Cleaning composition for semiconductors

Abstract

The purpose of the present invention is to provide a semiconductor cleaning agent composition that exhibits high removal performance with respect to ceria particles which are metal residue remaining on a substrate. The present invention is a semiconductor cleaning agent composition comprising a pH adjuster and a polymer that has a structural unit derived from a carboxylic acid-based monomer, wherein the weight-average molecular weight of the polymer is not less than 3,100, the pH adjuster is one or more compounds selected from the group consisting of metal hydroxides and amine compounds, and pH is not less than 7.

Description

[Technical Field]

[0001] The present invention relates to a cleaning composition for semiconductors. [Background technology]

[0002] Conventionally, the CMP (Chemical-Mechanical-Planarization / Polishing) process has been known as a process for planarizing wafer surfaces in semiconductor manufacturing processes. After the CMP process, metal residues such as abrasive grains and polishing debris remain on the wafer surface, and cleaning is performed to remove these. Various cleaning agents for such CMP processes have been known. For example, Patent Document 1 discloses a cleaning composition for cleaning after the CMP process, which contains ammonium that forms a salt with a specific water-soluble polymer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-41494 Summary of the Invention [Problem to be solved by the invention]

[0004] However, conventional cleaning chemicals for the CMP process are still insufficient in removing metal residues remaining on wafers after the CMP process, and there is room for improvement. In particular, when using abrasives containing ceria (cerium oxide: CeO2), conventional cleaning chemicals are insufficient in their ability to remove ceria particles, and are unable to fully remove the ceria particles remaining on the wafer, resulting in problems such as the residual components adhering to the substrate surface.

[0005] In view of the above-mentioned current situation, an object of the present invention is to provide a semiconductor cleaning composition that exhibits high removability of ceria particles, which are metal residues remaining on a substrate. [Means for solving the problem]

[0006] In order to solve the above problems, the present inventors have conducted various studies on cleaning compositions for semiconductors and have found that a cleaning composition containing a specific polymer and a pH adjuster and having a pH of 7 or higher exhibits high removability of metal residues including ceria particles, thereby completing the present invention.

[0007] That is, the present invention is described in the following [1] to [3]. [1] A semiconductor cleaning composition comprising a polymer having a structural unit derived from a carboxylic acid monomer and a pH adjuster, wherein the polymer has a weight-average molecular weight of 3,100 or more, the pH adjuster is one or more compounds selected from the group consisting of metal hydroxides and amine compounds, and the semiconductor cleaning composition has a pH of 7 or more. [2] The semiconductor cleaning composition according to the above [1], wherein the amine compound comprises one or more compounds selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2):

[0008] [ka] (In formula (1), R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. 1 , R 2 and R 3 At least two selected from may be linked to form a ring.)

[0009] [ka] (In formula (2), R 4 , R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. [3] The semiconductor cleaning composition according to the above [1] or [2], which contains a compound represented by the following general formula (3) and / or a compound represented by the following general formula (4):

[0010] [ka] (In formula (3), R 8 , R 9 and R 10 are the same or different and represent a hydrogen atom or an alkyl group. 11 and R 12 are the same or different and represent an alkylene group. x and y are the same or different and represent an integer of 0 to 50. (x+y) is an integer of 1 or more.

[0011] [ka] (In formula (4), R 13 , R 14 , R 15 and R 16 are the same or different and represent a hydrogen atom or an alkyl group. 17 , R 18 , R 19 , R 20 and R 21 are the same or different and represent an alkylene group or an alkynylene group. x and y are the same or different and represent an integer of 0 to 50. (x+y) is an integer of 1 or more. [Effects of the Invention]

[0012] The semiconductor cleaning composition of the present disclosure can exhibit high removability for ceria particles that are metal residues remaining on a substrate. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below. Note that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0014] [Semiconductor cleaning composition] <Polymer> The semiconductor cleaning composition of the present disclosure contains a polymer having a structural unit (A) derived from a carboxylic acid monomer.

[0015] (Structural unit (A) derived from carboxylic acid monomer) The semiconductor cleaning composition of the present disclosure contains a polymer having a structural unit (A) derived from a carboxylic acid monomer. In the present disclosure, the carboxylic acid monomer refers to a carboxyl group-containing monomer and / or a salt thereof. The polymer preferably has a structural unit derived from the carboxyl group-containing monomer and / or a salt thereof. In the present disclosure, for example, a "structural unit (A) derived from a carboxy group-containing monomer" refers to a structural unit having a structure in which at least one carbon-carbon double bond contained in the carboxy group-containing monomer is replaced with a carbon-carbon single bond. For example, if the carboxy group-containing monomer is acrylic acid (CH═CHCOOH), the structural unit derived from acrylic acid can be represented by -CH-CH(-COOH)-. Note that in the present disclosure, the structural unit derived from the carboxy group-containing monomer is not limited to a structural unit actually formed by polymerization of the carboxy group-containing monomer. Even a structural unit formed by a different method is included in the structural unit derived from the carboxy group-containing monomer, as long as it has the same structure as the structural unit having a structure in which at least one carbon-carbon double bond contained in the carboxy group-containing monomer is replaced with a carbon-carbon single bond.

[0016] The carboxyl group-containing monomer is not particularly limited as long as it is a monomer having a structure containing a polymerizable unsaturated bond (carbon-carbon double bond) and a carboxyl group, and examples thereof include monomers of unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and 2-methylene glutaric acid.

[0017] The salt of the carboxy group-containing monomer is not particularly limited, and examples thereof include metal salts, ammonium salts, organic amine salts of the unsaturated carboxylic acid compounds, etc. Preferred salts of carboxylic acids are potassium carboxylate, sodium carboxylate, ammonium carboxylate, or quaternary amines of carboxylic acids.

[0018] These carboxylic acid monomers may be used singly or in combination of two or more.

[0019] In the polymer, the proportion of the structural units derived from the carboxylic acid monomer is preferably 10 to 100 mol %, more preferably 20 to 100 mol %, and even more preferably 40 to 100 mol %, relative to 100 mol % of all structural units.

[0020] (Structural units derived from other monomers) The polymer of the present disclosure may contain one or more structural units derived from a monomer other than the structural unit (A) derived from the carboxylic acid monomer (hereinafter also referred to as "structural units derived from other monomers").

[0021] The structural units derived from the other monomers are structural units in which a carbon-carbon double bond (C=C) of an ethylenically unsaturated monomer other than the carboxylic acid monomer is replaced with a carbon-carbon single bond (CC) to form a bond with an adjacent structural unit. However, as long as the structure corresponds to such a structural unit, it does not necessarily have to be a structure in which the carbon-carbon double bond of the monomer is actually replaced with a carbon-carbon single bond.

[0022] Specific examples of the other monomers include hydroxyl group-containing alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and α-hydroxymethylethyl (meth)acrylate; alkyl (meth)acrylates that are esters of alkyl groups of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and lauryl (meth)acrylate; amino group-containing acrylates such as dimethylaminoethyl (meth)acrylate and its quaternized derivatives; amide group-containing monomers such as (meth)acrylamide, dimethylacrylamide, and isopropylacrylamide; vinyl esters such as vinyl acetate; alkenes such as ethylene and propylene; aromatic vinyl monomers such as styrene; maleimide derivatives such as maleimide, phenylmaleimide, and cyclohexylmaleimide. nitrile group-containing vinyl monomers such as (meth)acrylonitrile; aldehyde group-containing vinyl monomers such as (meth)acrolein; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; other functional group-containing monomers such as vinyl chloride, vinylidene chloride, allyl alcohol, and vinylpyrrolidone; polyethylene glycol (meth)acrylates such as diethylene glycol (meth)acrylate, triethylene glycol (meth)acrylate, and dipropylene glycol (meth)acrylate; alkoxypolyalkylene glycol (meth)acrylates such as ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and phenoxypolyethylene glycol (meth)acrylate;Examples of suitable monomers include polyalkylene glycol chain-containing monomers such as monomers having a structure in which 1 to 300 moles of alkylene oxide are added to an unsaturated alcohol such as vinyl alcohol, (meth)allyl alcohol, or isoprenol; and monomers having a sulfonic acid group such as 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and vinylsulfonic acid, and salts thereof. As for the other monomers, one type may be used alone, or two or more types may be used in combination.

[0023] The proportion of the structural units derived from the other monomers in the polymer is preferably 0 to 90 mol %, more preferably 0 to 80 mol %, and even more preferably 0 to 60 mol %, relative to 100 mol % of all structural units. By changing the type and amount, it is possible to appropriately adjust the solubility and cleaning performance of the polymer in the semiconductor cleaning composition.

[0024] The weight-average molecular weight of the polymer of the present disclosure is 3100 or more. When the weight-average molecular weight of the polymer is 3100 or more, the removability of metal residue can be further improved. The weight-average molecular weight of the polymer is more preferably 4000 or more, even more preferably 5000 or more, and most preferably 9000 or more. On the other hand, it is preferably 50000 or less, more preferably 24500 or less, even more preferably 23000 or less, and even more preferably 20000 or less. That is, the weight-average molecular weight of the polymer is preferably 3100 to 50000, more preferably 4000 to 24500, even more preferably 5000 to 23000, still more preferably 5000 to 20000, and particularly preferably 9000 to 20000. The weight average molecular weight can be determined by measurement using gel permeation chromatography (GPC), specifically, by the method described in the examples.

[0025] The content of the polymer contained in the semiconductor cleaning composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.3% by mass or more, and still more preferably 0.8% by mass or more, relative to the total amount of the semiconductor cleaning composition. On the other hand, it is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less. That is, the content of the polymer is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, even more preferably 0.3 to 5% by mass, and still more preferably 0.8 to 5% by mass, relative to the total amount of the semiconductor cleaning composition.

[0026] [Polymer manufacturing method] The method for producing the polymer is not particularly limited as long as it produces a polymer having the structural unit (A) derived from the carboxylic acid monomer, and examples thereof include a method of polymerizing a monomer component containing the carboxylic acid monomer and other monomers. The polymerization may be any of radical polymerization, cationic polymerization, and anionic polymerization. The polymerization may also be photopolymerization or thermal polymerization. The polymerization method is not particularly limited, but examples thereof include a method of adding a polymerization initiator, a method of irradiating with UV light, a method of applying heat, a method of irradiating with light in the presence of a photopolymerization initiator, etc. In the polymerization step, it is preferable to use a polymerization initiator.

[0027] Examples of the polymerization initiator include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (2,2'-azobis-2-amidinopropane dihydrochloride), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(1-imidazolin-2-yl)propane Suitable initiators include azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), and 2,2'-azobis(2-methylbutyronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, and cumene hydroperoxide; and redox initiators that generate radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, or persulfates and metal salts. Among these polymerization initiators, hydrogen peroxide, persulfates, and azo compounds are preferred because they tend to reduce residual monomers, with persulfates being more preferred.

[0028] These polymerization initiators may be used alone or in the form of a mixture of two or more. The amount of the polymerization initiator used is preferably 0.1 g or more and 30 g or less, more preferably 0.2 g or more and 20 g or less, and even more preferably 0.25 g or more and 15 g or less, per 100 g of the monomer used.

[0029] In the polymerization step, a chain transfer agent may be used as a molecular weight modifier for the polymer, if necessary. Specific examples of the chain transfer agent include mercaptocarboxylic acids such as thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutanoic acid, thiomalic acid, and salts thereof, mercaptoethanol, thioglycerol, and 2-mercaptoethanesulfonic acid; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary alcohols such as isopropanol and glycerin; phosphorous acid, hypophosphorous acid, hypophosphites, and hydrates thereof; and hydrogen sulfite (salts) and compounds capable of generating hydrogen sulfite (salts), such as bisulfite (salts), pyrosulfite (salts), dithionous acid (salts), and sulfurous acid (salts). Among these, compounds having a mercapto group such as hydrogen sulfite (salt), phosphorous acid (salt), and mercaptocarboxylic acid are preferred, and hydrogen sulfite (salt) and phosphorous acid (salt) are more preferred.

[0030] The amount of the chain transfer agent used is preferably 0 mol% or more and 30 mol% or less, more preferably 0 mol% or more and 25 mol% or less, even more preferably 0 mol% or more and 20 mol% or less, and most preferably 0 mol% or more and 10 mol% or less, relative to 100 mol% of the amount of monomers (total monomers) used.

[0031] The polymerization step may be carried out in a solvent. The polymerization solvent to be used is not particularly limited as long as the desired polymerization reaction proceeds, but in terms of facilitating the use of the obtained polymer solution as is for the preparation of a semiconductor cleaning agent composition, preferred examples include water, alcohol-based solvents such as isopropyl alcohol, ether-based solvents such as propylene glycol monomethyl ether, amide-based solvents such as N-methylpyrrolidone, sulfur-containing solvents such as dimethyl sulfoxide, lactone-based solvents such as δ-valerolactone, and water-soluble organic solvents.

[0032] In the above polymerization step, the polymerization temperature is preferably 40°C or higher and preferably 150°C or lower. More preferably, it is 50°C or higher, and even more preferably 55°C or higher. Also, more preferably, it is 120°C or lower, and even more preferably 110°C or lower. That is, the polymerization temperature is more preferably 50 to 120°C, and even more preferably 55 to 110°C.

[0033] In the above polymerization step, the method of introducing the monomer component into the reaction vessel is not particularly limited, and examples include a method of initially charging the entire amount into the reaction vessel at once; a method of dividing or continuously charging the entire amount into the reaction vessel; a method of initially charging a part into the reaction vessel and dividing or continuously charging the remainder into the reaction vessel, etc. When using the above polymerization initiator, it may be charged into the reaction vessel from the beginning, may be dropped into the reaction vessel, or these may be combined according to the purpose.

[0034] The polymerization time is not particularly limited, but is preferably 30 to 600 minutes, more preferably 30 to 500 minutes, and even more preferably 30 to 400 minutes.

[0035] The method for producing the above polymer may include other steps in addition to the above-described polymerization step. Examples of the above other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, a purification step, etc. These steps can be carried out by known methods.

[0036] <pH adjuster> The cleaning agent composition for semiconductors of the present disclosure contains a pH adjuster. The pH adjuster contained in the cleaning agent composition for semiconductors of the present disclosure is not particularly limited as long as it is a compound capable of adjusting to a desired pH, and examples include known acidic compounds or basic compounds. Among them, a basic compound is preferable from the viewpoint of cleaning performance.

[0037] The basic compound of the present disclosure is not particularly limited, but is preferably a metal hydroxide such as an alkali metal hydroxide or an alkaline earth metal hydroxide; a metal bicarbonate such as an alkali metal bicarbonate or an alkaline earth metal bicarbonate; a metal carbonate such as an alkali metal carbonate or an alkaline earth metal carbonate; or an organic basic compound, and particularly preferably a metal hydroxide or an organic basic compound.

[0038] The metal hydroxide of the present disclosure is preferably an alkali metal hydroxide or an alkaline earth metal hydroxide, specifically potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, etc.

[0039] As the organic basic compound of the present disclosure, an amine compound is particularly preferred, and although not particularly limited, specifically, one or more compounds selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2) are preferred.

[0040] [ka]

[0041] (In formula (1), R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. 1 , R 2 and R 3 At least two selected from may be linked to form a ring.)

[0042] [ka]

[0043] (In formula (2), R 4 , R 5 , R 6 and R 7are the same or different and represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms.

[0044] Regarding the amine compound of the present disclosure, in the above general formula (1), R 1 , R 2 and R 3 The hydrocarbon group represented by the formula (I) preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. The hydrocarbon group may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred, and an alkyl group being more preferred.

[0045] In the above general formula (1), R 1 , R 2 and R 3 The alkyl group represented by the formula (I) may be linear or branched.

[0046] Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, and an n-octadecyl group.

[0047] Examples of branched alkyl groups include sec-butyl, isobutyl, tert-butyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, isoamyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, tert-amyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, 1-methylpentyl, 1-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 2-ethyl-2-methylpropyl, sec-heptyl, tert-heptyl, isoheptyl, sec-octyl, tert-octyl, isooctyl, 1-ethylhexyl, 1-propylpentyl, 2-ethylhexyl, and 2-propylpentyl groups.

[0048] Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, a cyclohexadecyl group, and a cyclooctadecyl group.

[0049] The hydrocarbon group may have a substituent. The substituent is not particularly limited, but examples thereof include a hydroxyl group, an alkoxy group, a halogen atom, an ether group, a cyano group, a thiol group, and an amino group. A hydroxyl group or an alkoxy group is preferred, and a hydroxyl group is more preferred.

[0050] The number of substituents on the hydrocarbon group is not particularly limited, but is preferably 0 to 6, and more preferably 0 to 3, in terms of pH adjusting ability.

[0051] Above R 1 , R 2 and R 3 At least two selected from the above may be linked to form a ring. The ring formed may be saturated or unsaturated, and may be monocyclic or polycyclic. The atoms constituting the ring may contain a nitrogen atom. The ring may have a substituent. Examples of the substituent that the ring may have include the above-mentioned substituents and alkyl groups.

[0052] Specific examples of the amine compound of the present disclosure represented by the general formula (1) include alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, N,N-diisopropylethylamine, tetramethylethylenediamine, and hexamethylenediamine; organic amines such as aromatic amines such as aniline and toluidine, and nitrogen-containing heterocyclic compounds such as pyrrole, pyridine, picoline, lutidine, and diazabicycloundecene; and alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, N-methylethanolamine, and 2-(2-aminoethylamino)ethanol. Among these, alkanolamines are preferred.

[0053] Regarding the amine compound of the present disclosure, in the above general formula (2), R 4 , R 5 , R 6 and R 7 The hydrocarbon group represented by the formula (I) preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. R 4 , R 5 , R 6 and R 7 Examples of the hydrocarbon group represented by the formula (I) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these, an aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred.

[0054] In the above general formula (2), R 4 , R 5 , R 6 and R 7 The alkyl group represented by the formula (I) may be linear or branched. The alkyl group is not particularly limited, but may be any of the above-mentioned R 1 , R 2 and R 3 The alkyl group may be the same as the alkyl group represented by the following formula:

[0055] The hydrocarbon group may have a substituent. The substituent is not particularly limited, but examples thereof include a hydroxyl group, an alkoxy group, a halogen atom, an ether group, a cyano group, and a thiol group. A hydroxyl group or an alkoxy group is preferred, and a hydroxyl group is more preferred.

[0056] In the above general formula (2), R 4 , R 5 , R 6 and R 7 The number of substituents possessed by the hydrocarbon group represented by the following formula may be 1 or more, may be 2 or more, and is preferably 1 to 3.

[0057] Regarding the amine compound of the present disclosure, specific examples of the compound represented by the above general formula (2) include quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, trimethyl-2-hydroxyethylammonium (choline) hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, and methyltris(2-hydroxyethyl)ammonium hydroxide.

[0058] The semiconductor cleaning agent composition of the present disclosure may contain only one type of pH adjuster, or may contain two or more types of pH adjusters. The content of the pH adjuster in the semiconductor cleaning composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, relative to the total amount of the semiconductor cleaning composition, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. That is, the content of the pH adjuster is preferably 0.1 to 20 mass %, more preferably 0.3 to 15 mass %, and even more preferably 0.5 to 10 mass %, relative to the total amount of the semiconductor cleaning agent composition.

[0059] The content of the pH adjuster is preferably 10 to 2000 parts by mass, more preferably 20 to 1800 parts by mass, and even more preferably 25 to 1700 parts by mass, relative to 100 parts by mass of the polymer.

[0060] <Other ingredients> The semiconductor cleaning composition of the present disclosure may contain other components in addition to the above-mentioned components, including, but not limited to, a color transfer inhibitor, a softener, a fragrance, a solubilizer, a fluorescent agent, a colorant, a foaming agent, a foam stabilizer, a polishing agent, a disinfectant, a bleaching agent, a bleaching aid, an enzyme, a dye, a dispersant, a solvent, etc.

[0061] The semiconductor cleaning composition of the present disclosure may optionally contain a dispersant, but preferably contains a nonionic dispersant, which is not particularly limited, in order to further improve the removability of metal residues.

[0062] The nonionic dispersing agent is not particularly limited, but examples thereof include polyvinylpyrrolidone, polydimethylacrylamide, polyethylene glycol, polypropylene glycol, polyalkylene glycol, polyglycerin, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene Examples of suitable nonionic dispersants include ethylene derivatives, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, alkyl alkanolamide, etc. In particular, the nonionic dispersant preferably contains a compound represented by the following general formula (3) or (4) and an N-vinyl lactam polymer typified by N-vinylpyrrolidone, and more preferably contains a compound represented by the following general formula (3) and / or a compound represented by the following general formula (4).

[0063] [ka]

[0064] (In formula (3), R 8 , R 9 and R 10 are the same or different and represent a hydrogen atom or an alkyl group. 11 and R 12are the same or different and represent an alkylene group. x and y are the same or different and represent an integer of 0 to 50. (x+y) is an integer of 1 or more.

[0065] [ka]

[0066] (In formula (4), R 13 , R 14 , R 15 and R 16 are the same or different and represent a hydrogen atom or an alkyl group. 17 , R 18 , R 19 , R 20 and R 21 are the same or different and represent an alkylene group or an alkynylene group. x and y are the same or different and represent an integer of 0 to 50. (x+y) is an integer of 1 or more.

[0067] In the above general formula (3), R 8 , R 9 and R 10 The alkyl group represented by the formula (3) may be linear or branched. The number of carbon atoms in the alkyl group of the formula (3) is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. On the other hand, it is preferably 20 or less, more preferably 18 or less, and even more preferably 12 or less. That is, the number of carbon atoms in the alkyl group of the formula (3) is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, and even more preferably 12 or less. 8 , R 9 and R 10 The alkyl group represented by the formula (I) preferably has 1 to 20 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms.

[0068] Examples of the alkyl group of the general formula (3) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a heptyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 3-ethylpentyl group, a 2,4-dimethyl ... Examples of the alkyl group include linear or branched alkyl groups such as butyl, 2,2,3-trimethylbutyl, octyl, methylheptyl, dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, trimethylpentyl, 3-ethyl-2-methylpentyl, 2-ethyl-3-methylpentyl, 2,2,3,3-tetramethylbutyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups.

[0069] In the above general formula (3), R 11 and R 12 The alkylene group represented by the general formula (3) may be linear or branched. 11 and R 12 Examples of alkylene groups represented by the formula (I) include methylene, ethylene, n-propylene, 2-propylene, n-butylene, pentamethylene, hexamethylene, neopentylene, heptamethylene, octamethylene, nonamethylene, decamethylene, methylmethylene, methylethylene, 1-methylpentylene, and 1,4-dimethylbutylene. Alkylene groups having 2 to 4 carbon atoms are preferred, and alkylene groups having 2 to 3 carbon atoms are even more preferred. This tends to reduce adhesion of metal residues to the wafer surface.

[0070] In the above general formula (3), x and y may be the same or different and are numbers from 0 to 50, preferably from 0 to 40, more preferably from 0 to 30, even more preferably from 0 to 25, and still more preferably from 0 to 20.

[0071] In the general formula (3), x is an alkylene oxide (R 11 represents the average number of moles of alkylene oxide (R 12 O). x and y may be the same or different in any alkylene oxide.

[0072] In the above general formula (3), x is preferably a number from 0 to 30, more preferably from 0 to 25, and even more preferably from 0 to 20. y is preferably a number from 0 to 20, more preferably from 0 to 15, and even more preferably from 0 to 10. Here, x and y are preferably integers of 1 or more. This tends to make it easier to control hydrophilicity and hydrophobicity. In the above general formula (3), R 8 , R 9 and R 10 It is preferred that two or more of the groups be alkyl groups.

[0073] In the above general formula (4), R 13 , R 14 , R 15 and R 16 The alkyl group represented by the above-mentioned R 8 , R 9 and R 10 The alkyl group may be the same as the alkyl group represented by the following formula:

[0074] The number of carbon atoms in the alkyl group of the general formula (4) is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 18 or less, and even more preferably 12 or less.

[0075] In the above general formula (4), R 17 , R18 , R 19 , R 20 and R 21 The alkylene group represented by the above-mentioned R 11 and R 12 The alkylene group preferably has 2 to 4 carbon atoms, and more preferably has 2 to 3 carbon atoms.

[0076] In the above general formula (4), R 17 , R 18 , R 19 , R 20 and R 21 Examples of the alkynylene group represented by the formula (I) include an ethynylene group (-C≡C-), a propynylene group (-C≡C-CH2-), a 1-butynylene group (-C≡C-CH2-CH2-), a 2-butynylene group (-CH2-C≡C-CH2-), etc. Among these, an alkynylene group having 2 to 6 carbon atoms is preferred, and an alkynylene group having 2 to 4 carbon atoms is more preferred.

[0077] In the above general formula (4), x and y may be the same or different and are numbers from 0 to 50, preferably from 0 to 40, more preferably from 0 to 30, even more preferably from 0 to 25, and still more preferably from 0 to 20.

[0078] In the general formula (4), x is an alkylene oxide (R 17 O) and (R 19 represents the average number of moles of alkylene oxide (R 18 O) and (R 20 O). x and y may be the same or different in any alkylene oxide.

[0079] In the above general formula (4), x is preferably a number from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 18. y is preferably a number from 0 to 30, more preferably from 0 to 20, and even more preferably from 0 to 10. Here, x and y are preferably integers of 1 or greater.

[0080] The semiconductor cleaning agent composition of the present disclosure may contain a solvent. Examples of the solvent include water, lower alcohols, ether-based solvents, amide-based solvents, sulfur-containing solvents, lactone-based solvents, and water-soluble organic solvents. These solvents may be the same as the polymerization solvents described above. Among these, the solvent preferably contains water. The solvent may be a mixed liquid containing two or more types.

[0081] The content of the solvent in the semiconductor cleaning agent composition of the present disclosure is preferably 0 to 30 mass %, more preferably 0 to 20 mass %, and even more preferably 0 to 10 mass %, relative to the total amount of the semiconductor cleaning agent composition.

[0082] The content of other components other than the solvent in the semiconductor cleaning composition of the present disclosure is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.02% by mass or more, relative to the total amount of the semiconductor cleaning composition. On the other hand, it is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. That is, the content of the other components is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.02 to 5% by mass, relative to the total amount of the semiconductor cleaning composition.

[0083] In one or more embodiments, the content of each component, such as a polymer, a pH adjuster, or other components, contained in the semiconductor cleaning composition of the present disclosure refers to the content of each component in the semiconductor cleaning composition at the time of use in a cleaning step, i.e., at the start of use for cleaning (which may also be referred to as the time of use or the time of cleaning).

[0084] The semiconductor cleaning composition of the present disclosure may be prepared as a concentrate by reducing the amount thereof to the extent that storage stability is not impaired due to separation, precipitation, etc. The concentrated type of semiconductor cleaning composition is preferably 5 times or more in terms of transportation costs, and preferably 100 times or less in terms of storage stability.

[0085] The semiconductor cleaning composition concentrate of the present disclosure can be used by diluting it with water so that the content of each component is as described above (i.e., the content at the time of cleaning). Furthermore, the semiconductor cleaning composition concentrate can also be used by adding each component separately at the time of use. In the present disclosure, "at the time of use" or "at the time of cleaning" of the semiconductor cleaning composition concentrate refers to the diluted state of the semiconductor cleaning composition concentrate.

[0086] The pH of the semiconductor cleaning composition of the present disclosure is 7 or higher. When the semiconductor cleaning composition has a pH of 7 or higher, the removability of metal residue can be further improved. The pH is more preferably 8 or higher, even more preferably 9 or higher, and even more preferably 11 or higher, in terms of improving the removability of metal residue. On the other hand, the pH is preferably 14 or lower, more preferably 13.8 or lower, and even more preferably 13.6 or lower. The pH is preferably 7 to 14, more preferably 8 to 13.8, even more preferably 9 to 13.6, and even more preferably 11 to 13.6. The pH can be determined by measuring at 23°C using a pH meter.

[0087] [Method of manufacturing semiconductor cleaning composition] The method for producing the semiconductor cleaning composition of the present disclosure is not particularly limited, and any known method may be used, for example, a method in which the above-mentioned components are mixed and dispersed using various mixers, dispersers, etc. The mixing and dispersion is not particularly limited, and any known method may be used, and the composition may further include other commonly performed steps.

[0088] [How to use] The semiconductor cleaning composition of the present disclosure is preferably used in a cleaning step after the CMP step in the semiconductor manufacturing process. After the CMP step, polishing debris and organic residues from metal wiring, protective films, insulating films, etc. remain on the surface of the semiconductor substrate. Furthermore, the chemical abrasive used in the CMP step may remain. By cleaning the substrate surface containing such residues after the CMP step with the semiconductor cleaning composition of the present disclosure, the residues can be effectively removed.

[0089] The metal wiring, protective film, and insulating film are not particularly limited, and examples thereof include known metal wiring, protective films, and insulating films that are commonly used in semiconductor manufacturing processes. The chemical polishing agent is not particularly limited, and examples thereof include known ones such as slurries of abrasive grains made of metal oxides such as CeO2, Fe2O3, SnO2, MnO, and SiO2. The semiconductor cleaning composition of the present disclosure can effectively remove the above-mentioned residues, and is particularly excellent in removing CeO2 (ceria).

[0090] The method for cleaning the substrate surface after the CMP step with the semiconductor cleaning composition of the present disclosure is not particularly limited and can be a known method. Examples include a method in which the substrate after the CMP step is immersed in the semiconductor cleaning composition for cleaning, and a spin-type or spray-type cleaning method. The temperature of the semiconductor cleaning composition during use is not particularly limited, but is preferably 20 to 90°C, more preferably 20 to 70°C, and even more preferably 20 to 50°C, from the viewpoint of cleaning efficiency. [Example]

[0091] The present invention will be described in more detail below by showing examples, but the scope of the present invention is not limited to these examples, and all modifications and variations that do not deviate from the spirit of the present invention are included within the technical scope of the present invention. Unless otherwise specified, "%" and "wt%" mean "% by mass."

[0092] <Weight average molecular weight (Mw) measurement condition 1> Equipment: Waters Alliance e2695 (RI: 2414 PDA: 2998) Columns: Asahipak GF-7M HQ x 2, Asahipak GF-1G 7B Eluent: 0.1M sodium acetate aqueous solution (pH 7.4) Flow rate: 0.5mL / min Temperature: 40℃ Calibration curve: Polyacrylic acid standard manufactured by American Polymer Standards Corporation

[0093] <Weight average molecular weight (Mw) measurement condition 2> Equipment: Tosoh HLC-8320GPC Detector: RI Column: Tosoh TSK-GEL G3000PWXL Column temperature: 35℃ Flow rate: 0.5ml / min Calibration curve: Poly sodium acrylate standard manufactured by Sowa Scientific Co., Ltd. Eluent: A mixture of sodium dihydrogen phosphate dodecahydrate / disodium hydrogen phosphate dihydrate (34.5 g / 46.2 g) diluted to 5000 g with purified water.

[0094] [Polymer synthesis] <Synthesis Example 1> A 5-liter stainless steel reactor equipped with a reflux condenser and agitator was charged with 1,785 g of ion-exchanged water and heated to a boiling reflux state while stirring. Next, 504 g of 80% acrylic acid (AA) and 167 g of 15% sodium persulfate (NaPS) were added dropwise from separate nozzles to the polymerization system, which was still stirring and at a boiling reflux state. The addition times for each solution were 180 minutes for 80% AA, 185 minutes for 15% NaPS, and 170 minutes for ion-exchanged water. After the addition of the 15% NaPS solution was completed, the reaction solution was maintained at a boiling reflux state (aging) for an additional 30 minutes to complete the polymerization. In this way, a polymer aqueous solution 1 containing a polymer was obtained. The weight-average molecular weight of the resulting polymer was 14,100 (measurement condition 1).

[0095] <Synthesis Example 2> A 2.5-liter stainless steel separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 329.0 g of pure water (initial charge) and heated to the boiling point under stirring. Next, 900.0 g (i.e., 10.0 mol) of 80% by weight aqueous acrylic acid (hereinafter referred to as "80% AA") was added dropwise to the polymerization system, refluxing at the boiling point, over 180 minutes, followed by 59.2 g of 15% by weight aqueous sodium persulfate (hereinafter referred to as "15% NaPS") over 195 minutes, and 21.4 g of 45% by weight aqueous sodium hypophosphite (hereinafter referred to as "45% SHP") over 18 minutes, followed by 84.8 g over 162 minutes. Each component was added continuously at a constant rate, except for the 45% SHP. After the dropwise addition of 80% AA was completed, the reaction solution was maintained at a boiling point reflux state (aging) for an additional 30 minutes to complete the polymerization. After the polymerization was completed, 411.8 g of pure water was added to the reaction solution to obtain an aqueous polymer solution 2. The weight-average molecular weight of the obtained polymer was 4100 (measurement condition 2).

[0096] <Synthesis Example 3> 404 g of pure water and 0.0159 g of Mohr's salt were placed in a 5-liter stainless steel separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer, and the temperature was raised to 90°C with stirring. Next, with stirring, 1040 g of 80% AA, 48.1 g of 48% aqueous NaOH solution, 144.8 g of 15% NaPS, and 171 g of 35% sodium hydrogen sulfite (hereinafter referred to as SBS) were added from separate nozzles. The dropwise addition time for each solution was 180 minutes for the 80% AA and 48% NaOH aqueous solutions, and 185 minutes for the 15% NaPS and 35% SBS aqueous solutions. After the dropwise addition of the 15% NaPS solution, the mixture was aged for 30 minutes to complete the polymerization, yielding aqueous polymer solution 3. The weight-average molecular weight of the resulting polymer was 5700 (measurement condition 1).

[0097] <Synthesis Example 4> A 5-liter stainless steel separable flask equipped with a reflux condenser, a stirrer, and a thermometer was charged with 622 g of ion-exchanged water and 414 g of maleic anhydride, and then 703.6 g of a 48 wt % aqueous solution of sodium hydroxide (hereinafter referred to as 48% NaOHaq) was gradually added under stirring. The aqueous solution in the flask was then heated to its boiling point under normal pressure while being stirred. Next, under stirring, 469 g of 80 wt% acrylic acid aqueous solution (hereinafter referred to as 80% AA), 106.6 g of 35 wt% hydrogen peroxide aqueous solution (hereinafter referred to as 35% HO), 131.1 g of 15 wt% sodium persulfate aqueous solution (hereinafter referred to as 15% NaPS), and 217 g of ion-exchanged water were added dropwise from separate nozzles: 80% AA over 260 minutes, 15% NaPS and 35% HO were added simultaneously with 80% AA over 260 minutes, and ion-exchanged water was added 150 minutes after the start of 80% AA over 140 minutes. After all additions were completed, the reaction solution was maintained at boiling point reflux for an additional 20 minutes to complete the polymerization. In this way, acrylic acid-maleic acid copolymer (salt) was obtained. The pH of this acrylic acid-maleic acid copolymer (salt) was then adjusted to 7.5 with 48 wt% NaOH aqueous solution. The weight average molecular weight of the obtained polymer was 5600 (measurement condition 1).

[0098] <Synthesis Example 5> 1120 g of ion-exchanged water was placed in a 5-liter stainless steel separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer, and the temperature was raised to the boiling point reflux state while stirring. Next, 1480 g of 37% sodium acrylate (hereinafter referred to as SA), 65 g of 15% aqueous NaPS solution, and 157 g of ion-exchanged water were added dropwise from separate nozzles to the polymerization reaction system, which was still at the boiling point reflux state, while stirring. The addition times for each solution were 140 minutes for the 37% SA and 145 minutes for the 15% NaPS and ion-exchanged water. The weight-average molecular weight of the resulting polymer was 3000 (measurement condition 2).

[0099] <Synthesis Example 6> A 5-liter stainless steel separable flask equipped with a reflux condenser, a stirrer, and a thermometer was charged with 381 g of ion-exchanged water and 242.6 g of maleic anhydride, and then 408.5 g of a 48 wt % aqueous solution of sodium hydroxide (hereinafter referred to as 48% NaOHaq) was gradually added under stirring. The aqueous solution in the flask was then heated to its boiling point under normal pressure while being stirred. Next, under stirring, 498 g of 80 wt% acrylic acid aqueous solution (hereinafter referred to as 80% AA), 122.4 g of 35 wt% hydrogen peroxide aqueous solution (hereinafter referred to as 35% HO), 157.3 g of 15 wt% sodium persulfate aqueous solution (hereinafter referred to as 15% NaPS), and 250 g of ion-exchanged water were added dropwise from separate nozzles. 80% AA and 35% HO were added over 240 minutes, 15% NaPS was added simultaneously with 80% AA over 250 minutes, and ion-exchanged water was added over 160 minutes starting 110 minutes after the start of 80% AA. After all additions were completed, the reaction solution was maintained at boiling point reflux for an additional 30 minutes to complete the polymerization. In this way, acrylic acid-maleic acid copolymer (salt) was obtained. The pH of this acrylic acid-maleic acid copolymer (salt) was then adjusted to 8.5 with NaOH aqueous solution. The weight average molecular weight of the obtained polymer was 10,700 (measurement condition 1).

[0100] [Examples 1 to 9, Comparative Examples 1 and 2] As shown in Table 1, cleaning compositions were prepared by mixing water, a polymer, and a nonionic dispersant as an additive, and adding a pH adjuster to achieve a predetermined pH. The nonionic dispersant was added in an amount of 0.25% by mass relative to 100% by mass of the total amount of the cleaning composition. Water and a pH adjuster were added appropriately to achieve the pH shown in Table 1.

[0101] (How to create a contamination coupon) A wafer with a TEOS film purchased from Kyushu Semiconductor Co., Ltd. was cut into 1.5 cm squares. A contamination solution was prepared by diluting CeO2 slurry (HS0220, manufactured by Showa Denko Materials Co., Ltd.) 100 times. The cut wafers were immersed in the contamination solution for 1 minute. After immersion, they were immersed in a PFA pot containing ultrapure water for 30 seconds, and then rinsed with ultrapure water for at least 5 minutes. The wafer was dried and a contamination coupon was created.

[0102] (Cleaning process) 30 ml of the cleaning composition prepared for each example was placed in a PFA container, and the contaminated substrate was immersed in the cleaning composition and cleaned by irradiating it with ultrasound for 2 minutes (treatment conditions: output: 40 kHz) using an ultrasonic device (S8500 manufactured by Branson). After the ultrasonic treatment, the substrate was rinsed with ultrapure water for 5 minutes and air-dried.

[0103] (Cleaning rate calculation method) The surface of the TEOS film substrate before and after cleaning was analyzed using an X-ray photoelectron spectrometer under the following conditions. Equipment: SHIMADZU AXIS-NOVA Measurement conditions / excitation source: Al Kα 12mA 12kV, Pass Energy: 160eV The surface element ratio of Ce was quantified from the peak area ratio using Vision2 Processing software (KRATOS ANALYTICAL). The cleaning performance was determined by the difference (%) in Ce element content on the substrate surface before and after cleaning. The cleaning rate was calculated using the following formula: Cleaning rate (%) = (Ce ratio of substrate after cleaning - Ce ratio of substrate before cleaning) / Ce ratio of substrate before cleaning × 100 The cleaning rate (%) was determined according to the following criteria. Cleaning rate (%): Over 95% and up to 100%: ◎ More than 90% and less than 95%:○ Below 90%: ×

[0104] [Table 1]

[0105] The compounds in Table 1 are as follows: MEA: Monoethanolamine AH212: Dimethylbis(2-hydroxyethyl)ammonium hydroxide Nonionic dispersants (i):

[0106] [ka]

[0107] (In the formula, R 8 :H,R 9 and R 10 are all linear alkyl groups having 1 to 12 carbon atoms, and R 9 and R 10 The total number of carbon atoms is 11 to 13, R 11 :-C2H4-, R 12 :-CH2CH(CH3)-, x=12, y=3, x and y represent the average number of moles added.) A mixture of multiple compounds that satisfies the following conditions.

[0108] The results in Table 1 reveal that the cleaning compositions of the examples have high removability of ceria particles.

Claims

1. A semiconductor cleaning agent composition comprising a polymer having a structural unit derived from a carboxylic acid monomer and a pH adjuster, wherein the polymer has a weight average molecular weight of 3,100 or more; The semiconductor cleaning composition has a pH of 9 or higher, and the pH adjuster is one or more compounds selected from the group consisting of metal hydroxides and amine compounds.

2. 2. The semiconductor cleaning agent composition according to claim 1, wherein the amine compound comprises one or more compounds selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2): 【Chemistry 1】 (In formula (1), R １ , R ２ and R ３ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. １ , R ２ and R ３ At least two selected from may be linked to form a ring.) 【Chemistry 2】 (In formula (2), R ４ , R ５ , R ６ and R ７ are the same or different and represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms.

3. The semiconductor cleaning agent composition according to claim 1 or 2, comprising a compound represented by the following general formula (3) and / or a compound represented by the following general formula (4): 【Transformation 3】 (In formula (3), R ８ , R ９ and R １０ are the same or different and represent a hydrogen atom or an alkyl group. １１ and R １２ are the same or different and represent an alkylene group. x and y are the same or different and represent an integer of 0 to 50. (x+y) is an integer of 1 or more. 【Chemistry 4】 (In formula (4), R １３ , R １４ , R １５ and R １６ are the same or different and represent a hydrogen atom or an alkyl group. １７ , R １８ , R １９ , R ２０ and R ２１ are the same or different and represent an alkylene group or an alkynylene group. x and y are the same or different and represent an integer of 0 to 50. (x+y) is an integer of 1 or more.

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