferred.

[0101] The metal is preferably present as a metal layer containing the metal. Examples of the form of the metal contained in the metal layer include elemental metal M, alloys containing metal M, oxides of metal M, nitrides of metal M, and oxynitrides of metal M. In particular, the workpiece is preferably having a metal layer containing metal M, and more preferably having a metal layer containing at least one selected from the group consisting of tungsten, cobalt, ruthenium, copper, aluminum, titanium, titanium nitride, tantalum, tantalum nitride, and alloys consisting of two or more of these.

[0102] In addition to the metal layer described above, the object to be processed may also have, for example, a semiconductor substrate, an insulating film, a metal wiring film, and a barrier metal.

[0103] Examples of wafers constituting semiconductor substrates include silicon (Si) wafers, silicon carbide (SiC) wafers, and silicon-based wafers such as silicon-containing resin wafers (glass epoxy wafers), as well as gallium phosphide (GaP) wafers, gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers. Examples of silicon wafers include n-type silicon wafers doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb)), and p-type silicon wafers doped with trivalent atoms (e.g., boron (B) and gallium (Ga)). Examples of silicon in silicon wafers include single-crystal silicon, polysilicon (polycrystalline silicon), and amorphous silicon. Examples of insulating films include oxide films and nitride films, and more specifically, silicon oxide films (e.g., silicon dioxide (SiO₂)). ２ ) film and tetraethyl orthosilicate (Si(OC ２ H ５ ) ４ ) film (TEOS film, etc.), silicon nitride film (for example, silicon nitride (Si ３ N ４ Examples include silicon dioxide (SOC) and silicon carbide nitride (SiNC), and low-dielectric constant (Low-k) films (for example, carbon-doped silicon oxide (SiOC) films, black diamond (BD) films, and silicon carbide (SiC) films), with low-dielectric constant (Low-k) films being preferred.

[0104] The material to be treated preferably contains a silicon compound. The silicon compound preferably contains a silicon atom and at least one of an oxygen atom and a nitrogen atom. Specific examples of silicon compounds include the insulating film materials listed above.

[0105] Examples of wiring metals include copper (Cu), copper-aluminum alloy (CuAl), copper-titanium alloy (CuTi), copper-chromium alloy (CuCr), copper-manganese alloy (CuMn), copper-tantalum alloy (CuTa), copper-niobium alloy (CuNb), copper-tungsten alloy (CuW), silver (Ag), and gold (Au).

[0106] Examples of barrier metals include tantalum (Ta), tantalum nitride (TaN), titanium nitride (TiN), cobalt (Co), cobalt alloys, ruthenium (Ru), and ruthenium alloys.

[0107] The material to be treated preferably includes at least one selected from the group consisting of tungsten, cobalt, ruthenium, copper, aluminum, titanium, titanium nitride, tantalum, tantalum nitride, and alloys comprising two or more of these materials.

[0108] <CMP Treatment> The above-described CMP (chemical mechanical polishing) treatment is a process that planarizes the surface of a substrate having a layer selected from, for example, a metal wiring film, a barrier metal, and an insulating film, by a combined chemical action of chemical action and mechanical polishing using a polishing slurry containing polishing particles (abrasive grains). Specifically, for example, the surface of the workpiece is brought into contact with a polishing pad, and the workpiece and the polishing pad are moved relative to each other while supplying polishing slurry to the contact area. As a result, the material on the surface of the workpiece is removed and planarized by the frictional force between the polishing pad, the polishing slurry, and the surface of the workpiece, as well as the chemical action of the polishing slurry. The polishing pad is not particularly limited, and pads commonly used in CMP treatment, such as nonwoven fabrics, foamed polyurethanes, and porous fluororesins, can be used.

[0109] The surface of a workpiece subjected to CMP treatment may have residues such as abrasive particles used in the CMP treatment (e.g., silica and alumina), polished metal wiring films, and / or metal impurities derived from barrier metals. Organic substances derived from the CMP composition used during the CMP treatment may also remain as residues. These residues may, for example, short-circuit wirings and degrade the electrical properties of the semiconductor substrate; therefore, CMP-treated semiconductor substrates are subjected to a cleaning process to remove these residues from the surface. Specific examples of CMP-treated workpieces include, but are not limited to, the CMP-treated substrate described in the Journal of the Japan Society for Precision Engineering, Vol. 84, No. 3, 2018.

[0110] [Method for manufacturing a cleaned workpiece] As described above, this composition is used to clean a workpiece after CMP treatment, and the cleaned workpiece is obtained by the above cleaning. The method for manufacturing a cleaned workpiece according to the present invention includes a manufacturing method that includes a cleaning step using a pad, and a manufacturing method that includes a cleaning step without using a pad, as shown below. Each method will be described in detail below.

[0111] [Cleaning process using a pad] A manufacturing method including a cleaning process using a pad includes a step (hereinafter also referred to as "cleaning process A") in which the composition is supplied, a workpiece that has undergone chemical mechanical polishing treatment is brought into contact with the pad, the workpiece and the pad are moved relative to each other to clean the workpiece, and a cleaned workpiece is obtained. In the above manufacturing method, the composition is supplied to the contact area between the workpiece and the pad, and cleaning is performed. Preferred embodiments of the workpiece, pad, equipment and conditions used in cleaning process A are as described above.

[0112] In the cleaning process A, any method commonly used in this field can be used to bring the workpiece and the pad into contact, but it is preferable to move the workpiece and the pad relative to each other while the pad is pressed against the workpiece. The pressure applied during pressing is preferably 5 to 100 hPa, and more preferably 10 to 50 hPa.

[0113] The temperature of the composition is not particularly limited, but 10 to 60°C is preferred, and 15 to 50°C is more preferred, in terms of superior cleaning performance and reduced damage to the material. The pH of the composition is preferably in the preferred mode of pH described above. The contact time between the object to be treated and the composition may be appropriately changed depending on the type and content of each component contained in the composition, but 10 to 120 seconds is preferred, 20 to 90 seconds is more preferred, and 20 to 60 seconds is even more preferred.

[0114] The supply rate (feed rate) of this composition is preferably 50 to 5000 mL / min, and more preferably 100 to 2000 mL / min.

[0115] The processing method in washing step A may be either a single-wafer method or a batch method. The single-wafer method processes one item at a time, while the batch method processes multiple items simultaneously.

[0116] [Padless Cleaning Process] A manufacturing method including a padless cleaning process includes a step of bringing the composition into contact with a workpiece that has undergone chemical mechanical polishing (hereinafter also referred to as "cleaning process B"). Preferred embodiments of the workpiece, equipment used, and conditions in cleaning process B are as described above. There are no particular limitations on the method of bringing the workpiece into contact with the composition, and examples include immersing the workpiece in the composition placed in a tank, spraying the composition onto the workpiece, flowing the composition onto the workpiece, and combinations thereof. Contact between the workpiece and the composition in the contact process may be performed only once or two or more times. If it is performed two or more times, the same method may be repeated or different methods may be combined.

[0117] The temperature of the composition is not particularly limited, but 10 to 60°C is preferred, and 15 to 50°C is more preferred, in terms of superior cleaning performance and reduced damage to the material. The supply amount (supply rate) of the composition is preferably 50 to 5000 mL / min, and more preferably 500 to 2000 mL / min. The contact time between the object to be treated and the composition may be appropriately changed depending on the type and content of each component contained in the composition, as well as the target and purpose of use of the composition, but 10 to 120 seconds is preferred, 20 to 90 seconds is more preferred, and 30 to 60 seconds is even more preferred.

[0118] The cleaning process B may employ any method commonly used in this field. For example, it may be a scrubbing method in which a cleaning member such as a brush is physically brought into contact with the surface of the object to be treated while supplying the composition to remove residues, or a spin (dropping) method in which the composition is dropped onto the object to be treated while it is rotated. In the immersion method, it is preferable to apply ultrasonic treatment to the object immersed in the composition, as this can further reduce impurities remaining on the surface of the object to be treated.

[0119] In cleaning step B, a mechanical stirring method may be used to further enhance the cleaning ability of the composition. Examples of mechanical stirring methods include circulating the composition over the workpiece, flowing or spraying the composition over the workpiece, and stirring the composition with ultrasound or megasonic waves.

[0120] The method for producing a washed workpiece according to the present invention may further include a washing step using a treatment solution other than the present composition. As the treatment solution other than the present composition, known compositions can be used depending on the type of workpiece and the type and amount of residue to be removed. Examples of components that the treatment solution other than the present composition may contain include water-soluble polymers such as polyvinyl alcohol, dispersion media such as water, acids such as nitric acid, basic compounds such as amines, surfactants, antibacterial agents, and phosphonic acid compounds. The treatment solution other than the present composition may be acidic, basic, or neutral, and is preferably acidic (more preferably pH 6 or lower) or basic (more preferably pH 8 or higher).

[0121] <Rinsing Step> After the cleaning step described above, a step of bringing the workpiece into contact with a rinsing solution (hereinafter also referred to as the "rinsing step") may be performed. By performing the rinsing step, the workpiece obtained in the cleaning step can be washed with the rinsing solution, and residues can be efficiently removed. The rinsing step is preferably performed immediately after the cleaning step of the semiconductor substrate, and is a step of rinsing the workpiece with the rinsing solution. The rinsing step may be performed using the mechanical stirring method described above.

[0122] Examples of rinse solutions include water (preferably DI water), methanol, ethanol, isopropyl alcohol (IPA), N-methylpyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Alternatively, an aqueous rinse solution with a pH greater than 8.0 (such as diluted aqueous ammonium hydroxide) may be used.

[0123] As a method for bringing the rinsing solution into contact with the object to be treated, the method of bringing the above composition into contact with the object to be treated can be applied in the same manner. The contact time between the object to be treated and the rinsing solution can be appropriately changed depending on the type and content of each component contained in the composition, as well as the object and purpose of use of the composition. In practice, 10 to 120 seconds is preferred, 20 to 90 seconds is more preferred, and 30 to 60 seconds is even more preferred.

[0124] [Drying Process] If necessary, a drying process may be performed to dry the workpiece. Examples of drying methods include spin drying, passing a drying gas over the workpiece, heating the substrate with heating means such as a hot plate and infrared lamp, Marangoni drying, Rotagoni drying, IPA drying, and any combination thereof.

[0125] [Method for Manufacturing Electronic Devices] The above-described method for manufacturing the cleaned workpiece can be suitably applied to the manufacturing process of electronic devices. The above manufacturing method may be carried out in combination before or after other processes performed on the substrate. The above manufacturing method may be incorporated into other processes during the implementation of the above manufacturing method, or the above manufacturing method may be incorporated into other processes. Other processes include, for example, processes for forming structures such as metal wiring, gate structures, source structures, drain structures, insulating films, ferromagnetic layers, and non-magnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and modification), resist formation processes, exposure processes, removal processes, heat treatment processes, cleaning processes, and inspection processes.

[0126] The above manufacturing method may be carried out at any stage of the backend process (BEOL), middle process (MOL), or frontend process (FEOL), and is preferably carried out during the frontend process or middle process.

[0127] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0128] In the following examples, the pH of the detergent was measured at 25°C in accordance with JIS Z8802-1984 using a pH meter (Horiba, Ltd., model "F-74"). In the preparation of the compositions of the examples and comparative examples, the handling of containers, preparation of the compositions, filling, storage, and analytical measurements were carried out in a clean room. Containers used for the preparation, filling, and storage of the compositions were washed with the solvent used for preparation or with the prepared compositions before use.

[0129] [Raw Materials for the Composition] The following compounds were used to manufacture the composition. Note that all components used in the examples and comparative examples were of semiconductor grade or equivalent high-purity grade.

[0130] [Nonionic surfactants] Of the nonionic surfactants listed below, compound A10 was used as a comparative compound in the preparation of the comparative composition. • Compound A1: Emulgen A-500 (Polyoxyethylene distyrenated phenyl ether, manufactured by Kao Corporation) • Compound A2: Emulgen A-90 (Polyoxyethylene distyrenated phenyl ether, manufactured by Kao Corporation) • Compound A3: Emulgen 150 (Polyoxyethylene (47) lauryl ether, manufactured by Kao Corporation) • Compound A4: Emulgen 2025G (Polyoxyethylene (25) octyldodecyl ether, manufactured by Kao Corporation) • Compound A5: Amito 320 (Polyoxyethylene (20) alkyl (C14-18) amine, manufactured by Kao Corporation) • Compound A6: Emanone 3199VB (Polyethylene glycol monostearate (140 E.O. (average number of moles of ethylene oxide added)), manufactured by Kao Corporation) • Compound A7: Emanone CH-60 (Polyoxyethylene hydrogenated castor oil (60 E.O.), manufactured by Kao Corporation) Compound A8: Newpol PE-68 (Polyoxyethylene polyoxypropylene glycol (block polymer), manufactured by Sanyo Chemical Industries, Ltd.) Compound A9: Cellmolis B044 (Polyglyceryl-20 lauryl ether, manufactured by Daicel Corporation) Compound A10: Emulgen 108 (Polyoxyethylene (6) lauryl ether, manufactured by Kao Corporation)

[0131] [Specific Compound 1] Compound B1: Nitric acid Compound B2: Phosphoric acid Compound B3: Sulfuric acid Compound B4: Citric acid Compound B5: Etidronic acid

[0132] [Specific Compounds 2] • Compound C1: Trishydroxymethylaminomethane (Tris) • Compound C2: 2-amino-2-methyl-1-propanol (AMP) • Compound C3: 2-dimethylamino-2-methyl-1-propanol (DMAMP) • Compound C4: Tetraethylammonium hydroxide (TEAH) • Compound C5: Bis-trispropane (1,3-bis[tris(hydroxymethyl)methylamino]propane)

[0133] [Antibacterial agents] Compound D1: MIT (methylisothiazolinone) Compound D2: Dehydroacetic acid Compound D3: Cresol Compound D4: TBZ (2-(4-thiazolyl)benzimidazole) Compound D5: [(4-chlorophenoxy)methyl]-3-iodo-2-propynyl ether (IF1000)

[0134] [Corrosion inhibitors] Compound E1: L-arginine Compound E2: L-histidine Compound E3: L-lysine Compound E4: Bis(p-chlorophenyl diguanide) hexanedigluconate (chlorhexidine gluconate)

[0135] [Production of Compositions] The production method of the compositions will now be described. The above compounds and pure water were added in the amounts (mass%) shown in the table below and stirred thoroughly to obtain concentrated solutions (stock solutions). The obtained concentrated solutions were diluted with pure water as a diluent at the dilution ratios (volume ratios) shown in the dilution ratio column of the table below to prepare each composition. In the compositions, the remaining components (residue) that are not explicitly listed as components of the composition in the table are pure water. Finally, after preparing each of the above compositions, they were filtered through a 10 μm PP filter (Pall Co. product: HDCII J-100) to obtain compositions 1, 7, 24, 25, 27, and 29-31. In all of the compositions of the examples, the concentration of the nonionic surfactant was equal to or greater than the critical micelle concentration at 25°C. The compositions of the other examples and comparative examples were produced according to the same procedure as in the above examples.

[0136] [Polishing and Cleaning of Each Workpiece] Each workpiece was polished and cleaned using the compositions of Examples 1, 7, 24, 25, 27, and 29-31 according to the procedure shown below.

[0137] [Preparation of Workpieces] Workpieces 1 and 2 that had undergone CMP treatment were prepared according to the following procedure. First, a patterned wafer 10 having line sections and space sections (using SEMATEC754TEG as a mask, line / space: 0.18 μm / 0.18 μm) was prepared according to the following procedure. Figure 1 shows a cross-sectional view of the patterned wafer 10. The patterned wafer 10 has a 200 nm thick TEOS (silicon oxide) layer as an insulating layer 14 on a silicon wafer 12, or a 200 nm thick Si ３ N ４ A silicon nitride (SNI) layer was formed, and a portion of this insulating layer was processed using the above mask to form wiring. Then, a 10 nm thick TiN (titanium nitride) layer 16 was formed over the entire surface, and further, a W (tungsten) layer 18 was formed in the grooves to create the wafer. Following the above procedure, a patterned wafer 1 in which the insulating layer is a TEOS layer and a wafer in which the insulating layer is a Si ３ N ４ A wafer 2 with a patterned layer was prepared.

[0138] The patterned wafers 1 and 2 prepared using the above procedure were subjected to CMP processing according to the following procedure.

[0139] (Composition of polishing solution A) Colloidal silica (PL5D, manufactured by Fuso Chemical Industry Co., Ltd.): 3% by mass Malonic acid: 0.03% by mass Glycine: 0.5% by mass Hydrogen peroxide: 1% by mass Water: remainder pH: 2.2

[0140] (Polishing equipment and conditions) ・Polishing equipment: FREX-300II (manufactured by Ebara Corporation) ・Polishing pad: FUJIBO Pad H800 (manufactured by Fujibo Co., Ltd.) ・Polishing pressure: 105 hPa ・Polishing fluid supply rate: 250 ml / min ・Table rotation speed: 80 rpm ・Head rotation speed: 78 rpm

[0141] CMP treatment was performed on patterned wafers 1 and 2 using polishing solution B, which was obtained by adding 100 ppm of iron nitrate to polishing solution A, and a polishing apparatus under the above conditions. The end point of polishing was defined as the point when the TiN layer placed in the line area was exposed, and the end point detection device of the polishing apparatus was used to detect the end point. Subsequently, an additional 60 seconds of polishing was performed using polishing solution A. As a result of this additional polishing, a W layer was placed in the line area, and a TEOS layer or Si was placed in the space area. ３ N ４ Two polishing bodies, 1 and 2, were prepared with the layers arranged on them. The dishing values ​​of the W layer in polishing bodies 1 and 2 were measured using an AFM (Atomic Force Microscope), and the average value of 10 points was found to be 6 nm and 5 nm, respectively.

[0142] [Cleaning Treatment 1 (Cleaning using a resin pad)] Next, the polished objects 1 and 2 after the CMP treatment were cleaned using a resin pad with the respective compositions prepared according to the procedure in [Production of Composition] above, in the following procedure. The apparatus and cleaning conditions are shown below.

[0143] (Cleaning equipment and conditions) ・Cleaning (polishing) equipment: FREX-300X (manufactured by Ebara Corporation) ・Resin pad: FUJIBO Pad H800 (manufactured by Fujibo Co., Ltd.) ・Cleaning (polishing) pressure: 35 hPa ・Composition supply rate: 200 ml / min ・Table rotation speed: 90 rpm ・Head rotation speed: 85 rpm ・Cleaning time: 45 seconds

[0144] The polished objects 1 and 2, after the CMP treatment described above, were transferred onto the resin pad used in the CMP treatment, and each polished surface was cleaned using the cleaning apparatus and conditions described above. Each composition was filtered through a 1.0 μm PP filter (Pall Co. product: HDCII J-006) before being supplied onto the resin pad. The compositions used were those immediately after manufacturing.

[0145] [Cleaning Treatment 2 (Cleaning with Brush Scrub)] Each workpiece after Cleaning Treatment 1 was further cleaned with a brush scrub according to the procedure shown below. The work was carried out in a cleanroom at 23°C. The polishing surface of each workpiece after Cleaning Treatment 1 was cleaned with a brush scrub for 60 seconds in the cleaning unit 1 of the apparatus using the same composition and apparatus as in Cleaning Treatment 1, and then cleaned with a brush scrub for 30 seconds in the cleaning unit 2. Finally, after rinsing with pure water for 60 seconds, the workpieces were spin-dried at a rotation speed of 1000 rpm in the drying unit 2 while blowing nitrogen gas onto the workpieces to obtain cleaned workpieces 1 and 2 for evaluation. The composition used above was stored in a cleanroom (23°C) for two weeks, and then Cleaning Treatment 1 and Cleaning Treatment 2 were carried out in the same manner using the stored composition to obtain cleaned workpieces 1 and 2 using the stored composition.

[0146] [Evaluation] The following evaluations were performed using the polished objects 1 and 2 described above.

[0147] [Particle Removal and Organic Matter Removal] Using the composition immediately after manufacture, the particle removal and organic matter removal properties were evaluated using the following procedure with the polished works 1 and 2 obtained by performing the above-described [Washing Treatment 1] and [Washing Treatment 2]. Using a defect detection device (AMAT Corporation, Complus-II), the number of detected signal intensities corresponding to defects with a length of 0.1 μm or more remaining on the polished surfaces of each polished work 1 and 2 that had been washed with the composition immediately after manufacture was measured. The type of defect was identified by observing the defects corresponding to the above using a defect review SEM (AMAT Corporation, SEMVISION G5). From the obtained number of defects, the particle removal and organic matter removal properties were evaluated according to the following evaluation criteria. For both evaluations, an evaluation of D or higher is preferable in practical terms.

[0148] (Evaluation criteria: Particle removal capability) A: Less than 10 particle defects per substrate B: 10 or more, less than 20 particle defects per substrate C: 20 or more, less than 30 particle defects per substrate D: 30 or more, less than 50 particle defects per substrate E: 50 or more particle defects per substrate

[0149] (Evaluation criteria: Organic matter removal capability) A: Less than 20 organic matter defects per substrate B: 20 ​​or more, but less than 50 organic matter defects per substrate C: 50 or more, but less than 100 organic matter defects per substrate D: 100 or more, but less than 150 organic matter defects per substrate E: 150 or more organic matter defects per substrate

[0150] [Residue Removal Performance After Time-Long Test (Time-Long Performance)] The time-long performance of the composition was evaluated by checking the residue removal performance on polished works 1 and 2 obtained by performing the above-mentioned [Washing Treatment 1] and [Washing Treatment 2] using the composition after it had been stored for two weeks. Using a defect detection device (AMAT Corporation, ComPlus-II), the number of detected signal intensities corresponding to defects with a length of 0.1 μm or more remaining on each polished surface of polished works 1 and 2, which had been washed with the composition after it had been stored for two weeks as described above, was measured. The increase in defects when washing with the composition after it had been stored for two weeks was confirmed by comparing the total number of defects obtained with the total number of defects when washing with the composition immediately after preparation, which was evaluated in the above-mentioned [Particle Removal Performance and Organic Matter Removal Performance]. The time-long performance was evaluated from the obtained increase in defects according to the evaluation criteria below.

[0151] (Evaluation Criteria) A: Increase in defects per board is less than 10 B: Increase in defects per board is 10 or more but less than 15 C: Increase in defects per board is 15 or more but less than 20 D: Increase in defects per board is 20 or more but less than 50 E: Increase in defects per board is 50 or more

[0152] [Corrosion Resistance] For the polished object 1 obtained by performing the above-described [Cleaning Treatment 1] and [Cleaning Treatment 2], the dishing value of the W layer (10 μm line portion) was re-evaluated using AFM and the average value of 10 points was obtained. The change in dishing value was calculated by comparing the obtained dishing value with the dishing value of the polished object 1 before performing [Cleaning Treatment 1] and [Cleaning Treatment 2]. As mentioned above, the dishing value of the polished object 1 before performing [Cleaning Treatment 1] and [Cleaning Treatment 2] was 6 nm. From the obtained change in dishing value, the corrosion resistance was evaluated according to the evaluation criteria below.

[0153] A: Change in dishing value is less than 10 Å (1 nm) B: Change in dishing value is 10 Å or more and less than 30 Å C: Change in dishing value is 30 Å or more and less than 40 Å D: Change in dishing value is 40 Å or more

[0154] In addition, in other examples and comparative examples other than Examples 1, 7, 24, 25, 27, and 29-31, the cleaned polished objects 1-2 were prepared using the same procedure as in Examples 1, 7, 24, 25, 27, and 29-31, and evaluated using the same procedure as described above.

[0155] [Results] The composition of each composition in the examples and comparative examples, and the evaluation results are shown in the table below. In the table, the "mass%" column for each component indicates the content (mass%) of each component relative to the total mass of the concentrate. The remainder of the concentrate, other than (a) to (e), is pure water. In the table, the "(a) / (b) or (a) / (c)" column indicates the mass ratio of the content of (a) nonionic surfactant to the total content of (b) specific compound 1 and (c) specific compound 2. In the table, the "(a) / (d)" column indicates the mass ratio of the content of (a) nonionic surfactant to the content of (d) antibacterial agent. In the table, the "(a) / (e)" column indicates the mass ratio of the content of (a) nonionic surfactant to the content of (e) corrosion inhibitor. In the table, the "Dilution Ratio" column indicates the dilution ratio (volume ratio) of the concentrate when preparing the composition, as described above. In the table, the numerical value in the pH column indicates the pH of the composition at 25°C as measured by the pH meter described above. The values ​​in the "pH after dilution" column are the values ​​measured for compositions prepared by diluting the concentrated solution.

[0156]

[0157]

[0158] The results shown in the table above confirm that the composition of the present invention exhibits excellent particle removal and organic matter removal properties when applied to a workpiece containing a hydrophilic surface derived from an insulating film such as an oxide film or nitride film that has undergone CMP treatment.

[0159] From comparisons of Examples 1 to 11, it was confirmed that the time-dependent performance is superior when the composition further contains an antibacterial agent. From comparisons of Examples 12 and 14 to 17, it is shown that when the mass ratio of the nonionic surfactant content to the antibacterial agent content is greater than 5.0 and less than 10,000, the organic matter removal performance is superior. From comparisons of Examples 1 to 14, it is shown that when the mass ratio of the nonionic surfactant content to the total content of specific compounds is greater than 0.1, the particle removal performance is superior, and when it is less than 10,000, the organic matter removal performance is superior. From comparisons of Examples 7 to 12 and 18 with Example 17, and from comparisons of Examples 24 to 27, it was confirmed that the particle removal performance is superior when the pH of the composition is 6 or less or 7.5 or more. From comparisons of Examples 18 to 23, it is shown that when the pH of the composition is 9.5 or less, the particle removal performance is superior. Comparisons of Examples 23-28 and 37-41 show that the corrosion protection is better when the composition further contains a corrosion inhibitor. Comparisons of Examples 42-46 show that when the mass ratio of the content of nonionic surfactant A to the content of corrosion inhibitor is 5.0 to 10000, the organic matter removal performance is better, and when it is 10.0 to 5000, the organic matter removal performance is even better.

[0160] 10 Patterned wafer 12 Silicon wafer 14 Insulating layer 16 Titanium nitride (TiN) layer 18 Tungsten (W) layer

Claims

1. A composition used for cleaning a workpiece that has undergone chemical mechanical polishing, comprising: a nonionic surfactant having a polyoxyalkylene chain and a hydrophilic-lipophilic balance value of 14 to 20; and a specific compound selected from the group consisting of inorganic acids, amino alcohols, organic acids, quaternary ammonium compounds, and aliphatic polyamines (excluding zwitterionic compounds), wherein the organic acid has at least one group selected from the group consisting of carboxylic acid groups, phosphonic acid groups, and sulfonic acid groups, and the mass ratio of the content of the nonionic surfactant to the total content of the specific compound is 0.1 to 10000.

2. The composition according to claim 1, wherein the specified compound comprises nitric acid, phosphoric acid, or sulfuric acid.

3. The composition according to claim 1, wherein the pH is 6 or less.

4. The composition according to claim 1, wherein the pH is 1 to 6.

5. The composition according to claim 1, wherein the specific compound is the amino alcohol.

6. The composition according to claim 5, wherein the amino alcohol is selected from the group consisting of trishydroxymethylaminomethane, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, 1,3-bis[tris(hydroxymethyl)methylamino]propane, monoethanolamine, diethanolamine, N-methyldiethanolamine, 2-amino-2-methyl-1-propanol, triethanolamine, diethylene glycolamine, 2-(dimethylamino)-2-methyl-1-propanol, and 2-(2-aminoethylamino)ethanol.

7. The composition according to claim 1, wherein the pH is 7.5 or higher.

8. The composition according to claim 1, wherein the pH is 7.5 to 9.

5.

9. The composition according to claim 1, wherein the content of the nonionic surfactant is equal to or greater than the critical micelle concentration of the nonionic surfactant at 25°C.

10. The composition according to claim 1, wherein the polyoxyalkylene chain has a structure consisting of a group selected from the group consisting of an oxyethylene group and an oxypropylene group.

11. The composition according to claim 1, further comprising an antibacterial agent.

12. The composition according to claim 1, which is substantially free of abrasive particles.

13. The composition according to claim 1, wherein the workpiece subjected to the chemical mechanical polishing treatment comprises silicon atoms and at least one of oxygen atoms and nitrogen atoms.

14. The composition according to claim 1, wherein two or more different materials are exposed on the surface of the workpiece that has been subjected to chemical mechanical polishing.

15. The composition according to claim 1, wherein the workpiece subjected to the chemical mechanical polishing treatment comprises at least one selected from the group consisting of tungsten, cobalt, ruthenium, copper, aluminum, titanium, titanium nitride, tantalum, tantalum nitride, and alloys comprising two or more of these.

16. A method for producing a cleaned workpiece, comprising the step of bringing a composition according to any one of claims 1 to 15 into contact with a workpiece that has been subjected to chemical mechanical polishing.

17. A method for producing a cleaned workpiece, comprising the steps of supplying a composition according to any one of claims 1 to 15, bringing a workpiece subjected to chemical mechanical polishing treatment and a pad into contact, moving the workpiece and the pad relative to each other to clean the workpiece, and obtaining a cleaned workpiece.

18. The method for manufacturing a cleaned workpiece according to claim 17, wherein the workpiece and the pad are moved relative to each other while the pad is pressed against the workpiece.

19. A method for manufacturing an electronic device, comprising the method for manufacturing a cleaned workpiece as described in claim 17.

Images