Composition, method for manufacturing cleaned object to be processed, and method for manufacturing electronic device

Abstract

The present invention provides a composition that has excellent particle removability and organic matter removability when applied to an object to be processed which includes a hydrophobic surface that is derived from polysilicon, amorphous silicon, or the like that has been subjected to a CMP treatment. The present invention also provides a method for manufacturing a cleaned object to be processed, and a method for manufacturing an electronic device. A composition according to the present invention is used for cleaning of an object to be processed that has been subjected to a chemical mechanical polishing treatment. The composition contains: a nonionic surfactant that has a polyoxyalkylene chain and a hydrophilic-lipophilic balance value of 8.5 to 14; and a specific compound (excluding a zwitterionic compound) that is 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 that is 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 0.001 to 1,500.

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 materials (particles) have come to significantly affect the performance of equipment and, consequently, the yield of products.

[0003] Various contaminants and particles (hereinafter also referred to as residues) can be generated during each manufacturing process of semiconductor devices. To remove such residues during semiconductor manufacturing, substrate processing steps are appropriately performed.

[0004] For example, in the manufacturing of semiconductor devices, chemical mechanical polishing (CMP) is sometimes performed to planarize the surface of a semiconductor substrate having a metal wiring film, barrier metal, and insulating film using a polishing slurry containing polishing particles (e.g., silica and alumina).

[0005] In CMP processing, metallic components derived from the polishing particles used in the CMP process, the polished wiring metal film, and / or barrier metal tend to remain on the surface of the semiconductor substrate after polishing and on the materials used for polishing (e.g., polishing pads). Therefore, a step to remove these residues using a composition is generally performed after CMP processing.

[0006] 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.

[0007] As an example of a composition, Patent Document 1 discloses a polishing cleaning solution composition characterized by containing a nonionic surfactant and water, which can efficiently remove particles from the surface of a semiconductor substrate after chemical mechanical polishing.

[0008] Japanese Patent Publication No. 2004-323840

[0009] 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 hydrophobic surface derived from polysilicon or amorphous silicon (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"), it was confirmed that particles and organic residues were present on the workpiece, and that the removal of these was insufficient.

[0010] Here, "particles" refer to abrasive particles used in CMP processing, metallic 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 cleaning solution composition.

[0011] Therefore, the object of the present invention is to provide a composition that exhibits excellent particle removal and organic matter removal properties when applied to a workpiece containing a hydrophobic surface derived from polysilicon or amorphous silicon that has undergone CMP treatment.

[0012] Furthermore, the present invention also aims to provide a method for manufacturing a cleaned workpiece and a method for manufacturing an electronic device.

[0013] 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.

[0014] [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 8.5 to 14; 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 0.001 to 1500.

[0015] 〔2〕 The composition according to 〔1〕, wherein the specific compound contains nitric acid, phosphoric acid or sulfuric acid.

[0016] 〔3〕 The composition according to 〔1〕 or 〔2〕, wherein the pH is 6 or less.

[0017] 〔4〕 The composition according to any one of 〔1〕 to 〔3〕, wherein the pH is 1 to 6.

[0018] 〔5〕 The composition according to any one of 〔1〕 to 〔4〕, wherein the specific compound is an amino alcohol.

[0019] 〔6〕 The composition according to 〔5〕, wherein the amino alcohol is selected from the group consisting of tris (hydroxymethyl) aminomethane, 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.

[0020] 〔7〕 The composition according to 〔5〕 or 〔6〕, wherein the pH is 7.5 or more.

[0021] 〔8〕 The composition according to any one of 〔5〕 to 〔7〕, wherein the pH is 7.5 to 11.5.

[0022] 〔9〕 The composition according to any one of 〔1〕 to 〔8〕, wherein the content of the nonionic surfactant is not less than the critical micelle concentration of the nonionic surfactant at 25 °C.

[0023] 〔10〕 The composition according to any one of 〔1〕 to 〔9〕, wherein the polyoxyalkylene chain has a structure composed of a group selected from the group consisting of an oxyethylene group and an oxypropylene group.

[0024] 〔11〕 The composition according to any one of 〔1〕 to 〔10〕, further comprising an antibacterial agent.

[0025] 〔12〕 The composition according to any one of 〔1〕 to 〔11〕, substantially free of abrasive particles.

[0026]

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

[12] , wherein the workpiece subjected to the above chemical mechanical polishing treatment comprises at least one selected from the group consisting of polysilicon and amorphous silicon.

[0027]

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

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

[0028]

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

[14] , wherein the workpiece subjected to the above chemical mechanical polishing treatment contains 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.

[0029]

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

[15] into contact with a workpiece that has been subjected to chemical mechanical polishing.

[0030]

[17] A method for producing a cleaned workpiece, comprising the steps of supplying a composition described in any one of [1] to

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

[0031]

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

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

[0032]

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

[16] to

[18] .

[0033] According to the present invention, a composition is available that exhibits excellent particle removal and organic matter removal properties when applied to a workpiece containing a hydrophobic surface derived from polysilicon or amorphous silicon that has undergone CMP treatment.

[0034] 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.

[0035] The present invention will be described in detail below.

[0036] The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0037] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0038] Furthermore, in this specification, if there are two or more components, the "content" of those components means the total content of those two or more components.

[0039] In this specification, in numerical ranges described in stages, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples.

[0040] In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0041] In this specification, "total mass of components excluding the solvent in the composition" means the total mass of all components contained in the composition other than the solvent, such as water and organic solvents.

[0042] Unless otherwise specified, the compounds described herein may include structural isomers, optical isomers, and isotopes. Furthermore, structural isomers, optical isomers, and isotopes may be present individually or in groups of two or more.

[0043] In this specification, when there are multiple substituents and linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by a specific symbol, or when multiple substituents, etc. are specified simultaneously, it means that each substituent, etc. may be identical or different from the others. The same applies to the specification of the number of substituents, etc.

[0044] The bonding direction of divalent groups as expressed herein is not limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", if Y is -COO-, Y may also be -CO-O- or -O-CO-. Furthermore, the above compound may also be "X-CO-O-Z" or "X-O-CO-Z".

[0045] In this specification, "ppm" means "parts-per-million (10 －６ ) means "ppb" is "parts-per-billion (10 －９ It means ")".

[0046] In this specification, "weight-average molecular weight" means the weight-average molecular weight in terms of polyethylene glycol, as measured by GPC (gel permeation chromatography).

[0047] In this specification, the "Hydrophilic-Lipophilic Balance" (HLB) 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.

[0048] HLB value = 20 × [(molecular weight of hydrophilic group contained in surfactant) / (molecular weight of surfactant)] In this specification, "critical micelle concentration" (CMC) refers to the concentration at which the surface tension of an aqueous surfactant solution is inflected when the concentration of the aqueous surfactant is changed and the surface tension is measured using a surface tension meter such as a Wilhelmy surface tension meter at atmospheric pressure and 25°C. Depending on the case, catalog values ​​or values ​​calculated by other methods may be used. For example, commercially available kits that measure the critical micelle concentration of a surfactant by utilizing the fluorescence change of a fluorescent reagent that interacts with the surfactant can be used. [Composition] The composition of the present invention will be described in detail below.

[0049] The composition of the present invention (hereinafter also simply referred to as "this composition") is a composition used for cleaning a workpiece that has undergone chemical mechanical polishing, and comprises a nonionic surfactant having a polyoxyalkylene chain and a hydrophilic-lipophilic balance value of 8.5 to 14, 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 0.001 to 1500.

[0050] 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.

[0051] Furthermore, 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.

[0052] After CMP processing, the substrate tends to retain abrasive particles used in the CMP process, metallic components derived from polished wiring metal films and / or barrier metals, and organic components derived from the polishing slurry and cleaning solution composition. However, the nonionic surfactant effectively protects these residues, thereby suppressing their re-adhesion to the substrate. Therefore, this composition exhibits excellent particle and organic matter removal capabilities. Furthermore, since the nonionic surfactant has little effect on the dispersion and aggregation of residues, less residue remains on the substrate, and the substrate is less likely to be damaged.

[0053] Furthermore, although the detailed mechanism is unknown, certain compounds also contribute to particle and organic matter removal.

[0054] Furthermore, by setting the mass ratio of the nonionic surfactant content to the total content of specific compounds to 0.001 to 1500, the balance between particle removal and organic matter removal can be optimized.

[0055] As described above, it is believed that the problems of the present invention have been solved by having the above-described structure of this composition.

[0056] Hereinafter, when this composition is applied to a workpiece containing a hydrophobic surface derived from polysilicon or amorphous silicon that has undergone CMP treatment, the superiority of at least one of the particle removal properties and organic matter removal properties is also referred to as "the effects of the present invention being superior."

[0057] The following details each component of this composition and its physical properties. [Nonionic surfactant] This composition contains a nonionic surfactant (hereinafter also referred to as "nonionic surfactant A") having a polyoxyalkylene chain and a hydrophilic-lipophilic balance value of 8.5 to 14.

[0058] Nonionic surfactants, unlike ionic surfactants such as anionic and cationic surfactants, are compounds that possess surfactant properties by having hydrophilic and hydrophobic groups that do not exhibit ionic characteristics. However, nonionic surfactant A may have ionic groups such as amino groups, as long as it does not impair the effects of the present invention.

[0059] Also, it is also preferable that the nonionic surfactant A contains at least one of an ether bond (—O—) and an ester bond (—COO— or —OCO—) in addition to a hydrophilic group and a hydrophobic group.

[0060] The molecular weight of the 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.

[0061] When the nonionic surfactant A has a molecular weight distribution, the above molecular weight is intended to be the weight average molecular weight.

[0062] The polyoxyalkylene chain possessed by the nonionic surfactant A is 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.

[0063] 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.

[0064] n is preferably 2 to 200, more preferably 5 to 150, and still more preferably 5 to 100.

[0065] The polyoxyalkylene chain is preferably a structure composed of a group selected from the group consisting of an oxyethylene group (—CH ２ —CH ２ —O—), and a polyoxypropylene group (—CH ２ —CH(CH ３ )—O— or —(CH ２ ) ３ —O—). The polyoxyalkylene chain may be a structure composed of only one of an oxyethylene group and an oxypropylene group, or may be a structure composed of both.

[0066] Also, it is preferable that the nonionic surfactant A has at least one of a polyoxyethylene chain and a polyoxypropylene chain, and more preferably has a polyoxyethylene chain.

[0067] The hydrophilic-lipophilic balance (HLB) value of nonionic surfactant A is not particularly limited as long as it is between 8.5 and 14, but is preferably between 9.5 and 14, more preferably between 10 and 14, and even more preferably between 11 and 14.

[0068] 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.

[0069] Examples of hydrophobic groups in nonionic surfactant A include hydrocarbon groups, more specifically, aliphatic hydrocarbon groups, optionally substituted aromatic ring groups, and groups formed by combinations thereof. The valency of each of the above-mentioned groups is not particularly limited, for example, it can range from 1 to 4 valencies, and is often monovalent or divalent.

[0070] In particular, nonionic surfactant A preferably has a hydrocarbon group having 3 to 30 carbon atoms as a hydrophobic group, and more preferably has a hydrocarbon group having 10 to 25 carbon atoms.

[0071] The above-mentioned 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.

[0072] The number of carbon atoms in the linear or branched aliphatic hydrocarbon group is preferably 3 to 30, more preferably 6 to 25, and even more preferably 10 to 20.

[0073] 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.

[0074] 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 linking two or more rings selected from monocyclic and fused rings by single bonds.

[0075] Furthermore, the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle, 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 30, and even more preferably 6 to 25.

[0076] Examples of aromatic rings include benzene rings and naphthalene rings.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] In the above specific example, "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 is esterified.

[0081] The oxyalkylene group described above is preferably an oxyethylene group or an oxypropylene group.

[0082] Among the specific examples mentioned above, polyoxyalkylene alkyl ethers, polyoxyalkylene polyoxyalkylene alkyl ethers, polyoxyalkylene distyrene-phenyl ethers, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene hydrogenated castor oil, or polyoxyalkylene alkylamines are particularly preferred.

[0083] The oxyalkylene group described above is preferably an oxyethylene group or an oxypropylene group.

[0084] Among the nonionic surfactants A, polyoxyalkylene alkyl ethers or polyoxyalkylene polyoxyalkylene alkyl ethers are preferred, and compounds represented by the following formula (S1) are preferred.

[0085]

[0086] In formula (S1), R represents a monovalent hydrocarbon group.

[0087] Specific examples and preferred embodiments of hydrocarbon groups are as described in detail above for hydrophobic groups.

[0088] Among the monovalent hydrocarbon groups represented by R, aliphatic hydrocarbon groups are preferred, aliphatic hydrocarbon groups having 3 to 30 carbon atoms are more preferred, and alkyl groups having 10 to 20 carbon atoms are even more preferred.

[0089] In equation (S1), n ​​and m each independently represent a non-negative integer, provided that at least one of n and m is a non-negative integer of 2 or greater.

[0090] For n, 2 to 30 is preferred, 3 to 25 is more preferred, and 5 to 20 is even more preferred. Similarly, for m, 0 to 30 is preferred, 0 to 25 is more preferred, and 0 to 20 is even more preferred.

[0091] Of the values ​​of n and m, it is preferable that n is an integer between 3 and 25, and m is 0.

[0092] Among polyoxyalkylene alkyl ethers, polyoxyethylene alkyl ethers are particularly preferred. Specific examples of polyoxyethylene alkyl ethers include, for example, polyoxyethylene lauryl ether (e.g., Emulgen 108, manufactured by Kao Corporation), polyoxyethylene cetyl ether (e.g., Emulgen 220, manufactured by Kao Corporation), polyoxyethylene palmitoyl ether, polyoxyethylene stearyl ether (e.g., Emulgen 320P, manufactured by Kao Corporation), polyoxyethylene oleyl ether (e.g., Emulgen 408, manufactured by Kao Corporation), and polyoxyethylene octyldodecyl ether (e.g., Emulgen 2020G-HA, manufactured by Kao Corporation).

[0093] Nonionic surfactant A may be used alone or in combination of two or more types.

[0094] The content of nonionic surfactant A is preferably 0.001 to 10% by mass, more preferably 0.001 to 5% by mass, and even more preferably 0.01 to 1% by mass, based on the total mass of the composition.

[0095] Furthermore, the content of nonionic surfactant A is preferably 0.01 to 99.9% by mass, more preferably 10 to 98% by mass, and even more preferably 40 to 95% by mass, based on the total mass of the components excluding the solvent in the composition.

[0096] 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.

[0097] Furthermore, the mass ratio of the content of nonionic surfactant A to the content of the specific compound described later is 0.001 to 1500. In particular, a ratio of more than 0.001 and less than 1500 is preferred, 0.01 to 1000 is more preferred, and 0.01 to 500 is even more preferred, as it provides superior particle removal and organic matter removal.

[0098] Furthermore, the mass ratio of the nonionic surfactant A content to the antibacterial agent content, as described later, is not particularly limited, but is often between 0.1 and 10000. A ratio of more than 0.3 and less than 500 is preferred, and 1 to 100 is more preferred, as it provides superior organic matter removal.

[0099] Furthermore, the mass ratio of the content of nonionic surfactant A to the content of the corrosion inhibitor described later is not particularly limited, but is often 0.1 to 5000, preferably 0.3 to 500, and more preferably 1.0 to 100, in terms of superior organic matter removal performance. [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.

[0100] For superior effects of the present invention, it is more preferable that the composition comprises 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).

[0101] Furthermore, as mentioned above, the specified compounds are those excluding zwitterionic compounds (compounds that have both cationic and anionic parts), such as amino acids.

[0102] Although the detailed mechanism is unclear, it is thought that because the specific compound is not a zwitterionic compound, competitive reactions between promoting and inhibiting cleaning of the same compound are less likely to occur within a single compound, thus allowing the cleaning effect of the chemical solution to be fully achieved.

[0103] 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. <Inorganic Acid> Examples of inorganic acids include nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, nitrite, sulfurous acid, and boric acid, and nitric acid, phosphoric acid, or sulfuric acid are preferred in that they provide superior effects of the present invention. Salts of inorganic acids may be used as long as they become an acid or acid ion (anion) in aqueous solution.

[0104] The number of acid groups in an inorganic acid is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. <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.

[0105] As mentioned above, zwitterionic compounds are excluded from the list of 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.

[0106] The number of acid groups in an organic acid 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.

[0107] Organic acids preferably have at least one of a carboxylic acid group and a phosphonic acid group. • Carboxylic acid-based organic acids: Carboxylic acid-based organic acids refer to organic acids having at least one carboxyl group in their molecule.

[0108] As for carboxylic acid-based organic acids, aliphatic carboxylic acid-based organic acids are preferred, for example.

[0109] Aliphatic carboxylic acid organic acids may further contain hydroxyl groups.

[0110] 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. Phosphonic acid organic acids are organic acids that have at least one phosphonic acid group in their molecule.

[0111] Examples of phosphonic acid-based organic acids include aliphatic phosphonic acid-based organic acids.

[0112] Aliphatic phosphonic acid organic acids may also have a hydroxyl group in addition to the phosphonic acid group and the aliphatic group.

[0113] 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.

[0114] The number of carbon atoms in the phosphonic acid-based organic acid is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8.

[0115] 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. <Amino alcohols> Amino alcohols are compounds of amines that further have at least one hydroxylalkyl group in their molecule. Amino alcohols may have any of primary to tertiary amino groups, but it is preferable that they have a primary amino group.

[0116] The number of amino groups in an amino alcohol is, for example, 1 to 5, and preferably 1 to 3. The number of hydroxyl groups in an amino alcohol is, for example, 1 to 5, and more preferably 1 to 3.

[0117] 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.<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 cation group formed by the substitution of a nitrogen atom with four hydrocarbon groups (preferably alkyl groups).

[0118] Examples of quaternary ammonium compounds include quaternary ammonium hydroxides, quaternary ammonium fluorides, quaternary ammonium bromides, quaternary ammonium iodides, quaternary ammonium acetates, and quaternary ammonium carbonates.

[0119] Among these, quaternary ammonium hydroxides are preferred, and compounds represented by the following formula (a1) are more preferred.

[0120]

[0121] 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.

[0122] 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. <Aliphatic polyamines> Aliphatic polyamines are not particularly limited as long as they are compounds having two or more amino groups.

[0123] The number of amino groups in the aliphatic polyamine is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0124] Furthermore, the number of carbon atoms in the aliphatic polyamine is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.

[0125] Furthermore, if an aliphatic polyamine has a hydroxyl group, it is classified as an amino alcohol.

[0126] Among aliphatic polyamines, compounds represented by the following formula (A2) are preferred.

[0127]

[0128] In formula (A2), R Ａ４ ~R Ａ７ Each of these independently represents a hydrogen atom or an alkyl group which may have a substituent.

[0129] 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. Ａ４ and R Ａ７ , and R Ａ５ and RＡ６ Both may be bonded to each other via single bonds or divalent linking groups to form a ring.

[0130] 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.

[0131] R Ａ４ ~R Ａ７ Each of these independently represents a hydrogen atom or an alkyl group which may have a substituent.

[0132] 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.

[0133] Examples of substituents on the alkyl group include halogen atoms such as fluorine, chlorine, and bromine; alkoxy groups; acyl groups such as acetyl, propionyl, and benzoyl groups; cyano groups; and nitro groups.

[0134] Among them, R Ａ４ ~R Ａ７ Preferably, the alkyl group has 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group, and even more preferably a methyl group.

[0135] R 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.

[0136] 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.

[0137] 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.

[0138] The alkylene group described above has -NR Ａｘ The number of linking groups represented by - is preferably 0 to 3, and more preferably 0 to 1.

[0139] The number of linking groups represented by -O- in the alkylene group is preferably 0 to 3, and more preferably 0 to 1.

[0140] 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.

[0141] R Ａ４ ~R Ａ７ Two of these may be linked to each other via a single bond or a divalent linking group to form a ring. The resulting ring may be monocyclic or polycyclic.

[0142] Examples of the divalent linking groups mentioned above include divalent hydrocarbon groups, -O-, and -CO-, with alkylene groups being preferred.

[0143] 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).

[0144] The specific compound may be used alone or in combination of two or more compounds.

[0145] The specific compound is preferably present in an amount of 0.0001 to 10% by mass, more preferably 0.0001 to 1% by mass, and even more preferably 0.001 to 1% by mass, based on the total mass of the composition.

[0146] Furthermore, the content of the specific compound is preferably 0.01 to 99.5% by mass, more preferably 0.01 to 75% by mass, and even more preferably 0.1 to 50% by mass, based on the total mass of the components excluding the solvent in the composition. [Other components] The composition may also contain other components besides the nonionic surfactant and the specific compound described above. Examples of other components include water, antibacterial agents, corrosion inhibitors, organic solvents, polymers, oxidizing agents, reducing agents, fluorides, and pH adjusters. In terms of superior effects of the present invention, the composition preferably contains a compound selected from the group consisting of water, antibacterial agents, and corrosion inhibitors.

[0147] Note that other components such as antibacterial agents and corrosion inhibitors are compounds different from the specified compounds. For example, a compound that is of the type exemplified by the specified compounds and also has antibacterial activity will be treated as a specified compound. <Water> This composition preferably contains water.

[0148] The type of water used can be any type 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 manufacturing process.

[0149] The water content may be the remainder of the components that may be included in this composition.

[0150] The water content is preferably 60% by mass or more, more preferably 75% by mass or more, and even more preferably 85% by mass or more, based on the total mass of the 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 superior effects of the present invention. <Antibacterial agent> In terms of achieving superior effects of the present invention, the composition may further preferably contain an antibacterial agent.

[0151] The antibacterial agent is a compound having antibacterial activity against bacteria and / or antifungal activity against fungi, and is a different compound from each of the above components. The antibacterial agent may also be in the form of a salt (e.g., a known salt).

[0152] 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.

[0153] 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. Among these, cresol is preferred.

[0154] Examples of biguanide-based antimicrobial agents include bis(p-chlorophenyl diguanide) hexanedigluconate (chlorhexidine gluconate) and poly(hexamethylene biguanide) hydrochloride (hexamethylene biguanidine hydrochloride). Among these, chlorhexidine gluconate is preferred.

[0155] Examples of sulfamide-based antibacterial agents include N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide (dichlorofluanide) and N-dichlorofluoromethylthio-N',N'-dimethyl-N-p-tolylsulfamide (tolylfluanide). Among these, tolylfluanide is preferred.

[0156] Examples of peroxide-based antibacterial agents include hydrogen peroxide and peracetic acid. Of these, peracetic acid is preferred.

[0157] 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 are preferred, and MIT or OIT are more preferred.

[0158] Examples of imidazole-based antibacterial agents include 2-(4-thiazolyl)-bentimidazole (TBZ) and 2-bentimidazole methyl carbamate (Preventol BCM).

[0159] Examples of ester-based antibacterial agents include glycerol laurate (monoglyceride) and ethyl parahydroxybenzoate (ethylparaben).

[0160] Examples of alcohol-based antibacterial agents include ethyl alcohol (ethanol), 2-propanol (IPA), phenoxyethanol, 1,2-pentanediol, and 1,2-hexanediol.

[0161] An example of a carbamate-based antimicrobial agent is 3-iodo-2-propynylbutylcarbamate (Glycical).

[0162] Examples of iodine-based antibacterial agents include [(4-chlorophenoxy)methyl]-3-iodo-2-propynyl ether (IF1000).

[0163] Antimicrobial agents may be used individually or in combination of two or more types.

[0164] 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 0.001 to 1.0% by mass, based on the total mass of the composition.

[0165] Furthermore, the antibacterial agent content is preferably 0.01 to 80.0% by mass, more preferably 0.1 to 50.0% by mass, and even more preferably 0.1 to 20% by mass, based on the total mass of the components excluding the solvent in this composition. <Corrosion inhibitor> This composition is preferably further to contain a corrosion inhibitor.

[0166] The corrosion inhibitor is a compound that has the function of preventing corrosion of the exposed surface of the object to be treated, and is a different compound from each of the above components.

[0167] As a corrosion inhibitor, compounds having amino groups other than nitrogen-containing heterocyclic groups (hereinafter also referred to as "specific amino groups"), selected from primary amino groups, secondary amino groups, and tertiary amino groups, are preferred, and compounds having primary amino groups are more preferred.

[0168] Furthermore, it is preferable that the corrosion inhibitor has at least one carboxyl group in addition to the specific amino group. In other words, it is preferable that the corrosion inhibitor is an amino acid. The amino acid may be the D-form, L-form, or DL-form. If the corrosion inhibitor has carboxyl groups, the number of carboxyl groups is preferably 1 to 5.

[0169] Among the corrosion inhibitors, basic amino acids are preferred.

[0170] The number of specific amino groups in the corrosion inhibitor is preferably 2 to 5, and more preferably 2 to 4.

[0171] 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.

[0172] 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.

[0173] As histidine derivatives, compounds described in Japanese Patent Publication No. 2015-165561, Japanese Patent Publication No. 2015-165562, etc., can be used, and the contents of these publications are incorporated herein by reference. As salts, examples include alkali metal salts such as sodium salts and potassium salts, ammonium salts, carbonates, and acetates.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] The corrosion inhibitor may be used alone or in combination of two or more types.

[0179] The content of the corrosion inhibitor is preferably 0.00001 to 5.0% by mass, more preferably 0.001 to 1% by mass, and even more preferably 0.01 to 1% by mass, based on the total mass of the composition.

[0180] Furthermore, the content of the corrosion inhibitor is preferably 0.001 to 90% by mass, more preferably 0.1 to 50% by mass, and even more preferably 1 to 30% by mass, based on the total mass of the components excluding the solvent in this composition. <Organic solvent> This composition may further contain an organic solvent.

[0181] Examples of organic solvents include well-known organic solvents such as alcohol-based solvents, glycol-based solvents, glycol ether-based solvents, and ketone-based solvents.

[0182] The organic solvent is preferably miscible with water in any ratio.

[0183] As organic solvents, for example, compounds exemplified in paragraphs

[0135] to

[0140] of International Publication No. 2022 / 044893 can be referenced, and the contents thereof are incorporated herein by reference. [Physical properties of the composition] <pH> The composition may be either acidic or alkaline.

[0184] For the present invention to be more effective, if the composition is acidic, the pH is preferably 6 or less, more preferably 5.5 or less. The lower limit is preferably 0.5 or more, more preferably 1 or more, and even more preferably 2 or more.

[0185] Furthermore, if the composition is alkaline, the pH is preferably 7.5 or higher, and more preferably 8 or higher. The upper limit is preferably 13.5 or lower, more preferably 11.5 or lower, even more preferably 11 or lower, and particularly preferably 10.5 or lower.

[0186] Furthermore, when the pH of the composition is 7.5 or lower, the corrosion protection of the substrate is even better when this composition is applied to a workpiece including a CMP-treated metal surface (especially a tungsten surface).

[0187] The pH of this composition can be measured using a known pH meter in accordance with the method compliant with JIS Z8802-1984. The pH measurement temperature is 25°C. <Metal Content> The content (measured as ion concentration) of metals (e.g., 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. In the manufacture of state-of-the-art semiconductor devices, it is expected that even higher purity compositions will be required, so 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.

[0188] 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 materials used in the manufacture of the composition, or at a stage after the manufacture of the composition.

[0189] Other methods for reducing the metal content include using containers that minimize the elution of impurities, as described later, for the raw materials or the manufactured composition. Additionally, fluororesin lining can be applied to the inner walls of pipes to prevent metal components from leaching out during the production of the composition. <Coarse Particles> This composition may contain coarse particles, but a low content is preferred.

[0190] Coarse particles refer to particles whose diameter (particle size) is 0.03 μm or larger when the particle shape is considered to be spherical.

[0191] The coarse particles contained in this composition include dust, dirt, organic solids, and inorganic solids that are present as impurities in the raw materials, as well as dust, dirt, organic solids, and inorganic solids that are introduced as contaminants into the preparation of the composition, and which ultimately remain as particles in the composition without dissolving.

[0192] 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.

[0193] The amount of coarse particles present in this composition can be measured in the liquid phase using a commercially available measuring device that employs a light scattering type liquid particle measurement method with a laser as the light source. Methods for removing coarse particles include, for example, purification treatments such as filtering, as described later. <Abrasive particles> It is preferable that this composition substantially contains abrasive particles.

[0194] "Substantially free of abrasive particles" specifically means that the abrasive particle content is 1,000 ppm by mass or less, with a preference of 500 ppm by mass or less, and a preference of 100 ppm by mass or less, based on the total mass of the composition. The lower limit is preferably 0% by mass or more, based on the total mass of the composition.

[0195] Examples of abrasive particles include abrasive particles such as silicon dioxide contained in chemical mechanical polishing slurries and the descriptions in paragraphs

[0194] to

[0197] of International Publication No. 2021 / 131451.

[0196] One method for measuring the content of abrasive particles is to use a commercially available measuring device that employs a light scattering type liquid particle measurement method with a laser as the light source, and measure the particle content in the liquid phase.

[0197] Methods for adjusting the content of abrasive particles include, for example, known methods such as filtering. [Method for manufacturing this composition] This composition can be manufactured by known methods. The manufacturing method will be described in detail below. [Preparation process] This composition can be manufactured, for example, by mixing the above components.

[0198] 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 and mix the ingredients, 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.

[0199] 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.

[0200] The mixing of each component in the liquid 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. <Purification> It is preferable to perform a purification process on one or more of the raw materials for preparing this composition in advance. Examples of purification processes include known methods such as distillation, ion exchange, and filtration.

[0201] The degree of purification should preferably be such that the purity of the raw material is 99% by mass or higher, and more preferably 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.

[0202] 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.

[0203] As a purification process, multiple of the above purification methods may be combined. 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.

[0204] Furthermore, the purification process may be carried out multiple times.

[0205] The filters used for filtering are not particularly limited as long as they are 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 the raw material using filters made of these materials, highly polar foreign substances that are likely to cause defects can be effectively removed. <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 and other issues do not pose a problem.

[0206] 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 compartment 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.

[0207] Furthermore, containers as exemplified in paragraphs

[0121] to

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

[0208] 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.

[0209] 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, it may be at room temperature, or the temperature may be controlled in the range of -20°C to 20°C to prevent deterioration. <Cleanroom> It is preferable that all handling, including the manufacture of this composition, opening and cleaning of the container, filling of this composition, processing analysis, and measurement, be carried out in a cleanroom. It is preferable that the cleanroom 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. [Dilution Step] After a dilution step in which this composition is diluted with a diluent such as water, the diluted processing liquid (diluted composition) may be used to process the object to be processed.

[0210] Furthermore, a diluted composition is also a form of this composition, as long as it satisfies the requirements of the present invention.

[0211] 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.

[0212] Purification treatments include ion component reduction treatment using ion exchange resin or RO membrane, and foreign matter removal using filtering, as described for purification treatments of this composition, and it is preferable to perform one of these treatments.

[0213] 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.

[0214] Furthermore, it is preferable that this composition be diluted with water (preferably ultrapure water).

[0215] 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.

[0216] 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.

[0217] The specific method for diluting this composition may be carried out in accordance with the preparation step of 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 of the treatment liquid described above. [Applications] This composition is used for cleaning workpieces that have undergone chemical mechanical polishing (hereinafter also referred to as "workpieces after CMP treatment").

[0218] There are no particular restrictions on the cleaning method; known methods can be used.

[0219] The apparatus and conditions used in the washing process using this composition can be appropriately selected from known apparatus and conditions depending on the type of object to be treated and the type and amount of residue to be removed. For example, the processing method described in paragraphs

[0085] to

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

[0220] This composition can be particularly used when cleaning an object after CMP treatment using a pad.

[0221] The cleaning process using the pads described above is generally also called rinse polishing, buff polishing, or buff cleaning, and it is a process that uses pads to reduce the amount of residue present on the surface of the object being treated.

[0222] Specifically, the composition is supplied to the contact area between the workpiece and the pad, and the surface of the workpiece that has undergone CMP treatment is brought into contact with the pad, and the workpiece and the pad are moved relative to each other.

[0223] 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 the composition. [Pad] The pad is not particularly limited and can be appropriately selected depending on the type of workpiece, 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.

[0224] Specific examples of pads include, for example, resin pads such as foamed polyurethane buff pads, nonwoven fabrics, suede buff pads, and sponge buff pads. [Workpiece to be treated] It is preferable that, after the CMP treatment, two or more different materials are exposed on the surface of the workpiece that has undergone chemical mechanical polishing.

[0225] Examples of two or more materials include metal and silicon, and it is preferable to include all of these.

[0226] Specific examples of silicon include polysilicon, amorphous silicon, and silicon wafers (single-crystal silicon), with polysilicon or amorphous silicon being preferred. Polysilicon, amorphous silicon, and silicon wafers may be doped with dopants such as boron and phosphorus.

[0227] The material to be processed may be a semiconductor substrate. If the semiconductor substrate contains materials such as metal and silicon, the materials may be located anywhere on the semiconductor substrate, for example, on the front and back surfaces, sides, or within grooves. 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 present on the semiconductor substrate via other layers.

[0228] 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.

[0229] The metal preferably exists 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.

[0230] In particular, the workpiece preferably has a metal layer containing metal M, and more preferably has 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.

[0231] 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.

[0232] Examples of wafers that constitute a semiconductor substrate 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.

[0233] 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)).

[0234] Examples of silicon used in silicon wafers include single-crystal silicon, polycrystalline silicon, and amorphous silicon.

[0235] Examples of insulating films include 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.

[0236] In terms of achieving superior effects of the present invention, it is preferable that the treated material has silicon, selected from the group consisting of silicon compounds, polysilicon, and amorphous silicon, exposed on its surface, and more preferably that at least one of the group consisting of polysilicon and amorphous silicon is exposed on its surface.

[0237] 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).

[0238] Examples of barrier metals include tantalum (Ta), tantalum nitride (TaN), titanium nitride (TiN), cobalt (Co), cobalt alloys, ruthenium (Ru), and ruthenium alloys.

[0239] The workpiece 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. <CMP Treatment> The above CMP (chemical mechanical polishing) treatment is a treatment that flattens 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 flattened by the frictional force between the polishing pad, the polishing slurry, and the surface of the workpiece, and by 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.

[0240] On the surface of a workpiece that has undergone CMP treatment, 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 may remain. In addition, organic matter derived from the CMP composition used during the CMP treatment may remain as residue. Since these residues may, for example, short-circuit between wirings and degrade the electrical properties of the semiconductor substrate, CMP-treated semiconductor substrates are subjected to a cleaning process to remove these residues from the surface.

[0241] 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. [Method for manufacturing cleaned workpieces] As described above, this composition is used to clean workpieces after CMP treatment, and cleaned workpieces are obtained by the above cleaning.

[0242] The present invention includes a manufacturing method for a cleaned workpiece, which includes a manufacturing method that includes a washing step using a pad, and a manufacturing method that includes a washing step without using a pad, as described below. Each method will be described in detail below. [Washing step using a pad] The manufacturing method including a washing step using a pad includes a step (hereinafter also referred to as "washing step A") in which the composition is supplied, the 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 wash the workpiece, and a cleaned workpiece is obtained.

[0243] In the above manufacturing method, the composition is supplied to the contact area between the workpiece and the pad, and cleaning is performed. The preferred configuration of the workpiece, pad, equipment, and conditions used in cleaning step A is as described above.

[0244] 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.

[0245] The pressure applied during pressing is preferably 5 to 100 hPa, and more preferably 10 to 50 hPa.

[0246] The temperature of this composition is not particularly limited, but 10 to 60°C is preferred, and 15 to 50°C is more preferred, in terms of having better cleaning properties and being able to further suppress damage to the components.

[0247] The pH of this composition is preferably a preferred embodiment of the pH described above.

[0248] 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 is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and even more preferably 20 to 60 seconds.

[0249] The supply rate (feed rate) of this composition is preferably 50 to 5000 mL / min, and more preferably 100 to 2000 mL / min.

[0250] The processing method in cleaning step A may be either a single-wafer method or a batch method. The single-wafer method processes one workpiece at a time, while the batch method processes multiple workpieces simultaneously. [Cleaning step without pads] A manufacturing method including a cleaning step without pads includes a step of bringing the composition into contact with a workpiece that has undergone chemical mechanical polishing (hereinafter also referred to as "cleaning step B"). Preferred embodiments of the workpiece, equipment used, and conditions in cleaning step B are as described above.

[0251] The method for bringing the object to be treated into contact with the composition is not particularly limited and includes, for example, immersing the object to be treated in the composition in a tank, spraying the composition onto the object to be treated, flowing the composition over the object to be treated, and combinations thereof.

[0252] The contact between the workpiece and the composition during the contact process may be performed only once or two or more times. If the contact is performed two or more times, the same method may be repeated, or different methods may be combined.

[0253] The temperature of this composition is not particularly limited, but 10 to 60°C is preferred, and 15 to 50°C is more preferred, in terms of having better cleaning properties and being able to further suppress damage to the components.

[0254] The supply rate (feed rate) of this composition is preferably 50 to 5000 mL / min, and more preferably 500 to 2000 mL / min.

[0255] 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 is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and even more preferably 30 to 60 seconds.

[0256] 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.

[0257] 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.

[0258] The method for producing a cleaned workpiece according to the present invention may further include a washing step using a treatment liquid other than the present composition.

[0259] As a treatment solution other than this composition, known compositions can be used depending on the type of material to be treated and the type and amount of residue to be removed.

[0260] Examples of components that may be included in processing solutions other than this composition 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.

[0261] The processing solution other than this 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). <Rinsing step> After the washing step described above, a step of bringing the workpiece to be treated into contact with the rinsing solution (hereinafter also referred to as the "rinsing step") may be performed. By performing the rinsing step, the workpiece obtained in the washing step can be washed with the rinsing solution, and residues can be efficiently removed.

[0262] The rinsing step is preferably performed immediately after the semiconductor substrate cleaning step, and involves rinsing the workpiece with a rinsing solution. The rinsing step may also be performed using the mechanical stirring method described above.

[0263] 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.

[0264] 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 similarly.

[0265] The contact time between the workpiece and the rinsing solution can be appropriately changed depending on the type and content of each component in the composition, as well as the target 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. [Drying step] If necessary, a drying step may be performed to dry the workpiece.

[0266] 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 an infrared lamp, Marangoni drying, Rotagoni drying, IPA drying, and any combination thereof. [Manufacturing method for electronic devices] The above-described method for manufacturing the cleaned workpiece can be suitably applied to the manufacturing process of electronic devices.

[0267] The above manufacturing method may be carried out in combination with other processes performed on the substrate, either before or after. It may also be incorporated into other processes during the implementation of the above manufacturing method, or it may be incorporated into other processes.

[0268] Other processes include, for example, the formation of 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), the formation of resists, exposure processes, removal processes, heat treatment processes, cleaning processes, and inspection processes.

[0269] 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.

[0270] The present invention will be described in more detail below based on examples.

[0271] The materials, quantities, proportions, processing details, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0272] 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").

[0273] In preparing 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. [Raw materials for the compositions] The following compounds were used to prepare the compositions. In addition, each component used in the examples and comparative examples was classified as semiconductor grade or equivalent high-purity grade. [Nonionic surfactants] Of the nonionic surfactants shown below, compounds A9 and A10 were used as comparative compounds in the preparation of the comparative example compositions.

[0274] • Compound A1: Emulgen 320P (Polyoxyethylene (13) stearyl ether, manufactured by Kao Corporation) • Compound A2: Emulgen 108 (Polyoxyethylene (6) lauryl ether, manufactured by Kao Corporation) • Compound A3: Emulgen LS114 (Polyoxyethylene polyoxypropylene alkyl (C12-14) ether, manufactured by Kao Corporation) • Compound A4: Emulgen A-60 (Polyoxyethylene distyrenated phenyl ether, manufactured by Kao Corporation) • Compound A5: Rheodol 460V (Polyoxyethylene (60) sorbitol tetraoleate, manufactured by Kao Corporation) • Compound A6: Emanone CH-25 (Polyoxyethylene hydrogenated castor oil (25 E.O.), manufactured by Kao Corporation) • Compound A7: Amito 105A (Polyoxyethylene (5) coconut alkylamine, manufactured by Kao Corporation)・Compound A8: Emanone 1112 (polyoxyethylene (12) monolaurate, manufactured by Kao Corporation) ・Compound A9: Emulgen 150 (polyoxyethylene (47) lauryl ether, manufactured by Kao Corporation) ・Compound A10: Emulgen 103 (polyoxyethylene (3) lauryl ether, manufactured by Kao Corporation) [Specific Compound 1] ・Compound B1: Nitric acid ・Compound B2: Phosphoric acid ・Compound B3: Sulfuric acid ・Compound B4: Citric acid ・Compound B5: Etidronic acid [Specific Compound 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) [Antibacterial agent] ・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) [Corrosion inhibitor] ・Compound E1: L-arginine ・Compound E2: L-histidine ・Compound E3: L-lysine ・Compound E4: Bis(p-chlorophenyl diguanide)hexanedigluconate (chlorhexidine gluconate) [Production of composition] The production method of the composition will be described below.

[0275] The above compounds and pure water were added in the amounts (mass%) specified in the table below, and thoroughly stirred to obtain a concentrated solution (stock solution).

[0276] Each composition was prepared by diluting the obtained concentrate with pure water as a diluent at the dilution ratio (volume ratio) indicated in the table below. In each composition, any remaining component not explicitly listed as a component in the table is pure water.

[0277] Finally, after preparing each of the above compositions, they were filtered through a 10 μm PP filter (Pall Corporation product: HDCII J-100) to obtain compositions 1, 7, 24, 30-32, and 35.

[0278] In all of the examples, the concentration of the nonionic surfactant was equal to or greater than the critical micelle concentration at 25°C.

[0279] The compositions of the other examples and comparative examples were manufactured according to the same procedure as in the above examples. [Polishing and cleaning of each workpiece] Each workpiece was polished and cleaned using the compositions of Examples 1, 7, 24, 30-32 and 35 according to the procedure shown below. [Preparation of workpieces (polishing treatment)] Workpieces 1-3 were prepared as shown below, and CMP treatment was performed on each workpiece using the polishing liquid, polishing apparatus and conditions shown below.

[0280] ・Object to be polished 1: A 12-inch silicon wafer with a 100 nm tungsten (W) layer formed on its surface. ・Object to be polished 2: A 12-inch silicon wafer with a 500 nm polysilicon layer (poly-Si) formed on its surface. ・Object to be polished 3: A 12-inch silicon wafer with a 500 nm amorphous silicon layer (a-Si) formed on its surface. (Composition of polishing solution A) ・Colloidal silica (PL5D, manufactured by Fuso Chemical Industries, 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 (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: 85 rpm - Head rotation speed: 80 rpm - Polishing time: 45 seconds [Cleaning treatment 1 (Cleaning using a resin pad)] Next, the polishing bodies 1 to 3 after the CMP treatment were cleaned using a resin pad with each composition prepared according to the procedure in [Production of composition] above, in the following procedure.

[0281] The apparatus and cleaning conditions are as follows: (Cleaning apparatus and conditions) ・Cleaning (polishing) apparatus: 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: 80 rpm ・Head rotation speed: 78 rpm ・Cleaning time: 30 seconds The polished objects 1 to 3 after the CMP treatment were transferred onto the resin pad used in the CMP treatment, and each polished surface was cleaned using the above cleaning apparatus and conditions. Each composition was filtered through a 1.0 μm PP filter (Pall product: HDCII J-006) before being supplied onto the resin pad.

[0282] The compositions used above were those immediately after manufacturing. [Cleaning Treatment 2 (Cleaning with Brush Scrub)] Each abrasive after Cleaning Treatment 1 above was further cleaned with a brush scrub according to the procedure shown below. The work was carried out in a cleanroom at 23°C.

[0283] After the above cleaning process 1, the polished surface of each workpiece was subjected to single-sheet cleaning by brush scrubbing for 60 seconds in the cleaning unit 1 of the apparatus using the same composition and apparatus as in the above cleaning process 1, and then further single-sheet cleaning by brush scrubbing for 30 seconds in the cleaning unit 2.

[0284] Finally, after rinsing with pure water for 60 seconds, the polished surfaces were spin-dried at a rotation speed of 1000 rpm in drying unit 2 while blowing nitrogen gas onto them, thereby obtaining cleaned polished surfaces 1 to 3 for evaluation.

[0285] Furthermore, after storing the composition used above in a cleanroom (23°C) for two weeks, the above-mentioned [Cleaning Treatment 1] and [Cleaning Treatment 2] were performed using the stored composition to obtain polished objects 1 to 3 that had been cleaned with the stored composition. [Evaluation] The following evaluations were performed using the above-mentioned cleaned polished objects 1 to 3. [Particle removal and organic matter removal] The particle removal and organic matter removal properties were evaluated using the following procedure with respect to polished objects 2 to 3, which were obtained by performing the above-mentioned [Cleaning Treatment 1] and [Cleaning Treatment 2] using the composition immediately after manufacture.

[0286] 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 of the cleaned polished objects 2 and 3 was measured.

[0287] The defects described above were identified by observing them using a defect review SEM (SEMVISION G5, manufactured by AMAT).

[0288] Based on the number of defects obtained, particle removal performance and organic matter removal performance were evaluated according to the following evaluation criteria. For both evaluations, a rating of D or higher is preferable for practical purposes. (Evaluation criteria: Particle removal performance) A: Number of particle defects per substrate is less than 20 B: Number of particle defects per substrate is 20 or more but less than 40 C: Number of particle defects per substrate is 40 or more but less than 50 D: Number of particle defects per substrate is 50 or more but less than 100 E: Number of particle defects per substrate is 100 or more (Evaluation criteria: Organic matter removal performance) A: Number of organic matter defects per substrate is less than 30 B: Number of organic matter defects per substrate is 30 or more but less than 50 C: Number of organic matter defects per substrate is 50 or more but less than 100 D: Number of organic matter defects per substrate is 100 or more but less than 200 E: Number of organic matter defects per substrate is 200 or more [Residue removal performance after aging test (aging performance)] The composition's performance over time was evaluated by checking its ability to remove residue from polished objects 2-3, which were obtained by performing the above-described [washing treatment 1] and [washing treatment 2] using the composition after storage for two weeks.

[0289] Using a defect detection device (AMAT Corporation, ComPlus-II), as described above, 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 of the cleaned polished objects 2 and 3 was measured.

[0290] By comparing the total number of defects obtained with the total number of defects obtained when washing with the composition immediately after preparation, as evaluated in the above section on [particle removal and organic matter removal], the increase in defects when washing with the composition after two weeks of storage was confirmed.

[0291] The time-dependent performance was evaluated based on the increase in defects obtained, according to the following evaluation criteria. (Evaluation Criteria) A: Increase in defects per substrate is less than 20 B: Increase in defects per substrate is 20 or more but less than 30 C: Increase in defects per substrate is 30 or more but less than 50 D: Increase in defects per substrate is 50 or more but less than 100 E: Increase in defects per substrate is 100 or more [Corrosion Resistance] For the polished workpiece 1 obtained by performing the above [Cleaning Treatment 1] and [Cleaning Treatment 2], the corrosion resistance of the W layer to the composition was evaluated by measuring the surface roughness of the W layer with an AFM (Atomic Force Microscope).

[0292] Specifically, the surface roughness was measured at 10 points in a 1 μm × 1 μm area in the diametrical direction passing through the center point of the object to be polished (wafer), and the corrosion resistance was evaluated from the average value of these measurements according to the following evaluation criteria. (Evaluation Criteria) A: Surface roughness less than 10 Å (1 nm) B: Surface roughness 10 Å or more and less than 30 Å C: Surface roughness 30 Å or more and less than 50 Å D: Surface roughness 50 Å or more In addition, in other examples and comparative examples other than Examples 1, 7, 24, 30-32 and 35, cleaned objects to be polished 1-3 were prepared using the same procedure as in Examples 1, 7, 24, 30-32 and 35, and evaluated using the same procedure as above. [Results] The composition of each composition in the examples and comparative examples, and the evaluation results are shown in the table below.

[0293] 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.

[0294] In the table, the column "(a) / (b) or (a) / (c)" 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.

[0295] In the table, the "(a) / (d)" column shows the mass ratio of the content of (a) nonionic surfactant to the content of (d) antibacterial agent.

[0296] In the table, the "(a) / (e)" column shows the mass ratio of the content of (a) nonionic surfactant to the content of (e) corrosion inhibitor.

[0297] In the table, the "Dilution Ratio" column indicates the dilution ratio (volume ratio) of the concentrated solution used when preparing the composition, as described above.

[0298] In the table, the values ​​in the "pH" column indicate 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.

[0299]

[0300]

[0301] 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 hydrophobic surface derived from CMP-treated polysilicon or amorphous silicon.

[0302] From a comparison of Examples 1 to 7, it was confirmed that the long-term performance is superior when the composition further contains an antibacterial agent.

[0303] Comparisons of Examples 12 and 15-16 show that when the mass ratio of the nonionic surfactant content to the antibacterial agent content is 1 to 100, the organic matter removal performance is superior.

[0304] Comparisons of Examples 12 to 14 show that when the mass ratio of the nonionic surfactant content to the total content of the specific compound is 0.01 or higher, particle removal performance is superior, and when it is 1000 or lower, organic matter removal performance is superior.

[0305] Comparisons of Examples 17 to 23 indicate that the corrosion resistance is superior when the pH of the composition is 7.5 or lower.

[0306] Comparisons of Examples 17-23 and 24-27 indicate that particle removal performance is superior when the pH of the composition is 6 or less or 7.5-11.5.

[0307] Comparisons of Examples 36 to 40 indicate that the corrosion protection is even better when the composition further contains a corrosion inhibitor.

[0308] Comparisons of Examples 42 to 46 show that when the mass ratio of nonionic surfactant A to the content of corrosion inhibitor is 0.3 to 500, the organic matter removal performance is better, and when it is 1.0 to 100, the organic matter removal performance is even better.

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 8.5 to 14; 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 0.001 to 1500.

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 11.

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 at least one selected from the group consisting of polysilicon and amorphous silicon.

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.

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