Composition, stock solution, method for manufacturing cleaned object to be treated, and method for manufacturing electronic device

Abstract

The present invention provides: a composition that has excellent residue removability, maintains excellent residue removability even after long-term storage, and has low deterioration of CMP treatment polishing speed when used in cleaning processing involving repeated treatment by CMP treatment followed by cleaning treatment using a pad; methods for manufacturing a stock solution and a cleaned object to be treated; and a method for manufacturing an electronic device. This composition is a composition for use in cleaning, using a pad, an object to be treated that has been subjected to chemical mechanical polishing, wherein: the composition includes a compound that has a polyoxyalkylene chain and does not have an acidic group, a basic group, or any salt of said groups, and an antimicrobial agent; the content of the compound with respect to the total mass of the composition is 0.3–5.0% by mass; and the mass ratio of the content of the compound to the content of the antimicrobial agent is 5–10,000.

Description

Composition, raw solution, method for producing cleaned treated object, and method for producing electronic device

[0001] The present invention relates to a composition, a stock solution, a method for producing a cleaned object, and a method for producing an electronic device.

[0002] In the semiconductor field, with the remarkable progress in integration and performance, even trace amounts of impurities (contamination) and / or deposits (particles) have come to have a significant impact on device performance and ultimately product yield. Various types of contamination and particles (hereinafter also referred to as residues) can be generated during each manufacturing process of semiconductor devices. During semiconductor manufacturing, substrate processing processes are appropriately performed to remove such residues.

[0003] For example, in the manufacture of semiconductor devices, a chemical mechanical polishing (CMP) process may be performed to planarize a semiconductor substrate surface having a metal wiring film, a barrier metal, an insulating film, etc., using a polishing slurry containing abrasive particles (e.g., silica, alumina, etc.). In the CMP process, metal components derived from the abrasive particles used in the CMP process, the polished wiring metal film and / or the barrier metal, etc., tend to remain on the polished semiconductor substrate surface and on the members used for polishing (e.g., a polishing pad). For this reason, a process of removing these residues using a composition is generally performed after the CMP process.

[0004] As described above, in the semiconductor manufacturing process, compositions are used for treatments such as removing unnecessary metal-containing substances, resists, and residues from various components used in semiconductor manufacturing. For example, Patent Document 1 discloses a "polishing and cleaning liquid composition characterized by containing a nonionic surfactant and water" as a polishing and cleaning liquid capable of efficiently removing particles from the surface of a semiconductor substrate after chemical mechanical polishing.

[0005] Japanese Patent Application Laid-Open No. 2004-323840

[0006] The present inventors investigated the removal of residues after CMP processing using the polishing and cleaning liquid composition specifically disclosed in Patent Document 1, but found that the desired effect could not be achieved. Specifically, when a process of performing CMP processing on a workpiece such as a semiconductor substrate (hereinafter also referred to as the "CMP process") and a process of cleaning the workpiece after the CMP processing with the composition using a pad (hereinafter also referred to as the "cleaning process") were performed, a large amount of residue was observed on the workpiece, and it was confirmed that the residue removal ability was insufficient. Furthermore, compositions used for such cleaning are required to exhibit excellent residue removal ability even after storage for a predetermined period of time. Furthermore, the above-mentioned CMP process and cleaning process are repeatedly performed while changing the workpiece. It is required that the polishing rate of the CMP process does not deteriorate when such CMP process and cleaning process are repeatedly performed.

[0007] Therefore, an object of the present invention is to provide a composition that has excellent residue removal properties, maintains excellent residue removal properties even after long-term storage, and exhibits little deterioration in the polishing rate of the CMP treatment when applied to a cleaning treatment in which CMP treatment and a subsequent cleaning treatment using a pad are repeated.Another object of the present invention is to provide a stock solution, a method for producing a cleaned object, and a method for producing an electronic device.

[0008] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0009] [1] A composition used for cleaning a workpiece that has been subjected to chemical mechanical polishing using a pad, comprising: a compound having a polyoxyalkylene chain and having no acidic group, basic group, or salt thereof; and an antibacterial agent, wherein the content of the compound is 0.3 to 5.0 mass% relative to the total mass of the composition, and the mass ratio of the content of the compound to the content of the antibacterial agent is 5 to 10,000. [2] The composition according to [1], which has a pH of 4.5 or less. [3] The composition according to [1], which has a pH of 7.5 or more. [4] The composition according to any one of [1] to [3], which is substantially free of abrasive particles. [5] The composition according to any one of [1] to [4], which further comprises a pH adjuster selected from an acid and an amine, and wherein the mass ratio of the content of the compound to the content of the pH adjuster is more than 5 and less than 10,000. [6] The composition according to any one of [1] to [5], further comprising an acid selected from the group consisting of nitric acid, phosphoric acid, and sulfuric acid. [7] The composition according to any one of [1] to [6], further comprising an aminoalcohol. [8] The composition according to any one of [1] to [7], further comprising an anticorrosion agent. [9] The composition according to [8], wherein the mass ratio of the content of the compound to the content of the anticorrosion agent is 60 to 1,000.

[10] The composition according to any one of [1] to [9], wherein the hydrophilic-lipophilic balance value of the compound is 12.0 to 20.0.

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

[10] , wherein the content of the compound relative to the total mass of the composition is equal to or greater than the critical micelle concentration of the compound at 25°C.

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

[11] , wherein the compound has at least one of a polyoxyethylene chain and a polyoxypropylene chain.

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

[12] , wherein the compound contains an ester bond.

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

[13] , wherein the workpiece subjected to the chemical mechanical polishing treatment contains at least one selected from the group consisting of a silicon compound, polysilicon, and amorphous silicon, and the silicon compound contains a silicon atom and at least one of an oxygen atom, a nitrogen atom, and a carbon atom.

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

[14] , wherein the workpiece subjected to the chemical mechanical polishing treatment contains at least one selected from the group consisting of tungsten, cobalt, ruthenium, titanium, titanium nitride, tantalum, and tantalum nitride.

[16] A stock solution used to obtain the composition according to any one of [1] to

[15] by dilution.

[17] The stock solution according to

[16] , comprising: a compound having a polyoxyalkylene chain and having no acidic group, basic group, or salt thereof; and an antibacterial agent, wherein the mass ratio of the content of the compound to the content of the antibacterial agent is 5 to 10,000, the content of the compound is 1 to 30 mass% with respect to the total mass of the stock solution, and the content of the antibacterial agent is 0.001 to 10 mass% with respect to the total mass of the stock solution, and the stock solution is used by diluting it 2 to 500 times by volume with water.

[18] A method for producing a cleaned workpiece, comprising the steps of bringing a workpiece that has been subjected to chemical mechanical polishing into contact with a pad while supplying the composition according to any one of [1] to

[15] , and moving the workpiece and the pad relative to each other to clean the workpiece, thereby obtaining a cleaned workpiece.

[19] A method for producing a cleaned workpiece according to

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

[20] A method for producing an electronic device, comprising the method for producing a cleaned workpiece according to

[18] or

[19] .

[0010] According to the present invention, there is provided a composition having excellent residue removal properties, which maintains excellent residue removal properties even after long-term storage, and which, when applied to a cleaning process in which CMP processing and a subsequent cleaning process using a pad are repeated, exhibits little deterioration in the polishing rate of the CMP processing. Furthermore, according to the present invention, there are also provided a stock solution, a method for producing a cleaned object, and a method for producing an electronic device.

[0011] FIG. 1 is a cross-sectional view showing a patterned wafer.

[0012] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0013] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0014] As used herein, the term "total mass of components in a composition excluding solvents" refers to the total mass of all components contained in the composition other than solvents such as water and organic solvents. Unless otherwise specified, the compounds described herein may contain structural isomers, optical isomers, and isotopes. Furthermore, the structural isomers, optical isomers, and isotopes may be contained singly or in combination of two or more types.

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

[0016] In this specification, "ppm" means "parts-per-million (10 －６ ) and "ppb" stands for "parts-per-billion (10 －９In this specification, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth)acrylamide" is a concept that includes both acrylamide and methacrylamide.

[0017] As used herein, "weight average molecular weight" refers to the weight average molecular weight calculated as polyethylene glycol, measured by GPC (gel permeation chromatography). As used herein, the "hydrophile-lipophile 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, a catalog value or a value calculated by another method may be used. HLB value = 20 × [(molecular weight of hydrophilic group contained in surfactant) / (molecular weight of surfactant)] As used herein, the "critical micelle concentration (CMC)" refers to the concentration at which the surface tension of an aqueous surfactant solution is measured at atmospheric pressure and 25°C while varying the concentration using a surface tensiometer such as a Wilhelmy surface tensiometer, and the CMC is the inflection point. In some cases, a catalog value or a value calculated by another method may be used. For example, a commercially available kit that measures the critical micelle concentration of a surfactant by utilizing the change in fluorescence of a fluorescent reagent that interacts with the surfactant can be used.

[0018] [Composition] The composition of the present invention will be described in detail below. The composition of the present invention (hereinafter also referred to simply as "the composition") is a composition used for cleaning a workpiece that has been subjected to chemical mechanical polishing using a pad, and comprises a compound having a polyoxyalkylene chain and having no acidic group, basic group, or salt thereof (hereinafter also referred to as "specific compound"), and an antibacterial agent, wherein the content of the compound is 0.3 to 5.0 mass% relative to the total mass of the composition, and the mass ratio of the content of the compound to the content of the antibacterial agent is 5 to 10,000.

[0019] While the reason why the present composition having the above-described configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. 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 the one described below, it is still within the scope of the present invention. Residues containing silicon oxides derived from the CMP polishing solution or the substrate tend to remain on a substrate after CMP processing. However, the specific compound effectively protects the residues, thereby preventing them from reattaching to the substrate, and therefore the present composition has excellent residue removal properties. Furthermore, the specific compound does not contain acidic groups, basic groups, or salts thereof, and therefore does not affect the dispersion and aggregation of residues, so residues are less likely to remain on the substrate and the substrate is less likely to be damaged.

[0020] In addition, when the content of the specific compound is 0.3 mass% or more relative to the total mass of the composition, excellent residue removability is achieved, and when the content is 5.0 mass% or less, deterioration in the polishing rate of the CMP treatment is minimized when the composition is applied to a cleaning treatment in which CMP treatment and subsequent cleaning treatment using a pad are repeated. Furthermore, when the mass ratio of the content of the specific compound to the content of the antibacterial agent is 5 or more, excellent residue removability is achieved as described above, and when the mass ratio is 10,000 or less, deterioration in residue removability over time can be suppressed. Thus, it is believed that the problem of the present invention can be solved by the specific compound having the above-described configuration in the composition. Hereinafter, the term "excellent effects of the present invention" refers to the superiority of at least one of the effects of improved residue removability when the composition is used, improved removability of residues generated by CMP even when the composition is used after long-term storage, and minimal deterioration in the polishing rate of CMP when the composition is applied to a cleaning treatment in which CMP treatment and subsequent cleaning treatment using a pad are repeated. The components contained in the composition and the physical properties of the composition will be described in detail below.

[0021] [Specific Compound] The present composition contains a compound (specific compound) that has a polyoxyalkylene chain and does not have any of an acidic group, a basic group, or a salt thereof. The polyoxyalkylene chain is -(R ａ O) ｎ- is a structure represented by R ａ represents an alkylene group, and n represents an integer of 2 or more. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 2 to 6, and even more preferably 2 or 3. n is preferably 2 to 50, more preferably 4 to 30, and even more preferably 6 to 20. The polyoxyalkylene chain is, among others, a polyoxyethylene chain (—CH ２ -CH ２ -O-), and polyoxypropylene chain (-CH ２ -CH(CH ３ )-O- or -(CH ２ ) ３ -O-). In other words, it is preferable that the specific compound has at least one of a polyoxyethylene chain and a polyoxypropylene chain. The specific compound may have only one of a polyoxyethylene chain and a polyoxypropylene chain, or may have both.

[0022] In this specification, an alcoholic hydroxyl group does not fall under either an acidic group or a basic group. Examples of the acidic group include a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and a carboxylic acid group. Examples of the basic group include primary, secondary, and tertiary amino groups, and a quaternary ammonium group.

[0023] The specific compound preferably has a hydrophilic group and a hydrophobic group that do not exhibit ionicity, and is preferably a so-called nonionic surfactant. Unlike ionic surfactants such as anionic surfactants and cationic surfactants, nonionic surfactants are compounds that have a surface-active function due to the presence of a hydrophilic group and a hydrophobic group that do not exhibit ionicity. The hydrophilic group may at least be the polyoxyalkylene chain described above. Specific examples and preferred embodiments of the polyoxyalkylene chain are as described above.

[0024] Examples of the hydrophobic group include hydrocarbon groups, and more specifically, examples include aliphatic hydrocarbon groups, aromatic ring groups which may have a substituent, and groups formed by combining these. The valence of each of the above groups is not particularly limited, and examples include monovalent to tetravalent groups. In particular, the specific compound preferably has a hydrocarbon group having 3 to 18 carbon atoms as the hydrophobic group, and more preferably has a hydrocarbon group having 10 to 18 carbon atoms. In addition to the hydrophilic group and hydrophobicity, the specific compound also preferably contains an ester bond.

[0025] The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aliphatic hydrocarbon group may be a monovalent group or a divalent or higher valent group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The linear or branched aliphatic hydrocarbon group preferably has 2 to 30 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 10 to 18 carbon atoms. The cyclic aliphatic hydrocarbon group may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as an adamantane ring. The cyclic aliphatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 7 to 30 carbon atoms, and even more preferably 8 to 20 carbon atoms.

[0026] The aromatic ring constituting the aromatic ring group may be either a monocycle or a polycycle. Examples of polycycles include a fused ring formed by condensing two or more monocycles, and a linked ring formed by connecting two or more rings selected from the monocycles and the fused rings with a single bond. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle, but an aromatic hydrocarbon ring is preferred. The aromatic ring preferably has 4 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms. Specific examples of aromatic rings include a benzene ring and a naphthalene ring. 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 an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a halogen atom.

[0027] Specific examples of the specific compound 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 distyrenated 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 glycol fatty acid ester, polyoxyalkylene glycol Examples of the polyoxyalkylene glycol fatty acid esters include 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, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, and polyoxyethylene sorbit beeswax. In the above specific examples, "polyoxyalkylene polyoxyalkylene" refers to a state in which two different polyoxyalkylene groups are bonded to each other. The fatty acid ester may be a partially esterified fatty acid ester. The oxyalkylene group is preferably an oxyethylene group or an oxypropylene group.

[0028] Among the above-mentioned specific examples, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene distyrenated phenyl ethers, polyoxyalkylene polyoxyalkylene block copolymers, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene fatty acid esters, and polyoxyalkylene hydrogenated castor oils are preferred, and polyoxyalkylene sorbitan fatty acid esters are more preferred. The oxyalkylene group is preferably an oxyethylene group or an oxypropylene group.

[0029] Among these, polysorbates (polyoxyalkylene sorbitan fatty acid esters) are preferred as the specific compounds. Polysorbates are nonionic surfactants obtained by reacting sorbitan fatty acid esters with ethylene oxide, and specific examples thereof include compounds represented by the following general formula (1):

[0030]

[0031] In general formula (1), w, x, y, and z each independently represent an integer of 2 or greater. However, w+x+y+z is an integer selected from 3 to 60. w+x+y+z is preferably 12 to 25, and more preferably 15 to 20. In general formula (1), R each independently represent an aliphatic hydrocarbon group having 10 or more carbon atoms. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 12 to 25, more preferably 12 to 20, and even more preferably 12 to 17. The aliphatic hydrocarbon group is preferably an alkyl group or an alkenyl group.

[0032] Specific examples of polyoxyalkylene sorbitan fatty acid esters include polyoxyethylene sorbitan mono fatty acid esters such as polyoxyethylene sorbitan monostearate (6 E.O. (average number of moles of ethylene oxide added)), polyoxyethylene sorbitan monostearate (20 E.O.), polyoxyethylene sorbitan monolaurate (6 E.O.), polyoxyethylene sorbitan monopalmitate (20 E.O.), polyoxyethylene sorbitan monooleate (6 E.O.), and polyoxyethylene sorbitan monooleate (20 E.O.); and polyoxyethylene sorbitan tri fatty acid esters such as polyoxyethylene sorbitan tristearate (20 E.O.) and polyoxyethylene sorbitan trioleate (20 E.O.).

[0033] Commonly used polysorbates include polysorbate 20 (Tween 20), polysorbate 40 (Tween 40), polysorbate 60 (Tween 60), polysorbate 65 (Tween 65), and polysorbate 80 (Tween 80), and among these, polysorbate 20 or polysorbate 80 is preferred as the specific compound.

[0034] Polysorbate 20 contains primarily the monolaurate ester of polyoxyethylene (20) sorbitan. Polysorbate 40 contains primarily the monopalmitate ester of polyoxyethylene (20) sorbitan. Polysorbate 60 contains primarily the monostearate ester of polyoxyethylene (20) sorbitan. Polysorbate 65 contains primarily the tristearate ester of polyoxyethylene (20) sorbitan. Polysorbate 80 contains primarily the monooleate ester of polyoxyethylene (20) sorbitan.

[0035] Commercially available polyoxyalkylene sorbitan fatty acid esters include "Emersol S-120V," "Emersol L-120V," "Emersol O-120V," "Rheodol TW-S120V," "Rheodol TW-L120," "Rheodol TW-O120V," "Rheodol TW-L106," "Rheodol TW-P120," "Rheodol TW-O320V," "Rheodol Super TW-L120," "Rheodol 440V," and "Rheodol 460V" (all manufactured by Kao Corporation, trade names); "Solgen TW-60F", "Solgen TW-20F", "Solgen TW-80F" (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade names); "Admul T60K" and "Admul T80K" (all manufactured by Kerry, trade names); "T-Maz60K" and "T-Maz80K" (all manufactured by BASF, trade names); "Willsurf TF-60" and "Willsurf TF-80" (all manufactured by NOF Corporation, trade names); "Glycosperse S-20K FG" and "Glycosperse O-20K FG" (all manufactured by Lonza, trade names).

[0036] The molecular weight of the specific compound is preferably 500 to 5000, more preferably 1000 to 3000, and even more preferably 1000 to 2000. When the specific compound has a molecular weight distribution, the above molecular weight refers to the weight average molecular weight.

[0037] In terms of achieving superior effects of the present invention, the hydrophilic-lipophilic balance (HLB) value of the specific compound is preferably 9.0 to 20.0, more preferably 12.0 to 20.0, and even more preferably 12.0 to 18.0. As described in detail above, the HLB value is a value that indicates the affinity of a surfactant for water and oil, with a larger value indicating greater hydrophilicity and a smaller value indicating greater lipophilicity.

[0038] As described above, the content of the specific compound is 0.3 to 5.0% by mass, relative to the total mass of the composition. The content of the specific compound is preferably 0.5 to 4.0% by mass, more preferably 0.5 to 3.0% by mass, and even more preferably 0.5 to 2.0% by mass. In particular, in terms of achieving superior effects of the present invention, the content of the specific compound relative to the total mass of the composition is preferably equal to or greater than the critical micelle concentration (CMC) of the specific compound at 25°C. The definition and measurement method of CMC are as described above.

[0039] The mass ratio of the content of the specific compound to the content of the antibacterial agent described below is 5 to 10,000. This mass ratio is preferably 10 to 1,000, and more preferably 50 to 500. The mass ratio of the content of the specific compound to the content of the pH adjuster described below is preferably more than 5 and less than 10,000, more preferably 10 to 3,000, and even more preferably 100 to 1,000. The mass ratio of the content of the specific compound to the content of the anticorrosive agent described below is preferably 1 to 20,000, more preferably 5 to 10,000, even more preferably 60 to 1,000, and particularly preferably 5 to 100.

[0040] [Antibacterial Agent] The present composition further contains an antibacterial agent, and as described above, the mass ratio of the content of the specific compound to the content of the antibacterial agent is 5 to 10,000. The antibacterial agent is a compound having antibacterial activity against bacteria and / or antifungal activity against mold, and is a compound different from the specific compound and each component described below. The antibacterial agent may be in the form of a salt (for example, a known salt, etc.).

[0041] Examples of antibacterial agents include quaternary ammonium antibacterial agents, carboxylic acid antibacterial agents, phenol 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.

[0042] Quaternary ammonium antibacterial agents refer to compounds or salts thereof having at least one quaternary ammonium cation group in the molecule, which have antibacterial and / or antifungal properties. Examples of quaternary ammonium antibacterial agents include benzalkonium chloride, didecyldimethylammonium chloride (DDAC), hexadecylpyridinium chloride (CPC), 3,3'-(2,7-dioxaoctane)bis(1-dodecylpyridinium bromide) (Hygeria), benzethonium chloride, and domiphen bromide. Of these, benzethonium chloride is preferred. Examples of carboxylic acid antibacterial agents include unsaturated carboxylic acids such as sorbic acid (hexadienoic acid) and dehydroacetic acid, and aromatic carboxylic acids such as benzoic acid and salicylic acid. Of these, sorbic acid, dehydroacetic acid, or benzoic acid is preferred, sorbic acid or dehydroacetic acid is more preferred, and sorbic acid is even more preferred. Examples of phenolic antibacterial agents include 3-methyl-4-chlorophenol (PCMC), 3-methyl-4-isopropylphenol (Biosol), 4-chloro-3,5-dimethylphenol (PCMX), cresol, chlorothymol, dichloroxylenol, and hexachlorophene. Of these, cresol is preferred. Examples of biguanide antibacterial agents include bis(p-chlorophenyldiguanide)hexane digluconate (chlorhexidine gluconate) and poly(hexamethylenebiguanide) hydrochloride (hexamethylenebiguanidine hydrochloride). Of these, chlorhexidine gluconate is preferred. Examples of sulfamide antibacterial agents include N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide (dichloolanid) and N-dichlorofluoromethylthio-N',N'-dimethyl-N-p-tolylsulfamide (tolylfluanid). Among these, tolylfluanid is preferred. Examples of peroxide antibacterial agents include hydrogen peroxide, peracetic acid, and chlorine dioxide. Among these, peracetic acid is preferred.Examples of isothiazolinone antibacterial agents include 2-methyl-4-isothiazolin-3-one (MIT), 2-octyl-4-isothiazolin-3-one (OIT), 1,2-benzisothiazol-3(2H)-one (BIT), and 5-chloro-2-methyl-4-isothiazolin-3-one (CIT). Among these, MIT, OIT, or BIT are preferred, with MIT or OIT being more preferred. Examples of imidazole antibacterial agents include 2-(4-thiazolyl)-benzimidazole (TBZ) and 2-benzimidazole methylcarbamate (Preventol BCM). Examples of ester antibacterial agents include glycerol laurate (monoglyceride) and parahydroxybenzoic acid ethyl ester (ethylparaben). Examples of alcohol-based antibacterial agents include ethyl alcohol (ethanol), 2-propanol (IPA), phenoxyethanol, 1,2-pentanediol, and 1,2-hexanediol. Examples of carbamate-based antibacterial agents include 3-iodo-2-propynyl butylcarbamate (Glycical). Examples of iodine-based antibacterial agents include [(4-chlorophenoxy)methyl]-3-iodo-2-propynyl ether (IF1000).

[0043] The antibacterial agent is preferably a quaternary ammonium antibacterial agent, a carboxylic acid antibacterial agent, a phenol antibacterial agent, or an isothiazolinone antibacterial agent, and more preferably a carboxylic acid antibacterial agent or an isothiazolinone antibacterial agent. Among these, the antibacterial agent is preferably benzethonium chloride, sorbic acid, dehydroacetic acid, benzoic acid, salicylic acid, cresol, MIT, OIT, or BIT.

[0044] The antibacterial agent may be used alone or in combination of two or more. The content of the antibacterial agent is preferably 0.00001 to 1.0 mass%, more preferably 0.0001 to 0.01 mass%, based on the total mass of the composition. The content of the antibacterial agent is preferably 0.001 to 20.0 mass%, more preferably 0.01 to 5.0 mass%, based on the total mass of the components in the composition excluding the solvent.

[0045] [pH Adjuster] The present composition preferably further contains a pH adjuster selected from acids and amines. The pH adjuster is an acid or amine different from the specific compound, the antibacterial agent, and the components described below. However, it is acceptable to adjust the pH of the present composition by adjusting the amount of each component other than the pH adjuster.

[0046] The acid is a compound that exhibits acidity (pH less than 7.0) in an aqueous solution. Examples of the acid include inorganic acids and organic acids, with inorganic acids being preferred. Examples of inorganic acids include nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, nitrous acid, sulfurous acid, and boric acid, with nitric acid, sulfuric acid, or phosphoric acid being preferred. Examples of organic acids include carboxylic acid-based organic acids, sulfonic acid-based organic acids, and phosphonic acid-based organic acids. The acid salt may be used as the pH adjuster as long as it becomes an acid or acid ion (anion) in an aqueous solution.

[0047] The amine is a compound or salt thereof having, in its molecule, at least one group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium cation group. When an amine has amino groups of different series, the amine is classified as the amine having the highest series. Examples of amine salts include salts with inorganic acids formed by bonding hydrogen to at least one nonmetal selected from the group consisting of Cl, S, N, and P, and hydrochlorides, sulfates, or nitrates are preferred.

[0048] The above amine preferably exhibits alkaline properties in aqueous solution (a pH of greater than 7.0 at 25°C). Among these, amines that have a pH of 9.0 to 14.0 at 25°C when dissolved at a concentration of 0.1 mol / L are more preferred, and amines with a pH of 10.0 to 13.0 are even more preferred. The amine may be either chain (linear or branched) or cyclic. Examples of amines include amino alcohols (alkanolamines), alicyclic amines, aliphatic amines other than amino alcohols and alicyclic amines, and quaternary ammonium compounds. It is particularly preferred that the present composition contains an amino alcohol.

[0049] <Amino alcohol> An amino alcohol is an amine compound that further has at least one hydroxyl alkyl group in the molecule. The amino alcohol may have any of primary to tertiary amino groups, but preferably has a primary amino group. Among these, it is more preferable that the amino alcohol has only primary amino groups as amino groups. The number of amino groups that the amino alcohol has is, for example, 1 to 5, and preferably 1 to 3. The number of hydroxyl groups that the amino alcohol has is, for example, 1 to 5, and more preferably 1 to 3.

[0050] 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), 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), and 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-cyclohexylethanolamine, 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. Among these, Tris, AMP, or DMAMP is preferred.

[0051] <Alicyclic amines> Examples of alicyclic amines include cyclic amidine compounds and piperazine compounds. Compounds included in amino alcohols are not included in alicyclic amines.

[0052] The cyclic amidine compound is a compound having a heterocycle containing an amidine structure (>N—C═N—) in the ring. The number of ring members in the heterocycle of the cyclic amidine compound is preferably 5 to 6, and more preferably 6. Examples of cyclic amidine compounds include diazabicycloundecene (1,8-diazabicyclo[5.4.0]undec-7-ene: DBU), diazabicyclononene (1,5-diazabicyclo[4.3.0]non-5-ene: DBN), 3,4,6,7,8,9,10,11-octahydro-2H-pyrimido[1.2-a]azocine, 3,4,6,7,8,9-hexahydro-2H-pyrido[1.2-a]pyrimidine, 2,5,6,7-tetrahydro-3H-pyrrolo[1.2-a]imidazole, 3-ethyl-2,3,4,6,7,8,9,10-octahydropyrimido[1.2-a]azepine, and creatinine.

[0053] The piperazine compound is a compound having a 6-membered heterocyclic ring (piperazine ring) in which opposing >CH- groups of a cyclohexane ring are replaced with tertiary amino groups (>N-). Examples of the piperazine compound include piperazine, 1-methylpiperazine, 2-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1-butylpiperazine, 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 1-phenylpiperazine, N-(2-aminoethyl)piperazine (AEP), 1,4-bis(2-aminoethyl)piperazine (BAEP), 1,4-bis(3-aminopropyl)piperazine (BAPP), and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0054] Examples of alicyclic amines other than piperazine compounds and cyclic amidine compounds include compounds having a nitrogen-containing 5-membered ring or a nitrogen-containing 7-membered ring, such as 1,3-dimethyl-2-imidazolidinone.

[0055] <Aliphatic Amines> Examples of aliphatic amines other than amino alcohols and alicyclic amines include primary aliphatic amines (aliphatic amines having a primary amino group), secondary aliphatic amines (aliphatic amines having a secondary amino group), and tertiary aliphatic amines (aliphatic amines having a tertiary amino group).

[0056] Examples of primary aliphatic amines include methylamine, ethylamine, propylamine, dimethylamine, diethylamine, n-butylamine, 3-methoxypropylamine, tert-butylamine, n-hexylamine, n-octylamine, and 2-ethylhexylamine. Examples of secondary aliphatic amines include alkylenediamines such as ethylenediamine (EDA), 1,3-propanediamine (PDA), 1,2-propanediamine, 1,3-butanediamine, and 1,4-butanediamine; and polyalkylpolyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), bis(aminopropyl)ethylenediamine (BAPEDA), and tetraethylenepentamine. Examples of tertiary aliphatic amines include tertiary alkylamines such as trimethylamine and triethylamine; alkylenediamines such as 1,3-bis(dimethylamino)butane; and polyalkylpolyamines such as N,N,N',N'',N''-pentamethyldiethylenetriamine.

[0057] <Quaternary ammonium compound> The quaternary ammonium compound is not particularly limited as long as it is a compound having at least one quaternary ammonium cation group formed by substituting four hydrocarbon groups (preferably alkyl groups) on a nitrogen atom, or a salt thereof. Examples of the quaternary ammonium compound include quaternary ammonium hydroxide, quaternary ammonium fluoride, quaternary ammonium bromide, quaternary ammonium iodide, quaternary ammonium acetate, and quaternary ammonium carbonate. Among these, quaternary ammonium hydroxide is preferred, and a compound represented by the following formula (a1) is more preferred.

[0058]

[0059] In the above formula (a1), R ａ１ ~R ａ４ R each 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 the groups may be bonded to each other to form a ring structure.

[0060] As the compound represented by the above formula (a1), from the viewpoint of availability, 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, and TMAH, TEAH, or TBAH is more preferred.

[0061] When the amine is a compound having at least one group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group, or a salt thereof, the acid dissociation constant of these amines is preferably 7.5 or more, more preferably 8.0 or more, and even more preferably 8.2 or more. There is no particular upper limit, but it is preferably 12.0 or less. Here, the acid dissociation constant (hereinafter also referred to as "pKa") means the acid dissociation constant of the conjugate acid of the amine, and when multiple conjugate acids are present, it means the highest first acid dissociation constant. Examples of amines having a pKa in the above range include TEA (pKa: 7.8), Tris (pKa: 8.3), DEA (pKa: 8.9), MEA (pKa: 9.5), N-MAMP (pKa: 9.7), AMP (pKa: 9.7), DMAMP (pKa: 10.2), DBU (pKa: 10.6), and DBN (pKa: 10.6). The pKa of the amine is the value in water (temperature 25°C) calculated using Calculator Plugins (manufactured by Fujitsu). If the pKa cannot be measured in water, the value is calculated in dimethyl sulfoxide.

[0062] The amine is preferably a compound having at least one amino group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group in the molecule, or a salt thereof, more preferably an amino alcohol, and even more preferably the amino alcohol of the preferred embodiment described above. It is also preferable that the amine does not have at least one of a carboxy group, a carbonyl group, and an aromatic ring.

[0063] The present composition preferably further contains, as a pH adjuster, an acid selected from the group consisting of nitric acid, phosphoric acid, and sulfuric acid. The pH adjusters may be used singly or in combination of two or more. The content of the pH adjuster can be selected depending on the type and amount of other components and the desired pH of the composition. For example, the content of the pH adjuster is preferably 0.0001 to 10% by mass, more preferably 0.001 to 1.0% by mass, and even more preferably 0.001 to 0.1% by mass, relative to the total mass of the present composition.

[0064] [Water] The present composition preferably contains water. The type of water may 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 semiconductor substrate manufacturing process. The water content may be the balance of the components that can be contained in the water composition. The water content is preferably 60.0 mass% or more, more preferably 80.0 mass% or more, even more preferably 90.0 mass% or more, and particularly preferably 97.0 mass% or more, based on the total mass of the water composition. The upper limit is preferably 99.99 mass% or less, and more preferably 99.9 mass% or less, in order to achieve better effects of the present invention.

[0065] [Corrosion inhibitor] The present composition preferably further contains a corrosion inhibitor. The corrosion inhibitor is not particularly limited as long as it is a compound that has the function of preventing corrosion of the exposed surface of the workpiece. As the corrosion inhibitor, a compound having an amino group other than a nitrogen-containing heterocyclic group (hereinafter also referred to as a "specific amino group") selected from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group is preferred, and a compound having a primary amino group is more preferred. Note that a compound having the above-mentioned specific amino group that has the function of preventing corrosion of the exposed surface of the workpiece is treated as a corrosion inhibitor.

[0066] The number of specific amino groups in the corrosion inhibitor is preferably 2 to 5, and more preferably 2 to 4. The number of carbon atoms in the corrosion inhibitor is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less. There is no particular lower limit, and 3 or more is preferable. Furthermore, the corrosion inhibitor preferably has at least one carboxy group in addition to the specific amino group. In other words, the corrosion inhibitor is preferably an amino acid. The amino acid may be any of D-, L-, and DL-isomers. When the corrosion inhibitor has carboxy groups, the number of carboxy groups is preferably 1 to 5. Among these, the corrosion inhibitor is preferably a basic amino acid.

[0067] 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, and the compounds described in paragraphs

[0021] to

[0023] of JP 2016-086094 A, as well as salts thereof. Examples of histidine derivatives include compounds described in JP 2015-165561 A, JP 2015-165562 A, and the like, the contents of which are incorporated herein by reference. Examples of salts include alkali metal salts such as sodium salts and potassium salts, ammonium salts, carbonates, and acetates. The amino acid as the anticorrosive agent is preferably arginine, histidine, lysine, ornithine, 2,4-diaminobutyric acid, tryptophan, asparagine, or glutamine, more preferably arginine, histidine, or lysine, and even more preferably L-arginine, L-histidine, or L-lysine.

[0068] In addition to amino acids, nitrogen-containing polymers can also be preferably used as anticorrosive agents. A nitrogen-containing polymer is a polymer containing a repeating unit containing a nitrogen atom (N-containing repeating unit). When the nitrogen-containing polymer also contains repeating units other than the N-containing repeating unit, it is preferable that the content (molar ratio) of the N-containing repeating unit is the largest among all types of repeating units. The content of the N-containing repeating unit in the nitrogen-containing polymer is preferably 51 to 100 mol %, more preferably 75 to 100 mol %, based on the total repeating units of the polymer. The weight-average molecular weight of the nitrogen-containing polymer is preferably 400 to 50,000.

[0069] Examples of monomers from which the N-containing repeating unit is derived include ethyleneimine, vinylpyrrolidone, allylamine, vinylamine, vinylpyridine, acrylamide, hexadimethrine salts (halide salts, hydroxide salts, nitrate salts, sulfate salts, etc.), diallylamine, dimethyldiallylammonium salts (halide salts, hydroxide salts, nitrate salts, sulfate salts, etc.), ornithine, lysine, arginine, histidine, vinylimidazole, and methyldiallylamine. Furthermore, as the N-containing repeating unit, a repeating unit consisting of dimethylamine and epihalohydrin (preferably epichlorohydrin) may also be used.

[0070] The nitrogen atom-containing polymer is preferably at least one selected from the group consisting of polyethyleneimine, polyvinylpyrrolidone, polyvinylpyridine, polyallylamine, polyvinylamine, polyacrylamide, dimethylamine-epihydrin polymers (preferably dimethylamine-epihalohydrin copolymers, more preferably dimethylamine-epichlorohydrin copolymers), hexadimethrine salts (halide salts, hydroxide salts, nitrate salts, sulfate salts, etc.), polydiallylamine, polydimethyldiallylammonium salts (halide salts, hydroxide salts, nitrate salts, sulfate salts, etc.), poly(4-vinylpyridine), polyornithine, polylysine, polyarginine, polyhistidine, polyvinylimidazole, and polymethyldiallylamine.

[0071] As the nitrogen atom-containing polymer, the compounds described in paragraphs

[0053] to

[0055] of JP-A-2023-036214, paragraphs

[0018] to

[0061] of WO 2023 / 047959, and paragraphs

[0025] to

[0061] of WO 2023 / 054233 can be used, and the contents of these compounds are incorporated herein.

[0072] Heterocyclic compounds can also be used as anticorrosive agents. Among heterocyclic compounds, nitrogen-containing heterocyclic compounds in which at least one of the heteroatoms constituting the heterocycle is a nitrogen atom are preferred. Examples of nitrogen-containing heterocyclic compounds include azole compounds, purine compounds, pyrrole compounds, pyridine compounds, pyrazine compounds, pyrimidine compounds, indole compounds, indolizine compounds, indazole compounds, quinoline compounds, and oxazole compounds, with purine compounds or azole compounds being preferred. Specifically, examples of anticorrosive agents include the compounds described in paragraphs

[0046] to

[0050] of International Publication No. 2021 / 166571, the contents of which are incorporated herein by reference.

[0073] The anticorrosive agent may be used alone or in combination of two or more. The content of the anticorrosive agent is preferably 0.00001 to 5.0 mass%, more preferably 0.0001 to 1.0 mass%, and even more preferably 0.001 to 0.1 mass%, relative to the total mass of the composition. The content of the anticorrosive agent is preferably 0.001 to 35.0 mass%, more preferably 0.01 to 10.0 mass%, and even more preferably 0.1 to 5.0 mass%, relative to the total mass of the components in the composition excluding the solvent.

[0074] [Other Components] The composition may contain other components in addition to those described above. Examples of other components include organic solvents, polymers, polyhydroxy compounds with a molecular weight of 500 or more, oxidizing agents, reducing agents, and fluorides.

[0075] <Organic Solvent> Examples of the organic solvent include known organic solvents, such as alcohol-based solvents, glycol-based solvents, glycol ether-based solvents, and ketone-based solvents. The organic solvent is preferably miscible with water at any ratio. Examples of the organic solvent include the compounds exemplified in paragraphs

[0135] to

[0140] of WO 2022 / 044893, the contents of which are incorporated herein by reference.

[0076] <Polymer> The composition preferably contains a polymer, as this provides superior organic residue removal. The polymer is preferably a water-soluble polymer. The term "water-soluble polymer" refers to a compound in which two or more structural units are linked together in a linear or network-like manner via covalent bonds, and which dissolves in 100 g of water at 20°C in a mass of 0.1 g or more. More specific examples of the polymer include polyvinyl alcohol, hydroxyethyl cellulose, polyvinylpyrrolidone, poly(meth)acrylic acid, poly(meth)acrylamide, polystyrene sulfonic acid, polymaleic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, and copolymers of monomers having acid groups (e.g., (meth)acrylic acid monomers and monomers having sulfonic acid groups and polymerizable ethylene groups), as well as salts thereof. Polymers that do not ionize in aqueous solution are preferred. Examples of polymers include the compounds described in paragraphs

[0043] to

[0047] of JP 2016-171294 A, the contents of which are incorporated herein by reference. The weight average molecular weight (Mw) of the polymer is preferably 1000 or more, more preferably 2000 or more. The upper limit of the weight average molecular weight (Mw) of the water-soluble polymer is often 1.5 million or less, preferably 100,000 or less, more preferably 50,000 or less.

[0077] The content of the polymer is preferably 0.0001 to 5.0% by mass, more preferably 0.001 to 0.1% by mass, based on the total mass of the composition, and preferably 1.0 to 20.0% by mass, more preferably 3.0 to 15.0% by mass, and even more preferably 3.0 to 10.0% by mass, based on the total mass of the components in the composition excluding the solvent.

[0078] <Polyhydroxy Compound> The polyhydroxy compound having a molecular weight of 500 or more is a compound different from the above-mentioned compounds that can be contained in the composition. The polyhydroxy compound is an organic compound having two or more (e.g., 2 to 200) alcoholic hydroxyl groups per molecule. The molecular weight (weight average molecular weight when the polyhydroxy compound has a molecular weight distribution) of the polyhydroxy compound is 500 or more, preferably 500 to 100,000, and more preferably 500 to 3,000. As the polyhydroxy compound, the compounds exemplified in paragraphs

[0101] and

[0102] of WO 2022 / 014287 can also be used, and the contents of these can be incorporated herein.

[0079] <Oxidizing Agent> Examples of the oxidizing agent include peroxides (hydrogen peroxide, etc.), persulfides (e.g., monopersulfides and dipersulfides), percarbonates, acids thereof, and salts thereof. Examples of the oxidizing agent include oxide halides (periodic acids such as iodic acid, metaperiodic acid, and orthoperiodic acid, and salts thereof), perboric acid, perborates, cerium compounds, and ferricyanides (potassium ferricyanide, etc.).

[0080] <Reducing Agent> Examples of reducing agents include catechol or derivatives thereof (e.g., methylcatechol, gallic acid, pyrogallol, ellagic acid, catechol-4-acetic acid, catechin, and isoflavone), ascorbic acid or derivatives thereof (e.g., isoascorbic acid, ascorbic acid sulfate, and ascorbic acid phosphate), and mercapto compounds (e.g., mercaptosuccinic acid, 1-thioglycerol, 2-mercaptoethanol, 3-mercapto-1-propanol, and thioglycolic acid). Compounds described in paragraphs

[0054] to

[0065] of WO 2019 / 187868 can also be used as reducing agents, and the contents of these compounds are incorporated herein by reference.

[0081] Fluorides are compounds that serve as a source of fluorine-containing ions, and examples thereof include compounds containing fluorine-containing ions and cations. Examples of the fluorine-containing ions include fluoride ions (F － ), bifluoride ion (HF２ － ), and fluoride-containing ions (e.g., MF ６ ｎ－ , M: any atom, n: 1 to 3). Examples of M include B, Al, Si, P, Ti, Zr, Nb, Sb, and Ta. Specific examples of fluorides include HF, NH ４ F, H ２ SiF ６ , H ２ TiF ６ , H ２ ZrF ６ , HPF ６ , and HBF ４ Examples include:

[0082] [Physical Properties of Composition] <pH> The composition may be either acidic or alkaline. When the composition is acidic, the pH is preferably 6.0 or less, more preferably 5.0 or less, and even more preferably 4.5 or less, in terms of achieving superior effects of the present invention. When the composition is alkaline, the pH is preferably 7.5 or more, more preferably 8.0 or more, and even more preferably 8.5 or more. The pH of the composition can be measured using a known pH meter by a method in accordance with JIS Z8802-1984. The pH is measured at 25°C.

[0083] <Metal Content> The content (measured as ion concentration) of metals (e.g., metal elements Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) contained as impurities in the composition is preferably 5 mass ppm or less, more preferably 1 mass ppm or less. Since it is expected that compositions of even higher purity will be required in the manufacture of cutting-edge semiconductor devices, the content of the above metals is more preferably lower than 1 mass ppm, that is, on the order of ppb or less, particularly preferably 100 mass ppb or less, and most preferably less than 10 mass ppb. The lower limit is preferably 0.

[0084] Examples of methods for reducing the metal content include performing purification treatments such as distillation and filtration using an ion exchange resin or a filter at the stage of raw materials used in producing the composition or at the stage after production of the composition. Another method for reducing the metal content includes using a container that minimizes the elution of impurities, as described below, as a container for containing raw materials or the produced composition. Another method includes lining the inner wall of a pipe with a fluororesin to prevent elution of metal components from the pipe during production of the composition.

[0085] <Coarse Particles> The present composition may contain coarse particles, but the content thereof is preferably low. Coarse particles refer to particles having a diameter (particle size) of 0.03 μm or more when the particle shape is considered as a sphere. The coarse particles contained in the present composition include particles such as dust, dirt, organic solids, and inorganic solids contained as impurities in the raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids brought in as contaminants during the preparation of the composition, which ultimately exist as particles without dissolving in the composition.

[0086] The content of coarse particles in the present composition is preferably 10,000 or less, more preferably 5,000 or less, of particles with a particle size of 0.1 μm or more per mL of the composition. The lower limit is preferably 0 or more, more preferably 0.01 or more, per mL of the composition. The content of coarse particles present in the present composition can be measured in the liquid phase using a commercially available measuring device that uses a laser as a light source for light scattering liquid particle measurement. Methods for removing coarse particles include, for example, purification processes such as filtering, which will be described later.

[0087] <Abrasive Particles> Preferably, the present composition is substantially free of abrasive particles. "Substantially free of abrasive particles" specifically means that the content of abrasive particles is 1,000 ppm by mass or less, preferably 500 ppm by mass or less, and more preferably 100 ppm by mass or less, relative to the total mass of the present composition. The lower limit is preferably 0% by mass or more, relative to the total mass of the present composition. Examples of abrasive particles include abrasive particles such as silicon oxide contained in chemical mechanical polishing slurries and those described in paragraphs

[0194] to

[0197] of WO 2021 / 131451. Examples of methods for measuring the content of abrasive particles include, for example, a method of measuring in the liquid phase using a commercially available measuring device that uses a laser as a light source for light scattering liquid particle measurement. Examples of methods for adjusting the content of abrasive particles include known methods such as filtering.

[0088] [Method for producing the present composition] The present composition can be produced by a known method, which will be described in detail below.

[0089] [Preparation step] The present composition can be produced, for example, by mixing the above-mentioned components.As a method for preparing the present composition, for example, a specific compound, an antibacterial agent, and, if necessary, optional components are sequentially added to a container containing purified pure water, and then the mixture is stirred and mixed, and, if necessary, a pH adjuster is added to adjust the pH of the mixture, thereby preparing the composition.In addition, when adding each component to a container, they may be added all at once, or may be added in multiple divided portions.

[0090] The stirring device and stirring method used to prepare the composition may be a known device such as a stirrer or disperser. Examples of stirrers include industrial mixers, portable stirrers, mechanical stirrers, and magnetic stirrers. Examples of dispersers include industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.

[0091] The mixing of the components in the preparation step of the present composition, the purification treatment described below, and the storage of the produced composition are preferably carried out at 40° C. or lower, more preferably 30° C. or lower. The lower limit is preferably 5° C. or higher, more preferably 10° C. or higher. By preparing, treating, and / or storing the composition within the above temperature range, the performance can be stably maintained for a long period of time.

[0092] <Purification> It is preferable to perform a purification treatment in advance on one or more of the raw materials used to prepare the present composition. Examples of purification treatment include known methods such as distillation, ion exchange, and filtration. The degree of purification is preferably such that the raw materials have a purity of 99% by mass or more, and more preferably such that the purity of the raw solution has a purity of 99.9% by mass or more. The upper limit is preferably 99.9999% by mass or less.

[0093] Examples of purification methods include passing the raw material through an ion exchange resin or a reverse osmosis membrane (RO membrane), reprecipitation, distillation of the raw material, and filtering. A combination of the above purification methods may be used as the purification method. For example, the raw material may be subjected to primary purification by passing it through an RO membrane, and then subjected to secondary purification by passing it through a purification device consisting of a cation exchange resin, an anion exchange resin, or a mixed-bed ion exchange resin. Furthermore, the purification process may be performed multiple times.

[0094] The filter used for filtering is not particularly limited as long as it is one that has been conventionally used for filtering purposes. Examples include filters made of fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyallylsulfone (PAS), and polyolefin resins (including high-density or ultra-high molecular weight) such as polyethylene and polypropylene (PP). 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. Filtering raw materials using filters made of these materials can effectively remove highly polar foreign matter that is likely to cause defects.

[0095] <Container> The present composition (including the diluted composition described below) can be filled into any container for storage, transportation, and use, as long as corrosiveness and other factors do not pose a problem.

[0096] As a container, a container with a high degree of cleanliness within the container for semiconductor applications and suppressing the elution of impurities from the inner wall of the container's storage portion into each liquid is preferred. Examples of such containers include various containers commercially available as containers for semiconductor compositions, such as the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited to these. In addition, the containers exemplified in paragraphs

[0121] to

[0124] of WO 2022 / 004217 can also be used as containers, and the contents of these containers are incorporated herein.

[0097] The interior of these containers is preferably washed before filling with the composition. The liquid used for washing is preferably one that has a reduced amount of metal impurities. After production, the composition may be bottled in containers such as gallon bottles or quart bottles, and then transported and stored.

[0098] In order to prevent changes in the components of the composition during storage, the atmosphere inside the container may be replaced with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or more. During transportation and storage, the composition may be kept at room temperature, or the temperature may be controlled within the range of -20°C to 20°C to prevent deterioration.

[0099] <Clean Room> It is preferable that all of the manufacturing of the composition, handling including opening and cleaning of containers, filling of the composition, processing analysis, and measurement be carried out in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferable that the clean room 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.

[0100] Alternatively, the composition may be prepared by diluting the stock solution shown below.

[0101] <Concentrate> The concentrate of the present invention is a concentrate used to obtain the present composition described above by dilution.

[0102] The stock solution preferably contains a specific compound and an antibacterial agent, and the mass ratio of the specific compound content to the antibacterial agent content is 5 to 10,000. The specific compound and antibacterial agent are synonymous with the specific compound and antibacterial agent contained in the composition, and preferred embodiments are as described above. The preferred range of the mass ratio of the specific compound content to the antibacterial agent content in the stock solution is the same as the preferred range of mass ratio described above for the composition. The content of the specific compound in the stock solution is not particularly limited as long as the content of the specific compound is 0.3 to 5.0% by mass relative to the total mass of the composition upon dilution, but is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and even more preferably 3 to 25% by mass relative to the total mass of the stock solution. The content of the antibacterial agent is not particularly limited as long as the mass ratio is in the range of 5 to 10,000, but the content of the antibacterial agent is preferably 0.001 to 20 mass%, more preferably 0.001 to 10 mass%, and even more preferably 0.005 to 1 mass%, relative to the total mass of the stock solution.

[0103] The diluent is preferably water (preferably ultrapure water), and it is preferable to purify the diluent beforehand.

[0104] The dilution ratio may be adjusted appropriately depending on the type and content of each component, the concentration of each component in the stock solution, and the material to be treated, but is preferably 1.2 to 10,000 times by mass or volume (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. In particular, the stock solution is preferably diluted with water 2 to 500 times by volume, and more preferably 10 to 100 times by volume.

[0105] The change in pH before and after dilution (the difference between the pH of the original solution and the pH of the present composition obtained by dilution) is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.3 or less.

[0106] [Uses] The present composition is used for cleaning a workpiece that has been subjected to chemical mechanical polishing (hereinafter also referred to as a "workpiece after CMP processing") using a pad. This cleaning process is generally also called rinse polishing, buffing, or buff cleaning, and is a process that uses a pad to reduce residues present on the surface of the workpiece. Specifically, while supplying the present composition, the surface of the workpiece that has been subjected to CMP processing is brought into contact with a pad, and the workpiece and the pad are moved relative to each other. More specifically, the present composition is supplied to the contact point between the workpiece and the pad. As a result, residues on the surface of the workpiece are removed by the frictional force of the pad and the chemical action of the present composition.

[0107] The equipment and conditions used in the cleaning treatment using the present composition can be appropriately selected from known equipment and conditions depending on the type of object to be treated and the type and amount of residue to be removed. For example, the treatment method described in paragraphs

[0085] to

[0088] of WO 2017 / 169539 can be used, the contents of which are incorporated herein by reference.

[0108] [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 of semiconductor substrates, but is preferably a pad used in CMP processing. Specific examples of pads include resin pads such as foamed polyurethane buff pads, nonwoven fabric buff pads, suede buff pads, and buff pads such as sponges.

[0109] [Workpiece] The workpiece is often a semiconductor substrate, and a semiconductor substrate containing a metal is preferable. When the semiconductor substrate contains a metal, the metal may be located on the front, back, side, or in a groove of the semiconductor substrate, for example. When the semiconductor substrate contains a metal, the metal may be located not only directly on the surface of the semiconductor substrate, but also on the semiconductor substrate via another layer.

[0110] Examples of the metal 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). At least one metal M selected from the group consisting of tungsten, cobalt, ruthenium, titanium, and tantalum is preferred.

[0111] The metal is preferably present as a metal layer containing the metal. Examples of the form of the metal contained in the metal layer include a simple substance of the metal M and an alloy containing the metal M. In particular, the workpiece preferably has a metal layer containing the metal M, and more preferably has a metal layer containing tungsten, cobalt, ruthenium, titanium, or tantalum.

[0112] The workpiece may include, in addition to the metal layer described above, a semiconductor substrate, an insulating film, a metal wiring film, and a barrier metal, for example.

[0113] Examples of wafers constituting semiconductor substrates include wafers made of silicon-based materials such as silicon (Si) wafers, silicon carbide (SiC) wafers, and silicon-containing resin wafers (glass epoxy wafers), as well as gallium phosphide (GaP) wafers, gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers. Examples of silicon wafers include n-type silicon wafers doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb)), and p-type silicon wafers doped with trivalent atoms (e.g., boron (B) and gallium (Ga)). Examples of silicon in silicon wafers include single crystal silicon, polysilicon (polycrystalline silicon), and amorphous silicon.

[0114] The insulating film may be, for example, a silicon oxide film (e.g., silicon dioxide (SiO ２ ) film and tetraethyl orthosilicate (Si(OC ２ H ５ ) ４ ) film (TEOS film), silicon nitride film (e.g., silicon nitride (Si ３ N ４ ) and silicon carbide nitride (SiNC), etc.), and low dielectric constant (Low-k) films (for example, carbon-doped silicon oxide (SiOC) films, black diamond (BD) films, silicon carbide (SiC) films, etc.), with low dielectric constant (Low-k) films being preferred. The workpiece preferably contains at least one material selected from the group consisting of silicon compounds, polysilicon, and amorphous silicon. The silicon compound preferably contains a silicon atom and at least one of an oxygen atom, a nitrogen atom, and a carbon atom. Specific examples of silicon compounds include the materials listed above as insulating film materials.

[0115] 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).

[0116] Examples of barrier metals include tantalum (Ta), tantalum nitride (TaN), titanium nitride (TiN), cobalt (Co), cobalt alloys, ruthenium (Ru), and ruthenium alloys.

[0117] It is particularly preferable that the workpiece contains at least one selected from the group consisting of tungsten, cobalt, ruthenium, titanium, titanium nitride, tantalum, and tantalum nitride.

[0118] <CMP Treatment> The CMP (chemical mechanical polishing) treatment is a treatment for planarizing 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 action of chemical action and mechanical polishing using a polishing slurry containing abrasive 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 the polishing slurry to the contact portion. As a result, the material on the surface of the workpiece is removed and planarized by the frictional force between the polishing pad, the polishing slurry, and the surface of the workpiece, and the chemical action of the polishing slurry. The polishing pad is not particularly limited, and pads commonly used in CMP treatment, such as nonwoven fabric, polyurethane foam, and porous fluororesin, can be used.

[0119] Residues such as metal impurities derived from the abrasive grains (e.g., silica and alumina) used in the CMP process, the polished metal wiring film, and / or the barrier metal may remain on the surface of the workpiece after CMP. Organic matter derived from the CMP composition used during the CMP process may also remain as residue. These residues may, for example, cause short circuits between wirings and degrade the electrical properties of the semiconductor substrate. Therefore, the semiconductor substrate after CMP is subjected to a cleaning process to remove these residues from the surface. The composition of the present invention is a composition used for cleaning the workpiece after CMP, as described above, particularly when using a pad. Specific examples of workpieces after CMP include, but are not limited to, the CMP-treated substrates described in the Journal of the Japan Society for Precision Engineering, Vol. 84, No. 3, 2018.

[0120] [Method for producing a cleaned processed object] As described above, the present composition is used to clean a processed object after CMP processing using a pad, and a cleaned processed object is obtained by the above cleaning.

[0121] [Cleaning step using the present composition] The method for producing a cleaned workpiece of the present invention includes a step of contacting a workpiece that has been subjected to chemical mechanical polishing with a pad while supplying the present composition, and moving the workpiece and the pad relative to each other to clean the workpiece and obtain a cleaned workpiece (hereinafter also referred to as the "present cleaning step"). In the above production method, the present composition is supplied to the contact area between the workpiece and the pad, and the cleaning is performed. Preferred embodiments of the workpiece, pad, equipment used, and conditions in the present cleaning step are as described above.

[0122] In this cleaning process, the method for contacting the workpiece with the pad can be any method commonly used in this field, but it is preferable to move the workpiece and the pad relative to each other while the pad is pressed against the workpiece. The pressure during the pressing is preferably 5 to 100 hPa, more preferably 10 to 50 hPa.

[0123] The temperature of the composition is not particularly limited, but is preferably 10 to 60°C, more preferably 15 to 50°C, from the viewpoints of superior cleaning properties and suppressing damage to components. The pH of the composition is preferably the preferred pH embodiment described above. The contact time between the object to be treated and the composition may be appropriately changed depending on the type and content of each component contained in the composition, but is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and even more preferably 30 to 60 seconds.

[0124] The amount (feed rate) of the composition is preferably 50 to 5,000 mL / min, and more preferably 100 to 2,000 mL / min.

[0125] The processing method in this cleaning step may be either a single wafer method or a batch method. The single wafer method is a method in which workpieces are processed one by one, while the batch method is a method in which multiple workpieces are processed simultaneously.

[0126] [Cleaning Steps Other Than the Main Cleaning Step] The method for producing a cleaned workpiece of the present invention may include a cleaning step other than the main cleaning step, and preferably includes a cleaning step other than the main cleaning step. Examples of cleaning steps other than the main cleaning step include a cleaning step that does not use a pad and a rinsing step.

[0127] <Cleaning Step Without Using a Pad> An example of a cleaning step without using a pad is a step in which the object to be treated is brought into contact with a treatment liquid.

[0128] The treatment liquid may be a known composition, or may be the present composition, depending on the type of object to be treated and the type and amount of residue to be removed. Examples of components that treatment liquids other than the present composition may contain include water-soluble polymers such as polyvinyl alcohol, dispersion media such as water, acids such as nitric acid, basic compounds such as amines, surfactants, antibacterial agents, and phosphonic acid compounds. Treatment liquids other than the present composition may be acidic, basic, or neutral, and are preferably acidic (more preferably pH 6 or less) or basic (more preferably pH 8 or more).

[0129] The method for contacting the object to be treated with the treatment liquid is not particularly limited, and examples thereof include a method of immersing the object to be treated in the treatment liquid placed in a tank, a method of spraying the treatment liquid onto the object to be treated, a method of flowing the treatment liquid onto the object to be treated, and combinations thereof. The contact of the object to be treated with the treatment liquid in the contact step may be carried out only once, or may be carried out two or more times. When carried out two or more times, the same method may be repeated, or different methods may be combined.

[0130] The temperature of the treatment liquid is not particularly limited, but is preferably 10 to 60°C, more preferably 15 to 50°C, from the viewpoints of superior cleaning properties and suppressing damage to components. The supply amount (supply rate) of the treatment liquid is preferably 50 to 5,000 mL / min, more preferably 500 to 2,000 mL / min. The contact time between the object to be treated and the treatment liquid may be appropriately changed depending on the type and content of each component contained in the treatment liquid, and the object and purpose of use of the treatment liquid, but is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and even more preferably 30 to 60 seconds.

[0131] The cleaning process without using a pad may be performed in a manner generally employed in this field. For example, it may be performed by scrubbing, in which a cleaning member such as a brush is brought into physical contact with the surface of the workpiece while a treatment liquid is supplied to remove residues, or by a spin (drop) method, in which a treatment liquid is dropped onto the workpiece while the workpiece is rotating. In the immersion method, ultrasonic treatment is preferably performed on the workpiece immersed in the treatment liquid, since this method can further reduce impurities remaining on the surface of the workpiece.

[0132] In a cleaning step that does not use a pad, mechanical agitation may be used to further enhance the cleaning ability of the treatment solution, such as circulating the treatment solution over the workpiece, flowing or spraying the treatment solution over the workpiece, or agitating the treatment solution with ultrasonic waves or megasonics.

[0133] <Rinsing step> After the above-described cleaning step, a step of contacting the workpiece with a rinse liquid (hereinafter also referred to as the "rinsing step") may be performed. By performing the rinsing step, the workpiece obtained in the cleaning step can be washed with the rinse liquid, and residual matter can be efficiently removed. The rinsing step is preferably performed consecutively after the semiconductor substrate cleaning step, and is a step of rinsing the workpiece with the rinse liquid. The rinsing step may be performed using the above-described mechanical stirring method.

[0134] 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. Aqueous rinse solutions having a pH greater than 8.0 (such as diluted aqueous ammonium hydroxide) may also be used.

[0135] The method of contacting the rinse solution with the object to be treated can be the same as the method of contacting the composition with the object to be treated. The contact time between the object to be treated and the rinse solution can be appropriately changed depending on the type and content of each component contained in the composition, and the object and purpose of use of the composition. Practically, the contact time is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and even more preferably 30 to 60 seconds.

[0136] [Drying Step] If necessary, a drying step may be performed to dry the workpiece. Examples of the drying method include spin drying, flowing a dry gas over the workpiece, heating the substrate with a heating means such as a hot plate or an infrared lamp, Marangoni drying, Rotagoni drying, IPA drying, and any combination thereof.

[0137] [Method for Manufacturing Electronic Devices] The method for manufacturing a cleaned workpiece described above can be suitably applied to the manufacturing process of electronic devices. The manufacturing method described above may be performed before or after other processes performed on the substrate. The manufacturing method may be incorporated into other processes while the manufacturing method described above is being performed, or the manufacturing method may be incorporated into other processes. Examples of other processes include processes for forming structures such as metal wiring, gate structures, source structures, drain structures, insulating films, ferromagnetic layers, and non-magnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and modification), resist formation processes, exposure processes, removal processes, heat treatment processes, cleaning processes, and inspection processes.

[0138] The above manufacturing method may be performed at any stage of a back end process (BEOL: Back end of the line), a middle process (MOL: Middle of the line), or a front end process (FEOL: Front end of the line), and is preferably performed in a front end process or a middle process.

[0139] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0140] In the following examples, the pH of the cleaning agents was measured at 25°C using a pH meter (Horiba, Ltd., Model "F-74") in accordance with JIS Z8802-1984. In producing the compositions of the examples and comparative examples, handling of containers, preparation of the compositions, filling, storage, and analytical measurements were all carried out in a clean room, and containers used for preparing, filling, storing, etc. of the compositions were washed with the solvent used in the preparation or the prepared composition before use.

[0141] [Raw materials for the composition] The following compounds were used to produce the composition. Note that all of the components used in the examples and comparative examples were classified as semiconductor grade or equivalent high purity grade.

[0142] [Specific compounds] Compound A1: Polysorbate 20 Compound A2: Polysorbate 80 Compound A3: Emulgen A-60 (polyoxyethylene distyrenated phenyl ether, manufactured by Kao Corporation) Compound A4: Emulgen A-500 (polyoxyethylene distyrenated phenyl ether, manufactured by Kao Corporation) Compound A5: Emulgen 150 (polyoxyethylene (47) lauryl ether, manufactured by Kao Corporation) Compound A6: Rheodol 460V (polyoxyethylene (60) sorbitol tetraoleate, manufactured by Kao Corporation) Compound A7: Emanone CH-25 (polyoxyethylene hydrogenated castor oil, manufactured by Kao Corporation) Compound A8: Emanone CH-60 (polyoxyethylene hydrogenated castor oil, manufactured by Kao Corporation) Compound A9: Newpol PE-68 (polyoxyethylene polyoxypropylene glycol (block polymer), manufactured by Sanyo Chemical Industries, Ltd.) Compound A10: Celmolis B044 (polyglyceryl-20 lauryl ether, manufactured by Daicel Corporation) All of the above compounds A1 to A10 had a polyoxyalkylene chain and were compounds having no acidic group, basic group, or salts thereof. Furthermore, compounds A1 to A9 were compounds having a polyoxyethylene chain, and compound A9 further had a polyoxypropylene chain. Furthermore, compounds A1 to A8 and A10 all had a hydrocarbon group. Furthermore, compounds A1, A2, A6, A7, and A8 contained an ester bond.

[0143] [Antibacterial agents] Compound B1: MIT (methylisothiazolinone) Compound B2: dehydroacetic acid Compound B3: cresol Compound B4: TBZ (2-(4-thiazolyl)benzimidazole) Compound B5: [(4-chlorophenoxy)methyl]-3-iodo-2-propynyl ether (IF1000)

[0144] [pH adjusters] Compound C1: nitric acid Compound C2: phosphoric acid Compound C3: sulfuric acid Compound C4: citric acid Compound C5: etidronic acid Compound C6: trishydroxymethylaminomethane (Tris) Compound C7: 2-amino-2-methyl-1-propanol (AMP) Compound C8: 2-dimethylamino-2-methyl-1-propanol (DMAMP) Compound C9: tetraethylammonium hydroxide (TEAH) Compound C10: bis-trispropane

[0145] [Corrosion inhibitors] Compound D1: L-arginine Compound D2: L-histidine Compound D3: L-lysine Compound D4: bis(p-chlorophenyldiguanide)hexane digluconate (chlorhexidine gluconate) Compound D5: polyallylamine (Mw (weight average molecular weight) = 1000)

[0146] [Preparation of Compositions] The method for preparing the compositions will now be described. The above compounds and pure water were added in the amounts (mass %) corresponding to the formulations shown in the table below, and the mixture was thoroughly stirred to obtain a concentrated solution (stock solution). The obtained concentrated solution was diluted with pure water as a diluent at the dilution ratio (volume ratio) shown in the "Dilution Ratio" column in the table below to prepare each composition. Note that the remaining components (remainder) of the composition that are not explicitly listed as composition components in the table are pure water. Finally, after preparing each of the compositions, the mixture was filtered through a 10 μm PP filter (HDCII J-100, a product of Pall Corporation) to obtain each composition of the Examples and Comparative Examples. Note that in all of the compositions of the Examples, the concentration of the specific compound was equal to or higher than the critical micelle concentration at 25°C.

[0147] [Polishing and Cleaning of Each Object to be Polished] Each object to be polished was polished and cleaned using the compositions of each Example and Comparative Example according to the procedure described below.

[0148] [Preparation of Workpieces] Workpieces used in each evaluation were prepared by polishing each of the following objects to be polished.

[0149] <Object to be Polished> First, a 100 nm thick tungsten (W) layer, a 300 nm thick silicon oxide (TEOS) layer, and a 200 nm thick silicon nitride (Si) layer were formed on the surface of a 12-inch silicon wafer. ３ N ４ Polished objects 1 to 4 were fabricated by forming a 500 nm thick silicon dioxide (SiO2) layer and a 500 nm thick polysilicon (poly-Si) layer, respectively. Polished objects 5 and 6 were then fabricated using the procedure described below. As will be described later, polished objects 5 and 6 correspond to polished objects that have been subjected to CMP processing.

[0150] The CMP-treated polished bodies 5 and 6 were prepared by the following procedure. First, a patterned wafer 10 (using SEMATEC 754TEG as a mask, including line / space: 0.18 μm / 0.18 μm) having line and space portions was prepared by the following procedure. FIG. 1 shows a cross-sectional view of the patterned wafer 10. The patterned wafer 10 is made of a silicon wafer 12 on which a 200 nm thick TEOS layer or a 200 nm thick Si layer was formed as an insulating layer 14. ３ N ４ A layer was formed, and a part of this insulating layer was processed using the mask to form wiring, and then a TiN layer 16 with a thickness of 10 nm was formed on the entire surface, and further a W layer 18 was formed in the groove portion. By the above procedure, a patterned wafer 1 with a TEOS layer (silicon oxide layer) as the insulating layer and a patterned wafer 2 with a Si insulating layer were fabricated. ３ N ４ A patterned wafer 2 having a silicon nitride layer was prepared.

[0151] The patterned wafers 1 and 2 prepared in the above-described manner were subjected to CMP processing in the following manner.

[0152] (Polishing liquid composition) Colloidal silica (PL5D, manufactured by Fuso Chemical Co., Ltd.): 3 mass % Malonic acid: 0.03 mass % Glycine: 0.5 mass % Iron nitrate: 100 mass ppm Hydrogen peroxide: 1 mass % Water: balance pH: 2.2

[0153] (Polishing device and conditions) Polishing device: FREX-300II (manufactured by Ebara Corporation) Polishing pad: FUJIBO Pad H800 (manufactured by Fujibo Co., Ltd.) Polishing pressure: 105 hPa Polishing liquid supply rate: 250 ml / min Table rotation speed: 80 rpm Head rotation speed: 78 rpm

[0154] CMP processing was performed on patterned wafers 1 and 2 using the above polishing liquid and polishing apparatus. The point at which the TiN layer disposed in the line portion was exposed was determined as the polishing endpoint. The endpoint was detected using an endpoint detector of the polishing apparatus. Next, a polishing liquid was prepared from the above polishing liquid, but iron nitrate had been removed, and additional polishing was performed for another 60 seconds using this polishing liquid. As a result of the above additional polishing, a W layer was disposed in the line portion, and a TEOS layer or Si layer was disposed in the space portion. ３ N ４ A line and space pattern in which the patterned lines were arranged was obtained. Polished objects 5 and 6 were produced by the above procedure. The dishing values ​​of the tungsten layers of polished objects 5 and 6 were measured with an AFM (atomic force microscope) and averaged over 10 points to find values ​​of 6 nm and 5 nm, respectively.

[0155] [Cleaning Treatment 1 (Cleaning Using a Resin Pad)] Subsequently, the above-mentioned CMP-treated polished objects 5 to 6 were subjected to a resin pad cleaning treatment using the compositions prepared in the above-mentioned [Preparation of Composition] procedure, according to the following procedure. The apparatus and cleaning conditions are shown below.

[0156] (Cleaning device and conditions) Cleaning (polishing) device: 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

[0157] After the CMP treatment, the polished surface of each object to be polished was subjected to a cleaning treatment using the cleaning apparatus and conditions described above. Each composition was filtered through a 1.0 μm PP filter (HDCII J-006, manufactured by Pall Corporation) before being supplied. The pad used in the CMP treatment was the same as used above. The composition used above was a composition immediately after its production. The composition used above was stored in a clean room (23° C.) for two weeks, and then the same cleaning treatment 1 described above was carried out using the composition after storage.

[0158] [Cleaning Treatment 2 (Cleaning by Brush Scrubbing)] After the above cleaning treatment 1, each of the polished objects was further subjected to a cleaning treatment by brush scrubbing according to the procedure shown below. The work was carried out in a clean room in an environment of 23°C. The polished surface of each of the polished objects after the above cleaning treatment 1 was subjected to single-wafer cleaning by brush scrubbing for 60 seconds in cleaning unit 1 of the polishing apparatus using the same composition as used in the above cleaning treatment 1, and then single-wafer cleaning by brush scrubbing for 30 seconds in cleaning unit 2. Finally, after rinsing with pure water for 60 seconds, the object was spin-dried at 1000 rpm in drying unit 2 while spraying nitrogen gas onto the polished surface, thereby obtaining cleaned treated objects 5 to 6 for evaluation.

[0159] [Evaluation] The following evaluations were carried out using each of the above-mentioned washed objects to be treated.

[0160] [Residue Removability (Cleaning Performance)] The residue removability of the treated objects obtained by carrying out the above-mentioned [Cleaning Treatment 1] and [Cleaning Treatment 2] using the composition immediately after production was evaluated according to the following procedure. Using a defect detection device (ComPlus-II, manufactured by AMAT Corporation), the number of detected signal intensities corresponding to defects having a length of more than 0.1 μm was counted on the polished surfaces of treated objects 5 to 6, which had been cleaned with the above-mentioned composition immediately after production. The defect types were identified by observing the above-mentioned defects with a defect review SEM (SEMVISION G5, manufactured by AMAT Corporation). From the obtained number of defects, the residue removability was evaluated according to the following evaluation criteria. In practical terms, a rating of D or higher is preferable.

[0161] A: The number of defects per wafer (processed object) is less than 20. B: The number of defects per wafer is 20 or more but less than 50. C: The number of defects per wafer is 50 or more but less than 80. D: The number of defects per wafer is 80 or more but less than 100. E: The number of defects per wafer is 100 or more.

[0162] [Residue Removal Ability After Aging Test (Aging Performance)] The residue removability of the treated objects obtained by carrying out the above-mentioned [Cleaning Treatment 1] and [Cleaning Treatment 2] using the composition after two weeks of storage was evaluated according to the following procedure. Using a defect detection device (ComPlus-II, manufactured by AMAT Corporation), the number of detected signal intensities corresponding to defects with a length of more than 0.1 μm was counted on the polished surfaces of Treated Objects 5 to 6, which had been cleaned with the above-mentioned compositions after two weeks of storage. The defect types were identified by observing the above-mentioned defects with a defect review SEM (SEMVISION G5, manufactured by AMAT Corporation). From the obtained number of defects, the residue removability was evaluated according to the following evaluation criteria. In practical terms, a rating of D or higher is preferable.

[0163] A: The number of defects per wafer (processed object) is less than 20. B: The number of defects per wafer is 20 or more but less than 50. C: The number of defects per wafer is 50 or more but less than 80. D: The number of defects per wafer is 80 or more but less than 100. E: The number of defects per wafer is 100 or more.

[0164] [Polishing Rate Change Rate (Continuity Evaluation)] The [Polishing Treatment] described below, and the [Cleaning Treatment 1] and [Cleaning Treatment 2] described above were repeatedly performed on multiple polished objects, and the change in the polishing rate during the [Polishing Treatment] was evaluated to confirm the effect of each composition used in [Cleaning Treatment 1] and [Cleaning Treatment 2] on the polishing performance.

[0165] [Polishing Treatment] The objects to be polished 1 and 2 were subjected to CMP treatment using the following polishing liquid and polishing apparatus.

[0166] (Polishing liquid composition) Colloidal silica (PL5D, manufactured by Fuso Chemical Co., Ltd.): 3 mass % Malonic acid: 0.03 mass % Glycine: 0.5 mass % Hydrogen peroxide: 1 mass % Water: balance pH: 2.2

[0167] (Polishing device and conditions) Polishing device: FREX-300II (manufactured by Ebara Corporation) Polishing pad: FUJIBO Pad H800 (manufactured by Fujibo Co., Ltd.) Polishing pressure: 105 hPa Polishing liquid supply rate: 250 ml / min Table rotation speed: 80 rpm Head rotation speed: 78 rpm Polishing time: 45 seconds

[0168] First, ten pieces of each of the polished object 1 and the polished object 2 prepared in the above [Preparation of the object to be polished] were prepared. The first polished object 1 and the first polished object 2 were prepared by performing the above [Polishing Treatment] on the first polished object 1 and the first polished object 2. The respective polishing speeds at this time were defined as the initial polishing speeds. Next, the polishing pads used in the [Polishing Treatment] were dressed, and then the above-described operations, [Cleaning Treatment 1] and [Cleaning Treatment 2], were performed. Thereafter, the pads used for the first polished object 1 and the first polished object 2 were used as they were, and the same operations as for the first object were performed on the second to tenth polished objects, in order ([Polishing Treatment], [Cleaning Treatment 1], and [Cleaning Treatment 2]). The respective polishing speeds at which the [Polishing Treatment] was performed on the tenth polished object 1 and the tenth polished object 2 were defined as the final polishing speeds.

[0169] From the initial polishing rate and final polishing rate confirmed by the above-mentioned procedure, the "change rate of polishing rate" was calculated according to the following formula. The smaller the change rate of polishing rate, the less likely each composition used in [Cleaning Treatment 1] and [Cleaning Treatment 2] is to deteriorate the polishing performance, and this is preferable. Change rate of polishing rate (%) = 100 × | initial polishing rate - final polishing rate | / (initial polishing rate) From the obtained change rate of polishing rate, residue removability was evaluated according to the following evaluation criteria. In practice, a rating of D or higher is preferable.

[0170] A: The rate of change in polishing rate is less than 5%. B: The rate of change in polishing rate is 5% or more but less than 10%. C: The rate of change in polishing rate is 10% or more but less than 15%. D: The rate of change in polishing rate is 15% or more but less than 20%. E: The rate of change in polishing rate is 20% or more.

[0171] [Corrosion prevention performance] The dishing values ​​of the W layer (10 μm line portion) of the treated object 5 and treated object 6, which had been cleaned with the composition immediately after production and obtained by performing the above [Cleaning treatment 1] and [Cleaning treatment 2], were measured using an AFM and calculated as the average value of 10 points. The obtained dishing values ​​were compared with the dishing values ​​of the polished object 5 and polished object 6 before performing the cleaning treatment 1 and cleaning treatment 2, respectively, to calculate the change in dishing value. As described above, the dishing values ​​of the polished object 5 and polished object 6 before performing the cleaning treatment 1 and cleaning treatment 2 were 6 nm and 5 nm, respectively. The corrosion prevention performance was evaluated from the change in the obtained dishing value according to the following evaluation criteria.

[0172] A: The change in dishing value is less than 10 Å (1 nm). B: The change in dishing value is 10 Å or more but less than 30 Å. C: The change in dishing value is 30 Å or more.

[0173] [Results] Table 1 shows the composition of each composition in the Examples and Comparative Examples, as well as the evaluation results. In the table, the "mass %" column for each component indicates the content (mass %) of each component relative to the total mass of the concentrated solution. The remainder of the concentrated solution, other than (a) to (d), is pure water. In the table, the "(a) / (b)" column indicates the mass ratio of the content of the (a) specific compound to the content of the (b) antibacterial agent. In the table, the "(a) / (c)" column indicates the mass ratio of the content of the (a) specific compound to the content of the (c) pH adjuster. In the table, the "(a) / (d)" column indicates the mass ratio of the content of the (a) specific compound to the content of the (d) corrosion inhibitor. In the table, the "Dilution Ratio" column indicates the dilution ratio (volume ratio) of the concentrated solution when preparing the composition, as described above. In the table, the numerical value in the pH column indicates the pH of the composition at 25°C, measured using the pH meter described above. Note that the numerical value in the "pH after dilution" column is the value measured for a composition prepared by diluting the concentrated solution.

[0174]

[0175]

[0176]

[0177]

[0178] The results in the above table confirm that the composition of the present invention has high removability of residues generated in CMP treatment even when used after long-term storage (excellent performance over time), and furthermore, when applied to a cleaning treatment in a process in which CMP treatment and a subsequent cleaning treatment using a pad are repeated, there is little deterioration in the removal rate of the CMP treatment (excellent rate of change in removal rate).

[0179] Comparisons of Examples 1 to 6 and the like confirmed that the rate of change of polishing rate was superior when the composition contained an acid selected from the group consisting of nitric acid, phosphoric acid, and sulfuric acid. Comparisons of Examples 7 to 14 and the like confirmed that the rate of change of polishing rate was superior when the content of the specific compound was 0.8 to 1.2 mass% relative to the total mass of the composition. Comparisons of Examples 8 to 13 and 19 to 21 and the like confirmed that the rate of change of polishing rate was superior when the mass ratio of the content of the specific compound to the content of the antibacterial agent was 10 or more, and that the performance over time was superior when the mass ratio was 5,000 or less. Comparisons of Examples 14 and 22 and the like confirmed that the rate of change of polishing rate was superior when the composition contained a pH adjuster selected from an acid and an amine, and the mass ratio of the content of the specific compound to the content of the pH adjuster was 3,000 or less. Comparisons between Examples 22 and 27 confirmed that the polishing rate change rate was better when the composition contained a pH adjuster selected from an acid and an amine and the mass ratio of the content of the specific compound to the content of the pH adjuster was 10 or more. Comparisons between Examples 33 to 42 confirmed that the polishing rate change rate was better when the hydrophilic-lipophilic balance value of the specific compound was 12.0 to 20.0. Comparisons between Examples 33 and 43 to 47 confirmed that the corrosion prevention performance was better when the composition further contained an anticorrosion agent. Comparisons between Examples 48 to 52 confirmed that the corrosion prevention performance was better when the mass ratio of the content of the specific compound to the content of the anticorrosion agent was 10,000 or less, and that the polishing rate change rate was better when it was 5 or more.

[0180] As mentioned above, the polished objects 1 and 2 were used when evaluating the rate of change in polishing rate, but similar trends in the evaluation results were observed when the polished objects 3 and 4 were used.

[0181] 10: patterned wafer; 12: silicon wafer; 14: insulating layer; 16: TiN layer; 18: W layer

Claims

A composition used for cleaning a workpiece that has been subjected to chemical mechanical polishing using a pad, comprising: a compound having a polyoxyalkylene chain and having no acidic group, no basic group, or no salt thereof; an antibacterial agent, the content of the compound is 0.3 to 5.0% by mass relative to the total mass of the composition, The composition, wherein the mass ratio of the content of the compound to the content of the antibacterial agent is 5 to 10,000.

10. The composition of claim 1, wherein the pH is 4.5 or less.

10. The composition of claim 1, wherein the pH is 7.5 or greater. 　 The composition of claim 1 , which is substantially free of abrasive particles. 　 further comprising a pH adjuster selected from acids and amines; The composition according to claim 1, wherein the mass ratio of the content of the compound to the content of the pH adjuster is more than 5 and less than 10,000.

10. The composition of claim 1, further comprising an acid selected from the group consisting of nitric acid, phosphoric acid, and sulfuric acid. 　 The composition of claim 1 further comprising an amino alcohol. 　 The composition of claim 1 further comprising a corrosion inhibitor. 　 The composition according to claim 8, wherein the mass ratio of the content of the compound to the content of the corrosion inhibitor is 60 to 1000.

2. The composition of claim 1, wherein the compound has a hydrophilic-lipophilic balance value of 12.0 to 20.

0. The composition according to claim 1, wherein the content of the compound relative to the total mass of the composition is equal to or greater than the critical micelle concentration of the compound at 25°C. 　 The composition of claim 1 , wherein the compound has at least one of a polyoxyethylene chain and a polyoxypropylene chain. 　 The composition of claim 1 , wherein the compound comprises an ester bond. 　 the workpiece subjected to the chemical mechanical polishing treatment contains at least one selected from the group consisting of a silicon compound, polysilicon, and amorphous silicon; The composition of claim 1 , wherein the silicon compound comprises a silicon atom and at least one of an oxygen atom, a nitrogen atom, and a carbon atom.

2. The composition according to claim 1, wherein the workpiece subjected to the chemical mechanical polishing treatment contains at least one selected from the group consisting of tungsten, cobalt, ruthenium, titanium, titanium nitride, tantalum, and tantalum nitride. 　 A concentrate used to obtain the composition according to any one of claims 1 to 15 by dilution. 　 a compound having a polyoxyalkylene chain and having no acidic group, no basic group, or no salt thereof; and an antibacterial agent; the mass ratio of the content of the compound to the content of the antibacterial agent is 5 to 10,000; the content of the compound is 1 to 30% by mass relative to the total mass of the stock solution, The content of the antibacterial agent is 0.001 to 10% by mass relative to the total mass of the stock solution, The concentrate according to claim 16, wherein the concentrate is diluted with water 2 to 500 times by volume. 　 A method for producing a cleaned processed object, comprising the steps of: bringing a processed object that has been subjected to chemical mechanical polishing treatment into contact with a pad while supplying the composition according to any one of claims 1 to 15; and moving the processed object and the pad relative to each other to clean the processed object, thereby obtaining a cleaned processed object. 　 The method for producing a cleaned processed object according to claim 18, wherein the object and the pad are moved relative to each other while the pad is pressed against the object. 　 A method for manufacturing an electronic device, comprising the method for manufacturing a cleaned object according to claim 18.

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