Semiconductor cleaning agent composition

Abstract

To provide a composition of cleaning agent for semiconductors that is capable of highly removing metal residues, especially ceria, remaining on wafers.SOLUTION: A composition of cleaning agent for semiconductors contains a polymeric material and a pH adjuster, and the polymeric material contains a structural unit (A) derived from an ethylenically unsaturated monomer having two or more carboxy groups (including salts of two or more carboxy groups and anhydrides of carboxy groups) in one molecule and the pH is 7 or higher.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a cleaning agent composition for semiconductors. [Background technology]

[0002] Conventionally, in semiconductor manufacturing processes, with the miniaturization and high integration of semiconductor elements, cleaning is performed to remove metal residues such as abrasive particles and polishing debris remaining on the wafer during wafer planarization in the CMP (chemical mechanical polishing) process. Cleaning compositions used for cleaning include, for example, certain polycarboxylic acids (Patent Document 1) and ammonium compounds that form salts with certain water-soluble polymers (Patent Document 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 11-181494 [Patent Document 2] Japanese Patent Publication No. 2006-41494 [Overview of the project] [Problems that the invention aims to solve]

[0004] As described above, there was room for improvement in semiconductor cleaning agents regarding the removal of metal residue remaining on wafers. In particular, when using abrasives containing ceria (cerium oxide: CeO2) particles in the CMP (chemical mechanical polishing) process, ceria abrasive particles tend to remain on the wafer, making it necessary to remove the ceria particles. Therefore, the present invention aims to provide a semiconductor cleaning agent composition that can exhibit high removal efficiency against metal residues, particularly ceria, remaining on wafers. [Means for solving the problem]

[0005] The inventors of the present invention have conducted various studies to achieve the above objectives and have arrived at the present invention. That is, the present invention is a semiconductor cleaning agent composition comprising a polymer and a pH adjusting agent, wherein the polymer contains structural units (A) derived from ethylenically unsaturated monomers having two or more carboxyl groups (including salts of two or more carboxyl groups or anhydrides of carboxyl groups) in one molecule, and the pH is 7 or higher. [Effects of the Invention]

[0006] The semiconductor cleaning agent composition disclosed herein can exhibit high removal efficiency against metal residues, particularly ceria, remaining on wafers. [Modes for carrying out the invention]

[0007] The present invention will be described in detail below. Furthermore, combinations of two or more of the individual preferred embodiments of the present invention described below are also preferred embodiments of the present invention. [Semiconductor cleaning agent composition] <polymer> The semiconductor cleaning agent composition of this disclosure contains a polymer having a structural unit (A) (hereinafter sometimes referred to as "structural unit (A)") derived from an ethylenically unsaturated monomer having two or more carboxyl groups (including salts of two or more carboxyl groups or anhydrides of carboxyl groups) in one molecule.

[0008] In this disclosure, structural unit (A) refers to a structural unit having the same structure as a structure formed by the polymerization of monomers, and is a structure in which at least one of the carbon-carbon unsaturated double bonds, which are usually found in the monomer, is replaced by a carbon-carbon single bond. It should be noted that a structural unit derived from a monomer does not necessarily have to be a structural unit actually formed by the polymerization of monomers; any structural unit that has the same structure as a structure formed by the polymerization of monomers, even if formed by a method other than monomer polymerization, is included as a structural unit derived from a monomer. For example, in the case of maleic acid, CH(―COOH)=CH(―COOH), the structural unit derived from maleic acid can be represented as ―CH(―COOH)―CH(―COOH)―.

[0009] The ethylenically unsaturated monomers (hereinafter sometimes referred to as "unsaturated polycarboxylic acids") having two or more carboxyl groups (including salts of two or more carboxyl groups or anhydrides of carboxyl groups) in one molecule of the disclosure preferably contain two or more carboxyl groups or salts of carboxyl groups, and more preferably two.

[0010] The unsaturated polycarboxylic acid contained in this disclosure preferably contains one or more carboxyl anhydrides, namely -C(=O)-O-C(=O)-. The ethylenically unsaturated monomers having two or more carboxyl groups of this disclosure may also have other functional groups. Examples of other functional groups include amide groups, nitrile groups, ether groups, sulfone groups, salts of sulfone groups, phosphate groups, salts of phosphate groups, thiol groups, halogen atoms, and the like.

[0011] Examples of ethylenically unsaturated monomers having two or more carboxyl groups in this disclosure include maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, 1,2-cyclohexenedicarboxylic acid, 1,3-cyclohexenedicarboxylic acid, 1,4-cyclohexenedicarboxylic acid, etc., as well as monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof, and anhydrides thereof.

[0012] The carboxyl group in this disclosure may be either acidic or salty. Preferably, the salty form is an alkali metal salt, an alkaline earth metal salt, or a quaternary ammonium salt; more preferably, an alkali metal salt or a quaternary ammonium salt. Preferably, the alkali metal salt is a sodium salt or a potassium salt; more preferably, a sodium salt. The salt of the carboxyl group in this disclosure may be monosal or disal.

[0013] The carboxyl anhydride of this disclosure may be, for example, an ethylenically unsaturated monomer having a -C(=O)-O-C(=O)- structure, which is an anhydride of the unsaturated carboxylic acid mentioned above, and more preferably anhydrides of dicarboxylic acids such as maleic anhydride, phthalic anhydride, and itaconic anhydride.

[0014] The polymers of this disclosure preferably contain 38% by mass or more of unsaturated polycarboxylic acid, more preferably 40% by mass or more, and even more preferably 45% by mass, based on the total amount of polymer. On the other hand, it is preferably 100% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.

[0015] (Other monomers) The polymers of this disclosure may contain structures derived from monomers other than ethylenically unsaturated monomers having two or more carboxyl groups (including salts of two or more carboxyl groups or anhydrides of carboxyl groups) in one molecule (hereinafter sometimes referred to as "structural units derived from other monomers"). The polymers of this disclosure may contain one type of other monomer or two or more types.

[0016] Other monomers include, for example, dicarboxylic acid esters such as dimethyl maleate, dibutyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, and dibutyl fumarate; (meth)acrylic acid; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxypropyl 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate; dienes such as 1,3-butadiene and isoprene; and olefins such as hexene, heptene, decene, and isobutylene. Examples include: styrene monomers such as styrene, bromostyrene, chlorostyrene, methylstyrene, and vinyltoluene; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; vinyl esters such as vinyl acetate; allyl esters such as allyl acetate; nitrogen atom-containing monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, N-vinylpyrrolidone, and (meth)acrylonitrile; polyalkylene glycol chain-containing monomers such as monomers having a structure in which 1 to 300 moles of alkylene oxide are added to unsaturated alcohols such as vinyl alcohol, (meth)allyl alcohol, and isoprenol; and monomers having sulfonic acid groups such as 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and vinylsulfonic acid, as well as their salts.

[0017] The proportion of structural units derived from other monomers in the above polymer is preferably 0 to 90 mol%, more preferably 0 to 50 mol%, and still more preferably 0 to 40 mol%, based on 100 mol% of all structural units. By changing the type and amount, the dispersibility of the polymer in the detergent composition for semiconductors can be appropriately adjusted.

[0018] The weight average molecular weight of the polymer of the present disclosure is preferably 4100 or more, more preferably 5000 or more, and still more preferably 5500 or more. On the other hand, it is preferably 400000 or less, more preferably 300000 or less, and still more preferably 200000 or less.

[0019] The content of the polymer contained in the detergent composition for semiconductors of the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more, based on the total amount of the detergent composition for semiconductors. On the other hand, it is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

[0020] <pH Adjusting Agent> The pH adjusting agent contained in the detergent composition for semiconductors of the present disclosure is not particularly limited, and examples thereof include acidic compounds such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and boric acid, and basic compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, amines, and ammonium-based compounds.

[0021] Preferred examples of the basic compound contained in the detergent composition for semiconductors of the present disclosure include compounds represented by the following general formula (1) and the following general formula (2).

[0022]

Chemical Formula

[0023] (In formula (1), R 1 , R 2 and R 3, which may be the same or different, each independently represents hydrogen or an alkyl group having 1 to 18 carbon atoms.)

[0024]

Chemical Formula

[0025] (In formula (2), R 4 , R 5 , R 6 and R 7 , which may be the same or different, each independently represents hydrogen or an alkyl group having 1 to 18 carbon atoms.) For the amine compound of the present disclosure, in the general formula (1), R 1 , R 2 and R 3 preferably have 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. In the general formula (1), R 1 , R 2 and R 3 , as the alkyl group, may be linear or branched.

[0026] 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, an n-octadecyl group, an n-nonadecyl group, an n-icosyl group, an icosyl group, a henicosyl group, a triacontyl group, a tetracontyl group, and the like.

[0027] Examples of branched alkyl groups include sec-butyl group, isobutyl group, tert-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, isoamyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, tert-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-methylpentyl group, 1-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, sec-heptyl group, tert-heptyl group, isoheptyl group, sec-octyl group, tert-octyl group, isooctyl group, 1-ethylhexyl group, 1-propylpentyl group, 2-ethylhexyl group, and 2-propylpentyl group.

[0028] Examples of cyclic alkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, cyclohexadecyl, and cyclooctadecyl groups.

[0029] The alkyl group may have substituents. The substituents are not particularly limited, but examples include hydroxyl groups, alkoxy groups, halogen atoms, ether groups, cyano groups, and thiol groups. Preferably, the substituent is a hydroxyl group or an alkoxy group, and more preferably, a hydroxyl group.

[0030] Regarding the amine compounds of this disclosure, examples of compounds represented by the above 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.

[0031] The amine compounds disclosed herein are represented by the above general formula (2), R 4 , R 5 , R 6 and R 7 The number of carbon atoms is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, and even more preferably 1 to 4.

[0032] R represented in the general formula (2) above 4 , R 5 , R 6 and R 7 Regarding the alkyl group, it may be linear or branched. The alkyl group is not particularly limited, but as mentioned above, 2 Examples include alkyl groups similar to those represented by . Alkyl groups may have substituents. The substituents are not particularly limited, but examples include hydroxyl groups, alkoxy groups, halogen atoms, ether groups, cyano groups, and thiol groups. Preferably, the substituents are hydroxyl groups and alkoxy groups, and more preferably, hydroxyl groups.

[0033] R represented in the general formula (2) above 4 , R 5 , R 6 and R 7 Regarding this, the alkyl group may have one or more substituents, or it may have two or more substituents.

[0034] Regarding the amine compounds of this disclosure, specific examples of compounds 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.

[0035] The pH adjusting agent contained in the semiconductor cleaning agent composition of this 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, based on the total amount of the semiconductor cleaning agent composition. On the other hand, it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0036] <Other ingredients> The semiconductor cleaning agent composition disclosed herein may contain other components. These other components are not limited to, but include, for example, color transfer inhibitors, softeners, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching aids, enzymes, dyes, dispersants, solvents, and the like.

[0037] The semiconductor cleaning agent compositions of this disclosure preferably contain a dispersant, although this is optional. The dispersant is not particularly limited, but it is preferably a nonionic dispersant.

[0038] The nonionic dispersant (hereinafter sometimes referred to as a nonionic polymer) is not particularly limited, but examples 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, and polyoxyalkylene alkyl Examples include ethers, polyoxyethylene 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 alkylamines, polyoxyethylene hydrogenated castor oil, alkyl alkanolamides, etc. In particular, it is preferable to include compounds represented by the following general formulas (3) and (4) and N-vinyl lactam polymers represented by N-vinylpyrrolidone.

[0039] [ka]

[0040] (In formula (3), R 8 , R 9 and R 10 R represents a hydrogen atom or an alkyl group, either identical or different. 11 and R 12 x and y represent alkylene groups, either identical or distinct. x and y represent integers between 0 and 50, either identical or distinct. (x+y) is an integer greater than or equal to 1.

[0041] [ka]

[0042] (In formula (4), R 13 , R 14 , R 15 and R 16 R represents a hydrogen atom or an alkyl group, either identical or different. 17 , R 18 , R 19 , R 20 and R 21 x and y represent either the same or different alkylene group or an alkynylene group. x and y represent either the same or different integers between 0 and 50. (x+y) is an integer greater than or equal to 1. In the above general formula (3), R 8 , R 9 and R 10 The alkyl group represented by may be linear or branched. The alkyl group of the general formula (3) above preferably has 1 or more carbon atoms, 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.

[0043] Examples of alkyl groups in the above general formula (3) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, iso-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, and 3-ethylpentyl group. Examples include linear or branched alkyl groups such as pentyl group, 2,2,3-trimethylbutyl group, octyl group, methylheptyl group, dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-tetramethylbutyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group.

[0044] In the above general formula (3), R 11 and R 12 The alkylene group represented by may be linear or branched.

[0045] In the above general formula (3), R 11 and R 12 Examples of alkylene groups represented by include methylene group, ethylene group, n-propylene group, 2-propylene group, n-butylene group, pentamethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, methylmethylene group, methylethylene group, 1-methylpentylene group, and 1,4-dimethylbutylene group. Preferably, it is an alkylene group having 2 to 4 carbon atoms, and more preferably, an alkylene group having 2 to 3 carbon atoms. It tends to reduce the adhesion of metal residue to the wafer surface.

[0046] 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 even more preferably from 0 to 20.

[0047] x is alkylene oxide (R 11 This represents the average number of moles added of O), where y is alkylene oxide (R 12 This represents the average number of moles added (O). x and y may be the same or different for each alkylene oxide.

[0048] x is preferably a number between 0 and 30, more preferably between 0 and 25, and even more preferably between 0 and 20. y is preferably a number between 0 and 20, more preferably between 0 and 15, and even more preferably between 0 and 10. Here, x and y are preferably integers of 1 or greater. Hydrophilicity and hydrophobicity tend to be easily controlled.

[0049] In the above general formula (3), the molecular structure becomes compact and high permeability can be achieved, R 8 , R 9 and R 10 It is preferable that two or more of them are alkyl groups.

[0050] In the above general formula (4), R 13 , R 14 , R 15 and R 16 The alkyl group represented by the above R 8 , R 9 and R 10 Examples of alkyl groups similar to those represented by the symbol are shown.

[0051] The number of carbon atoms in the alkyl group of the above general formula (4) is preferably 1 or more, more preferably 2 or more. On the other hand, it is preferably 20 or less, more preferably 18 or less, and even more preferably 12 or less.

[0052] In the above general formula (4), R17 , R 18 , R 19 , R 20 and R 21 The alkylene group represented by the above R 11 and R 12 Examples include alkylene groups similar to those represented by . Preferably, the alkylene group has 2 to 4 carbon atoms, and more preferably, it has 2 to 3 carbon atoms.

[0053] 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 even more preferably from 0 to 20.

[0054] x is alkylene oxide (R 17 O) and (R 19 This represents the average number of moles added of O), where y is alkylene oxide (R 18 O) and (R 20 This represents the average number of moles added (O). x and y may be the same or different for each alkylene oxide. x is preferably a number between 1 and 30, more preferably between 1 and 20, and even more preferably between 1 and 18. y is preferably a number between 0 and 30, more preferably between 0 and 20, and even more preferably between 0 and 10. Here, x and y are preferably integers greater than or equal to 1.

[0055] The other components contained in the semiconductor cleaning agent composition of this disclosure may consist of one type or two or more types. The other components contained in the semiconductor cleaning agent composition of this disclosure are 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. On the other hand, they are preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0056] The content of each component, such as polymers, pH adjusters, and other components, contained in the semiconductor cleaning agent composition of this disclosure refers to the content of each component of the semiconductor cleaning agent composition at the time of use in the cleaning process, i.e., at the start of use for cleaning (which may also be referred to as use or cleaning), in one or more embodiments.

[0057] The semiconductor cleaning agent composition disclosed herein may be prepared as a concentrated product with a reduced amount that does not impair storage stability due to separation, precipitation, etc. The concentrated type of the semiconductor cleaning agent composition is preferably 5 times or more from the viewpoint of transportation costs, and preferably 100 times or less from the viewpoint of storage stability.

[0058] The concentrate of the semiconductor cleaning agent composition can be used after diluting it with water so that each component is present in the above-mentioned amounts (i.e., the amounts present during cleaning) at the time of use. Furthermore, the concentrate of the semiconductor cleaning agent composition can also be used by adding each component separately at the time of use. In this disclosure, "at the time of use" or "at the time of cleaning" of the concentrate of the semiconductor cleaning agent composition refers to the state in which the concentrate of the semiconductor cleaning agent composition has been diluted.

[0059] The pH of the semiconductor cleaning agent composition of this disclosure is preferably 7 or higher, more preferably 8 or higher, and even more preferably 9 or higher. On the other hand, it is preferably 14 or lower, more preferably 13.8 or lower, and even more preferably 13.6 or lower. [Method for manufacturing a cleaning agent composition for semiconductors] Polymers can be produced by polymerizing ethylenically unsaturated monomers having two or more carboxyl groups in one molecule (including salts of two or more carboxyl groups or anhydrides of carboxyl groups), or other monomers, in an aqueous solvent.

[0060] <Polymerization method> The method for producing the above polymer is not particularly limited, and any polymerization reaction of radical polymerization, cationic polymerization, or anionic polymerization may be used. Furthermore, the polymerization reaction may be either photopolymerization or thermal polymerization.

[0061] The polymerization method is not particularly limited, but examples include adding a polymerization initiator, irradiating with UV light, applying heat, or irradiating with light in the presence of a photopolymerization initiator. In the above polymerization step, it is preferable to use a polymerization initiator.

[0062] Examples of polymerization initiators 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, and 2,2'-azobis(1-imidazolin-2-yl)propane. Suitable polymerization initiators include azo compounds such as (no-1-pyrrolidino-2-methylpropane) dihydrochloride, 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 cumenehydroperoxide; 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. Of these polymerization initiators, hydrogen peroxide, persulfates, and azo compounds are preferred, and persulfates are more preferred, as they tend to reduce the amount of residual monomers.

[0063] These polymerization initiators may be used individually or in the form of a mixture of two or more. The amount of polymerization initiator used is preferably 0.1 g to 30 g, more preferably 0.2 g to 20 g, and even more preferably 0.25 g to 15 g, per 100 g of monomer used.

[0064] In the polymerization process described above, a chain transfer agent may be used as a molecular weight modifier of the polymer as needed. Examples of chain transfer agents include mercaptocarboxylic acids such as thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutanoic acid, thiomalic acid and their salts, as well as mercaptoethanol, thioglycerol, 2-mercaptoethanesulfonic acid, etc.; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, etc.; secondary alcohols such as isopropanol and glycerin; phosphorous acid, hypophosphorous acid, hypophosphate and their hydrates, etc.; bisulfite (salt) and compounds that can generate bisulfite (salt) (bisulfite (salt), pyrosulfite (salt), dithionic acid (salt), sulfite (salt), etc.). Among these, compounds having a mercapto group, such as bisulfite (salt), phosphorous acid (salt), and mercaptocarboxylic acid, are preferred, and bisulfite (salt) and phosphorous acid (salt) are more preferred.

[0065] In the production of the copolymer of the present invention, the amount of chain transfer agent used is preferably 0 mol% to 30 mol%, more preferably 0 mol% to 25 mol%, even more preferably 0 mol% to 20 mol%, and most preferably 0 mol% to 10 mol%, based on 100 mol% of the amount of monomer (total monomer) used. (Since it is not used in this case, 0 is included.) In the polymerization process described above, the polymerization temperature is preferably 40°C or higher, and preferably 150°C or lower. More preferably 50°C or higher, and even more preferably 55°C or higher. Furthermore, it is more preferably 120°C or lower, and even more preferably 110°C or lower.

[0066] In the polymerization process described above, the method of adding the monomer components to the reaction vessel is not particularly limited. Examples include adding the entire amount to the reaction vessel all at once at the beginning; adding the entire amount to the reaction vessel in installments or continuously; adding a portion to the reaction vessel initially and then adding the remainder in installments or continuously. When using a radical polymerization initiator, it may be added to the reaction vessel from the beginning, added dropwise to the reaction vessel, or a combination of these methods may be used depending on the purpose.

[0067] 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.

[0068] <Examples of preferred forms of semiconductor cleaning agent compositions of this disclosure> [1] A semiconductor cleaning agent composition comprising a polymer and a pH adjuster, wherein the polymer comprises structural units (A) derived from ethylenically unsaturated monomers having two or more carboxyl groups (including salts of two or more carboxyl groups or anhydrides of carboxyl groups) in one molecule, and the pH is 7 or higher. [2] The semiconductor cleaning agent composition according to [1], wherein the weight-average molecular weight of the polymer is 4100 or more. [3] The semiconductor cleaning agent composition according to [1] or [2], comprising 38% by mass or more of structural units (A) derived from an ethylenically unsaturated monomer having two or more carboxyl groups (including salts of two or more carboxyl groups or anhydrous carboxyl groups) in one molecule, based on the total amount of the polymer. [4] The semiconductor cleaning agent composition according to [1] to [3] above, wherein the pH adjusting agent 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).

[0069] [ka] (In formula (1), R 1 , R 2 and R 3each, identically or differently, independently represent hydrogen or an alkyl group having 1 to 18 carbon atoms.)

[0070]

Chemical Formula

[0071]

Chemical Formula

[0072]

Chemical Formula

Examples

[0073] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited thereto, and any modifications or implementations that do not depart from the spirit of the invention are all included within the technical scope of the present invention. Unless otherwise specified, "%" means "mass%". <Measurement conditions for weight-average molecular weight (Mw)> 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 [Synthesis of polymers] <Synthesis Example 1> In a 5-liter stainless steel separable flask equipped with a reflux condenser, stirrer, and thermometer, 606 g of deionized water and 403 g of maleic anhydride were charged. Under stirring, 684.7 g of 48 wt% sodium hydroxide aqueous solution (hereinafter referred to as 48% NaOHaq) was gradually added. Subsequently, the aqueous solution in the flask was heated to its boiling point under atmospheric pressure while stirring. Next, under stirring, 369.4 g of 80 wt% acrylic acid aqueous solution (hereinafter referred to as 80% AA), 103.7 g of 35 wt% hydrogen peroxide aqueous solution (hereinafter referred to as 35% H2O2), 127.6 g of 15 wt% sodium persulfate aqueous solution (hereinafter referred to as 15% NaPS), and 211 g of deionized water were added dropwise from separate nozzles. The 80% AA was added for 260 minutes, the 15% NaPS and 35% H2O2 were added dropwise simultaneously with the 80% AA for 260 minutes, and the deionized water was added dropwise for 140 minutes, 150 minutes after the start of the 80% AA addition. After all additions were completed, the reaction solution was held under reflux at the boiling point for another 20 minutes to complete the polymerization. In this way, an acrylic acid-maleic acid copolymer (salt) was obtained. Subsequently, the pH of this acrylic acid-maleic acid copolymer (salt) was adjusted to 7.5 with an aqueous NaOH solution. The weight-average molecular weight of the obtained polymer was 5600.

[0074] <Synthesis Example 2> In a 5-liter stainless steel separable flask equipped with a reflux condenser, stirrer, and thermometer, 381 g of deionized water and 242.6 g of maleic anhydride were charged. Under stirring, 408.5 g of 48 wt% sodium hydroxide aqueous solution (hereinafter referred to as 48% NaOHaq) was gradually added. Subsequently, the aqueous solution in the flask was heated to its boiling point under atmospheric pressure while stirring. 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% H2O2), 157.3 g of 15 wt% sodium persulfate aqueous solution (hereinafter referred to as 15% NaPS), and 250 g of deionized water were added dropwise from separate nozzles. The 80% AA and 35% H2O2 were added for 240 minutes, the 15% NaPS was added dropwise starting simultaneously with the 80% AA and continued for 250 minutes, and the deionized water was added dropwise for 160 minutes, starting 110 minutes after the start of the 80% AA addition. After all additions were completed, the reaction solution was held under reflux at the boiling point for another 30 minutes to complete the polymerization. In this way, an acrylic acid-maleic acid copolymer (salt) was obtained. Subsequently, the pH of this acrylic acid-maleic acid copolymer (salt) was adjusted to 8.5 with an aqueous NaOH solution. The weight-average molecular weight of the obtained polymer was 10700.

[0075] <Synthesis Example 3> In a 5-liter stainless steel separable flask equipped with a reflux condenser, stirrer, and thermometer, 145.7 g of deionized water and 332.3 g of maleic anhydride were charged. Under stirring, 564.8 g of 48 wt% sodium hydroxide aqueous solution (hereinafter referred to as 48% NaOHaq) was gradually added. Subsequently, the aqueous solution in the flask was heated to its boiling point under atmospheric pressure while stirring. Next, under stirring, 482 g of 80 wt% acrylic acid aqueous solution (hereinafter referred to as 80% AA), 12.8 g of 35 wt% hydrogen peroxide aqueous solution (hereinafter referred to as 35% H2O2), 72.8 g of 15 wt% sodium persulfate aqueous solution (hereinafter referred to as 15% NaPS), and 511 g of deionized water were added dropwise from separate nozzles. The 80% AA was added for 140 minutes, the 15% NaPS and deionized water were added simultaneously with the 80% AA for 170 minutes, and the 35% H2O2 was added simultaneously with the 80% AA for 185 minutes. After all additions were complete, the reaction solution was held under reflux at the boiling point for another 30 minutes to complete the polymerization. In this way, an acrylic acid-maleic acid copolymer (salt) was obtained. Subsequently, the pH of this acrylic acid-maleic acid copolymer (salt) was adjusted to 8 with an aqueous NaOH solution. The weight-average molecular weight of the obtained polymer was 49400.

[0076] [Examples 1-6, Comparative Example 1] As shown in Table 1, a detergent composition was prepared by mixing water, polymer, and a dispersant as an additive, and adding a pH adjuster to achieve a predetermined pH. The amount of dispersant added was 0.25% by mass as solid content relative to the detergent composition. (How to create a contamination coupon) I cut a TEOS film-coated wafer, purchased from Kyushu Semiconductor Co., into 1.5cm squares. A contamination solution was prepared by diluting CeO2 slurry (HS0220, manufactured by Showa Denko Materials) purchased from Showa Denko Materials 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 more than 5 minutes. The above wafers were dried, and contamination coupons were created. (Cleaning process) 30 ml of the cleaning agent composition prepared for each example was placed in a PFA container, and the contaminated substrate was immersed in the cleaning agent composition. The substrate was then cleaned by ultrasonic irradiation for 2 minutes using an ultrasonic device (BRANSON S8500) (processing conditions: output 40 kHz). After ultrasonic treatment, the substrate was rinsed with ultrapure water for 5 minutes and then air-dried to complete the cleaning process. (Method for calculating cleaning efficiency) The surface analysis of the TEOS film substrate before and after cleaning was performed using an X-ray photoelectric spectrometer under the following conditions. Equipment: SHIMADZU AXIS-NOVA Measurement conditions / excitation source: Al Kα 12mA 12kV, Pass Energy: 160eV Based on the analysis, cleaning performance was determined by the difference (%) of Ce elements present on the substrate surface before and after cleaning. The cleaning rate was calculated according to the following formula. Cleaning rate (%) = (Ce ratio of substrate before cleaning - Ce ratio of substrate after cleaning) / Ce ratio of substrate before cleaning × 100 Furthermore, the cleaning rate was determined according to the following criteria. Cleaning rate evaluation criteria: Cleaning rate Over 95%~100%:◎ Over 90%~95%:○ Over 86%~90% or less:△ 86% or less: ×

[0077] [Table 1]

[0078] The compounds in Table 1 are as follows: MEA: Monoethanolamine AH212: Dimethylbis(2-hydroxyethyl)ammonium hydroxide Nonionic dispersant (i):

[0079] [ka] (In the formula, R 8 :H, R 9 and R 10each is a linear alkyl group having 1 to 12 carbon atoms, and R 9 and R 10 has a total number of carbon atoms of 11 to 13, R 11 is -C2H4-, R 12 is -CH2CH(CH3)-, x=12, y=3, and x and y represent average number of added moles). which is a mixture of a plurality of compounds satisfying the above conditions). From the results in Table 1, it is clear that the composition has high removal performance for ceria particles.

Claims

1. A semiconductor cleaning agent composition comprising a polymer and a pH adjuster, The polymer contains structural units (A) derived from ethylenically unsaturated monomers (excluding itaconic acid) having two or more carboxyl groups (including salts of two or more carboxyl groups or anhydrides of carboxyl groups) in one molecule, and the polymer contains 38% by mass or more of these structural units (A) relative to the total amount of the polymer. A semiconductor cleaning agent composition wherein the pH adjusting agent contains one or more compounds selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by general formula (2), and the pH is greater than 7. 【Chemistry 1】 (In formula (1), R1, R2, and R3 are the same or different, and each independently represents hydrogen or an alkyl group having 1 to 18 carbon atoms.) 【Chemistry 2】 (In formula (2), R4, R5, R6, and R7 are the same or different, and each independently represents hydrogen or an alkyl group having 1 to 18 carbon atoms.)

2. The semiconductor cleaning agent composition according to claim 1, wherein the weight-average molecular weight of the polymer is 4100 or more.

3. A semiconductor cleaning agent composition according to claim 1 or 2, comprising a compound represented by the following general formula (3) and / or (4). 【Transformation 3】 (In formula (3), R8, R9, and R10 represent a hydrogen atom or an alkyl group, either the same or different. R11 and R12 represent an alkylene group, either the same or different. x and y represent integers from 0 to 50, either the same or different. (x + y) is an integer of 1 or more.) 【Chemistry 4】 (In formula (4), R13, R14, R15, and R16 represent a hydrogen atom or an alkyl group, either identically or differently. R17, R18, R19, R20, and R21 represent an alkylene group or an alkynylene group, either identically or differently. x and y represent integers from 0 to 50, either identically or differently. (x + y) is an integer of 1 or greater.)

4. The semiconductor cleaning agent composition according to claim 1 or 2, wherein the pH is 9 or higher.

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