Treatment solution, method for treating object, and method for producing semiconductor device

Abstract

The present invention provides a treatment solution that, when the treatment solution is applied to an object having a copper surface which has been subjected to chemical-mechanical polishing treatment, causes little corrosion of copper and is excellent in ability to remove an organic residue on the copper surface. The present invention also provides a method for treating an object using the treatment solution, and a method for producing a semiconductor device using the treatment solution.　A treatment solution according to the present invention comprises an anionic polymer, a phosphonic acid compound, and hydroxyl-group-containing carboxylic acid, wherein the mass ratio of the phosphonic acid compound content to the anionic polymer content is 0.1-1000, and the pH is 0.1-7.0. The treatment solution is used in a semiconductor production process.

Description

Treatment liquid, method for treating object, and method for manufacturing semiconductor device

[0001] The present invention relates to a processing liquid, a method for processing an object, and a method for manufacturing a semiconductor device.

[0002] A semiconductor device is manufactured by forming a resist film on a laminate having a metal film, an etching stop layer, and an interlayer insulating layer on a substrate, and then performing a photolithography process. In the photolithography process, a method of etching or removing foreign matter from the substrate surface using a treatment liquid that dissolves metals and / or organic substances is widely known.

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

[0004] As a treatment liquid used in the cleaning step, for example, Patent Document 1 discloses "a water-based formulation having choline hydroxide together with a polymer selected from the group consisting of an acrylamide-methyl-propanesulfonate polymer, an acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer, and mixtures thereof, and a quaternary ammonium hydroxide having more than 4 carbon atoms or a non-acetylenic surfactant, as a post-CMP cleaning formulation."

[0005] JP 2011-040722 A

[0006] The present inventors have investigated the removability of residues present on copper surfaces of objects after CMP treatment using the post-CMP cleaning formulations described in Patent Document 1, and have found that it is difficult to simultaneously inhibit corrosion of the copper surface and remove organic residues on the copper surface.

[0007] Therefore, an object of the present invention is to provide a treatment solution that, when applied to an object having a copper surface that has been subjected to chemical mechanical polishing, causes little corrosion of the copper and is excellent in removing organic residues from the copper surface. Another object of the present invention is to provide a method for treating an object using the treatment solution, and a method for manufacturing a semiconductor device.

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

[0009] [1] A treatment solution used in a semiconductor manufacturing process, comprising: an anionic polymer; a phosphonic acid compound; and a hydroxyl group-containing carboxylic acid, wherein the mass ratio of the content of the phosphonic acid compound to the content of the anionic polymer is 0.1 to 1000; and the pH is 0.1 to 7.0. [2] The treatment solution according to [1], wherein the hydroxyl group-containing carboxylic acid is selected from the group consisting of citric acid, malic acid, tartaric acid, glycolic acid, lactic acid, tartronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ-hydroxybutyric acid, citramalic acid, isocitric acid, leucinic acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinelaideic acid, cerebronic acid, quinic acid, shikimic acid, salicylic acid, creosote acid, vanillic acid, syringic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orselliic acid, gallic acid, mandelic acid, benzilic acid, atrolactic acid, mellotic acid, phloretic acid, coumaric acid, umbellic acid, caffeic acid, ferulic acid, and sinapic acid. [3] The treatment solution according to [1] or [2], wherein the phosphonic acid compound is selected from the group consisting of etidronic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid. [4] The treatment solution according to any one of [1] to [3], wherein the anionic polymer is selected from the group consisting of polyacrylic acid, polystyrenesulfonic acid, polyvinylsulfonic acid, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, polyvinylphosphonic acid, poly(N-vinylacetamide), and styrenesulfonic acid-acrylic acid-vinylphosphonic acid copolymer. [5] The treatment solution according to any one of [1] to [4], wherein the anionic polymer does not have a repeating unit derived from an acrylamide-based monomer. [6] The treatment liquid according to any one of [1] to [5], wherein the mass ratio of the content of the hydroxyl group-containing carboxylic acid to the content of the anionic polymer is at least 10. [7] The treatment liquid according to any one of [1] to [6], wherein the mass ratio of the content of the hydroxyl group-containing carboxylic acid to the content of the anionic polymer is at least 100.[8] The treatment liquid according to any one of [1] to [7], wherein the mass ratio of the content of the anionic polymer to the total solid content of the treatment liquid is 0.0001 to 0.1. [9] The treatment liquid according to any one of [1] to [8], further comprising an anionic surfactant selected from the group consisting of sulfonic acid surfactants, carboxylic acid surfactants, and phosphate ester surfactants.

[10] The treatment liquid according to [9], wherein the anionic surfactant is the sulfonic acid surfactant having an alkyl chain having 6 or more carbon atoms.

[11] The treatment liquid according to any one of [1] to

[10] , which is used to clean an object that has been subjected to chemical mechanical polishing.

[12] The treatment liquid according to

[11] , which is used to clean a copper surface that has been subjected to chemical mechanical polishing, and which is used to clean the copper surface.

[13] The treatment liquid according to any one of [1] to

[12] , which is diluted with a diluent containing water.

[14] The treatment liquid according to any one of [1] to

[13] , which does not contain a quaternary ammonium salt.

[15] A method for treating an object, comprising a step of contacting an object that has been subjected to chemical mechanical polishing treatment with the treatment liquid according to any one of [1] to

[14] .

[16] A method for manufacturing a semiconductor device, comprising the method for treating an object according to

[15] .

[0010] According to the present invention, there is provided a treatment solution that, when applied to an object having a copper surface that has been subjected to chemical mechanical polishing, causes little corrosion of the copper and is excellent in removing organic residues from the copper surface. Furthermore, there are also provided a method for treating an object using the treatment solution and a method for manufacturing a semiconductor device.

[0011] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] The following describes the meaning of each description in this specification.

[0013] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In this specification, "total solid content" means the total mass of all components contained in the treatment liquid other than water and solvents such as organic solvents. In this specification, when two or more types of a component are present, the "content" of that component means the total content of those two or more components. Unless otherwise specified, the compounds described in this specification may contain structural isomers, optical isomers, and isotopes. Furthermore, structural isomers, optical isomers, and isotopes may be contained alone or in combination.

[0014] In this specification, when there are multiple substituents and linking groups, etc. (hereinafter referred to as substituents, etc.) represented by a specific symbol, or when multiple substituents, etc. are specified simultaneously, this means that the respective substituents, etc. may be the same or different from each other. The same applies to the specification of the number of substituents, etc. The bonding direction of a divalent group represented in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. Furthermore, the above compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0015] In this specification, "(meth)acrylic" is a generic term including acrylic and methacrylic, and means "at least one of acrylic and methacrylic." Similarly, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid."

[0016] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight. In this specification, when the polymer used is a commercially available product and catalog values ​​(nominal values ​​from the manufacturer) are available for the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (also called molecular weight distribution) (Mw / Mn) of the polymer, the catalog values ​​are used. When catalog values ​​are not available or when the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (Mw / Mn) of a polymer are determined by measurement, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (Mw / Mn) are measured by Gel Permeation Chromatography (GPC) using a GPC device (Shimadzu Corporation, Prominence UFLC) (eluent: phosphate buffer (pH = 7) and acetonitrile in a volume ratio of 9:1, flow rate (sample injection amount): 50 μL, column: Tosoh Corporation, TSK guard column α + TSK gel α-6000 + TSK gel α-3000, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector (Refractive Index Detector)). The above description of "TSK guard column α + TSK gel α-6000 + TSK gel α-3000" indicates that the above three columns were used in conjunction with each other.

[0017] In this specification, "ppm" means "parts-per-million (10 －６ ) and "ppb" stands for "parts-per-billion (10 －９ In this specification, 1 Å (angstrom) corresponds to 0.1 nm.

[0018] [Treatment Solution] The treatment solution of the present invention is a treatment solution used in semiconductor manufacturing processes, comprising an anionic polymer, a phosphonic acid compound, and a hydroxyl group-containing carboxylic acid, wherein the mass ratio of the phosphonic acid compound content to the anionic polymer content is 0.1 to 1000, and the pH is 0.1 to 7.0. The mechanism by which the treatment solution of the present invention having the above-described configuration can solve the problems of the present invention is not necessarily clear, but the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effects are obtained. In other words, even if the effects are obtained by a mechanism other than the one described below, it is still within the scope of the present invention.

[0019] The treatment solution of the present invention is characterized by the inclusion of an anionic polymer. While acid compounds such as hydroxyl-containing carboxylic acids and phosphonic acid compounds are effective in removing copper-containing organic residues generated after CMP treatment, they also corrode copper. The present inventors investigated the composition of the treatment solution and surprisingly found that adding an anionic polymer to the treatment solution containing the hydroxyl-containing carboxylic acid and phosphonic acid compound not only inhibits copper corrosion but also effectively removes organic residues.

[0020] The components contained in the treatment solution of the present invention are described in detail below. In this specification, the term "excellent effect of the present invention" refers to the fact that, when the treatment solution is applied to an object having a copper surface that has been subjected to chemical mechanical polishing, at least one of the effects of reducing copper corrosion and being excellent in the removability of organic residues on the copper surface is obtained.

[0021] [Anionic Polymer] The treatment liquid of the present invention contains an anionic polymer. An anionic polymer is a polymer containing a functional group (hereinafter also referred to as an "anionic functional group"), such as a carboxy group, that exhibits anionic properties when dissolved in water. The anionic polymer is preferably a polymer containing a repeating unit having an anionic functional group (hereinafter also referred to as "repeating unit A"). As described in detail below, the anionic polymer may contain repeating units other than repeating unit A, but is preferably a polymer consisting only of repeating unit A. The anionic polymer may contain two or more types of repeating unit A. When the anionic polymer has two or more types of repeating units, the polymerization mode is not particularly limited, and may be a graft copolymer, a block copolymer, or the like.

[0022] <Repeating Unit A> The anionic functional group contained in the repeating unit A is not particularly limited, and examples thereof include an acid group or a salt thereof. Specific examples of the acid group include a carboxy group, a sulfonic acid group, a phosphonic acid group, and a phenolic hydroxyl group. Examples of salts of the acid group include ammonium salts, potassium salts, sodium salts, and lithium salts. The number of acid groups or salts thereof contained in the repeating unit A is not particularly limited, and is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0023] In terms of achieving better effects of the present invention, the anionic polymer is preferably a polymer containing a repeating unit A selected from the group consisting of a repeating unit having a carboxy group or a salt thereof, and a repeating unit having a sulfonic acid group or a salt thereof, more preferably a polymer consisting only of a repeating unit A selected from the group consisting of a repeating unit having a carboxy group or a salt thereof, and a repeating unit having a sulfonic acid group or a salt thereof, and even more preferably a polymer consisting only of a repeating unit A having a carboxy group or a polymer consisting only of a repeating unit A having a sulfonic acid group.

[0024] Examples of the repeating unit A include repeating units derived from a compound having an acid group or a salt thereof, and an ethylenically unsaturated group. Specific examples of the acid group or a salt thereof are as described above. The ethylenically unsaturated group is a functional group having an ethylenically unsaturated bond. Examples of the ethylenically unsaturated group include an aromatic vinyl group, an acryloyloxy group (CH ２ ═CH—COO—), methacryloyloxy group (CH ２ = CCH ３ -COO-), acrylamide group (CH ２ ═CH—CONH—), methacrylamide group (CH ２ = CCH ３ Examples of the ethylenically unsaturated group include an aromatic vinyl group, an acryloyloxy group, a methacryloyloxy group, an acrylamide group, or a vinyl group. A styryl group is preferred as the aromatic vinyl group. The repeating unit A may be a repeating unit derived from a compound having an acrylamide group (an acrylamide-based monomer). However, when the anionic polymer does not have a repeating unit derived from an acrylamide-based monomer, this is preferred because, even when a copper-containing object is treated with a treatment solution that has been stored over time, the physical properties of the treatment solution change little over time and copper corrosion is minimal.

[0025] The repeating unit A is preferably a repeating unit represented by formula (a).

[0026]

[0027] In formula (a), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acid group or a salt thereof. ａ represents a single bond or a (k+1)-valent linking group. A represents an acid group or a salt thereof. k represents an integer of 1 to 4. When a plurality of acid groups or salts thereof are present in formula (a), the plurality of acid groups or salts thereof may be the same or different.

[0028] R ａ１ , Rａ２ and R ａ３ is preferably a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a methyl group, an ethyl group, a carboxy group, or a salt thereof, and more preferably a hydrogen atom, a methyl group, or a carboxy group, or a salt thereof. ａ１ , R ａ２ and R ａ３ It is preferred that one of represents a hydrogen atom, a methyl group, a carboxy group, or a salt thereof, and the remaining two each represent a hydrogen atom.

[0029] L ａ The (k+1)-valent linking group represented by the formula (I) is not particularly limited as long as it is a group having a valence corresponding to the number of A, and examples thereof include an optionally substituted di- to pentavalent aliphatic hydrocarbon group, an optionally substituted di- to pentavalent aromatic hydrocarbon group, an optionally substituted di- to pentavalent aromatic heterocyclic group, -O-, -CO-, -SO ２ -, -NR Ｌ -, -N<, and groups formed by combining these. Ｌ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic. k is preferably 1, and in this case, L ａ Examples of the divalent linking group represented by the formula (I) include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, —O—, —CO—, —SO ２ -, -NR Ｌ Among these, a single bond, —CO—O—, —CO—NH—, an alkylene group having 1 to 5 carbon atoms, a phenylene group, and a group formed by combining these are preferred.

[0030] Examples of the acid group represented by A or a salt thereof include a carboxy group, a sulfonic acid group, a phosphonic acid group, a phenolic hydroxyl group, and salts thereof. A carboxy group or a salt thereof, or a sulfonic acid group or a salt thereof is preferred, and a carboxy group or a salt thereof is more preferred.

[0031] Examples of the repeating unit A include repeating units derived from a compound selected from the group consisting of acrylic acid, maleic acid, itaconic acid, vinylacetic acid, allylacetic acid, fumaric acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, vinylphosphonic acid, and N-vinylacetamide.

[0032] The content of the repeating unit A is not particularly limited, but is preferably 50 to 100 mol %, more preferably 75 to 100 mol %, and even more preferably 90 to 100 mol %, based on the total repeating units of the anionic polymer.

[0033] <Repeating Unit B> The anionic polymer may contain a repeating unit B that is different from the repeating unit A. The repeating unit B is not particularly limited, and examples thereof include repeating units derived from compounds selected from the group consisting of alkylene oxide compounds, aromatic vinyl compounds, (meth)acrylic acid alkyl ester compounds which may have a hydroxyl group, unsaturated alcohol compounds, aliphatic conjugated diene compounds, vinyl cyanide compounds, and amide compounds having a polymerizable double bond.

[0034] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene.

[0035] The content of repeating unit B is not particularly limited, but is preferably 0.1 to 50 mol %, more preferably 1 to 25 mol %, and even more preferably 1 to 15 mol %, based on the total repeating units of the anionic polymer.

[0036] The anionic polymer is preferably selected from the group consisting of polyacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, polyvinylphosphonic acid, poly(N-vinylacetamide), and styrenesulfonic acid-acrylic acid-vinylphosphonic acid copolymer.

[0037] The weight average molecular weight of the anionic polymer is preferably from 500 to 80,000, more preferably from 1,000 to 30,000, still more preferably from 2,000 to 20,000, and particularly preferably from 4,000 to 10,000.

[0038] The anionic polymer may be used alone or in combination of two or more. The content of the anionic polymer is preferably 0.0001 to 10.0% by mass, more preferably 0.001 to 1.0% by mass, and even more preferably 0.01 to 1.0% by mass, relative to the total mass of the treatment liquid. The mass ratio of the content of the anionic polymer to the total solids content of the treatment liquid is preferably 0.00001 to 1.0, more preferably 0.0001 to 0.1, and even more preferably 0.001 to 0.05.

[0039] [Phosphonic Acid Compound] The treatment liquid of the present invention contains a phosphonic acid compound. The phosphonic acid compound refers to a compound containing at least one phosphonic acid group (a group formed by removing one hydrogen atom on the phosphorus atom from phosphonic acid) in the molecule, and is a compound different from the anionic polymer described above. The number of phosphonic acid groups contained in the phosphonic acid compound is preferably 2 to 8, more preferably 2 to 4, and even more preferably 2 to 3. The phosphonic acid compound is preferably a low-molecular-weight compound that does not have a repeating unit. In other words, the phosphonic acid compound is preferably not a polymeric compound having multiple repeating units, but a compound that does not have a repeating unit (corresponding to a low-molecular-weight compound). The molecular weight of the phosphonic acid compound is preferably 50 to 1,000, more preferably 100 to 600, and even more preferably 100 to 450.

[0040] The phosphonic acid compound is preferably an organic acid. That is, the phosphonic acid compound is preferably a phosphonic acid-based organic acid. The number of carbon atoms (carbon number) contained in the phosphonic acid compound is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8. Examples of phosphonic acid-based organic acids include aliphatic phosphonic acid-based organic acids and aminophosphonic acid-based organic acids. The aliphatic phosphonic acid-based organic acids may further have a hydroxyl group in addition to the phosphonic acid group and the aliphatic group. Examples of phosphonic organic acids include ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (etidronic acid, HEDP), nitrilotris(methylenephosphonic acid) (NTMP), ethylenediaminetetra(methylenephosphonic acid) (EDTMP), 2-phosphonobutane-1,2,4-tricarboxylic acid, diethylenetriaminepenta(methylenephosphonic acid) (DEPPO), 1-hydroxypropylidene-1,1'-diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, ethylaminobis(methylenephosphonic acid), and dodecylaminobis(methylenephosphonic acid). Examples of suitable phosphonic acid compounds include 1,2-diaminopropanetetra(methylenephosphonic acid), 1,6-hexamethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(ethylenephosphonic acid), triethylenetetraminehexa(methylenephosphonic acid), and triethylenetetraminehexa(ethylenephosphonic acid). The phosphonic acid compound is preferably selected from the group consisting of etidronic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid.

[0041] In addition to the above, examples of phosphonic acid-based organic acids include the compounds described in paragraphs

[0026] to

[0036] of WO 2018 / 020878, the contents of which are incorporated herein by reference. Furthermore, commercially available phosphonic acid-based organic acids include those that contain water such as distilled water, deionized water, and ultrapure water in addition to the phosphonic acid-based organic acid, and such water-containing phosphonic acid-based organic acids may also be used.

[0042] The phosphonic acid compound may be used alone or in combination of two or more. The content of the phosphonic acid compound is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass, and even more preferably 0.01 to 1% by mass, relative to the total mass of the treatment liquid. The mass ratio of the content of the phosphonic acid compound to the total solid content of the treatment liquid is preferably 0.001 to 10, more preferably 0.01 to 1.0, and even more preferably 0.01 to 0.1.

[0043] The mass ratio of the phosphonic acid compound content to the anionic polymer content is not particularly limited as long as it is 0.1 to 1000, but is preferably 0.1 to 500, more preferably 0.1 to 50, and even more preferably 0.1 to 10.

[0044] [Hydroxyl-Containing Carboxylic Acid] The treatment liquid of the present invention contains a hydroxyl-containing carboxylic acid. The hydroxyl-containing carboxylic acid refers to a compound having at least one hydroxyl group and at least one carboxy group in the molecule, and is a compound different from the anionic polymer described above. The number of carboxy groups in the hydroxyl-containing carboxylic acid is preferably 2 to 8, more preferably 2 to 4, and even more preferably 2 to 3. The number of hydroxyl groups in the hydroxyl-containing carboxylic acid is preferably 1 to 5, and more preferably 1 to 3. The hydroxyl-containing carboxylic acid is preferably a low-molecular-weight compound having no repeating units. The molecular weight of the hydroxyl-containing carboxylic acid is preferably 50 to 1,000, more preferably 100 to 600, and even more preferably 100 to 450. The number of carbon atoms in the hydroxyl-containing carboxylic acid is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8.

[0045] The hydroxyl group-containing carboxylic acid is preferably an α-hydroxycarboxylic acid (a carboxylic acid having a hydroxyl group (hydroxy group) on the carbon atom to which the carboxy group is bonded). The hydroxyl group-containing carboxylic acid may be either an aliphatic hydroxycarboxylic acid or an aromatic hydroxycarboxylic acid, but is preferably an aliphatic hydroxycarboxylic acid, and more preferably an aliphatic hydroxycarboxylic acid having 1 to 15 carbon atoms.

[0046] As the carboxylic acid-based organic acid, a compound represented by formula (D) is preferred, and a compound represented by formula (D1) is more preferred.

[0047]

[0048] In formula (D), L ｄ represents a divalent linking group having a hydroxyl group. Examples of the divalent linking group include an ether group, a carbonyl group, an ester group, a thioether group, and —SO ２ Examples of the substituents include -, -NT-, divalent hydrocarbon groups (e.g., alkylene groups, alkenylene groups, alkynylene groups, and arylene groups), and combinations thereof. T represents a hydrogen atom or a substituent. The divalent linking group may further have a substituent in addition to the hydroxyl group. Examples of the substituent include an alkyl group, an aryl group, a carboxy group, an amino group, and a halogen atom. Among these, L ｄ is preferably a divalent hydrocarbon group having a hydroxyl group, more preferably an alkylene group having a hydroxyl group. The number of hydroxyl groups in the divalent linking group is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the divalent linking group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.

[0049]

[0050] In formula (D1), R ｄ１ and R ｄ２ each independently represents a hydrogen atom, a hydroxyl group, or a carboxyl group, and n represents an integer of 1 to 5. However, when n is 1, R ｄ１ and R ｄ２ At least one of R represents a hydroxyl group, and when n is 2 or more, a plurality of R ｄ１ and Rｄ２ At least one of these represents a hydroxyl group.

[0051] The total number of carboxy groups contained in the compound represented by formula (D1) is preferably 2 to 8, more preferably 2 to 4, and still more preferably 2 to 3. The total number of hydroxyl groups contained in the compound represented by formula (D1) is preferably 1 to 5, and more preferably 1 to 3.

[0052] n represents an integer of 1 to 5. n is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0053] The hydroxyl group-containing carboxylic acid is preferably selected from the group consisting of citric acid, malic acid, tartaric acid, gluconic acid, heptonic acid, glycolic acid, lactic acid, tartronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ-hydroxybutyric acid, citramalic acid, isocitric acid, leucinic acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinelaideic acid, cerebronic acid, quinic acid, shikimic acid, phenyllactic acid, hydroxyphenyllactic acid, salicylic acid, creosote acid, vanillic acid, syringic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orselliic acid, gallic acid, mandelic acid, benzilic acid, atrolactic acid, mellotic acid, phloretic acid, coumaric acid, umbellic acid, caffeic acid, ferulic acid, and sinapic acid.

[0054] The hydroxyl-containing carboxylic acid may be used alone or in combination of two or more. The content of the hydroxyl-containing carboxylic acid is preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass, and even more preferably 1 to 30% by mass, relative to the total mass of the treatment liquid. The mass ratio of the content of the hydroxyl-containing carboxylic acid to the total solid content of the treatment liquid is preferably 0.001 to 10, more preferably 0.1 to 1.0.

[0055] The mass ratio of the content of the hydroxyl group-containing carboxylic acid to the content of the anionic polymer is not particularly limited, but is preferably 1 to 12,000, more preferably 10 to 1,000, even more preferably 10 to 250, and particularly preferably 100 to 250.

[0056] [Anionic Surfactant] The treatment liquid of the present invention may contain an anionic surfactant, and preferably further contains an anionic surfactant selected from the group consisting of sulfonic acid surfactants, carboxylic acid surfactants, and phosphate ester surfactants. The anionic surfactant is a compound different from the above-mentioned components. The anionic surfactant is preferably a low-molecular-weight compound that does not have a repeating unit. The molecular weight of the anionic surfactant is preferably 50 to 1,000, more preferably 100 to 600, and even more preferably 100 to 450.

[0057] Anionic surfactants often have at least one hydrophobic group selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. When the hydrophobic group contains an aromatic hydrocarbon group, the carbon number of the hydrophobic group contained in the anionic surfactant is preferably 6 or more, more preferably 10 or more. When the hydrophobic group does not contain an aromatic hydrocarbon group and is composed only of an aliphatic hydrocarbon group, the carbon number of the hydrophobic group contained in the anionic surfactant is preferably 9 or more, more preferably 13 or more, and even more preferably 16 or more. The upper limit of the carbon number of the hydrophobic group contained in the anionic surfactant is preferably 20 or less, more preferably 18 or less. Among these, sulfonic acid surfactants having an alkyl chain with 6 or more carbon atoms are preferred as anionic surfactants.

[0058] (Sulfonic Acid Surfactants) Examples of sulfonic acid surfactants include alkyl sulfonic acids, alkyl benzene sulfonic acids, alkyl naphthalene sulfonic acids, alkyl diphenyl ether disulfonic acids, alkyl methyl taurines, sulfosuccinic acid diesters, polyoxyalkylene alkyl ether sulfonic acids, and salts thereof. More specific examples of sulfonic acid surfactants include lauryl sulfonic acid, dodecyl benzene sulfonic acid, alkyl diphenyl ether disulfonic acids (the alkyl group preferably has 12 to 14 carbon atoms), and naphthalene sulfonic acid formalin condensates.

[0059] (Carboxylic Acid Surfactants) Examples of carboxylic acid surfactants include alkyl carboxylic acids, alkenyl carboxylic acids, alkyl benzene carboxylic acids, polyoxyalkylene alkyl ether carboxylic acids, anhydrides thereof, and salts thereof. More specific examples of carboxylic acid surfactants include trideceth-4 carboxylic acid, dodecenyl succinic anhydride, lauric acid, myristic acid, palmitic acid, stearic acid, polyoxyethylene lauryl ether acetic acid, and polyoxyethylene tridecyl ether acetic acid.

[0060] (Phosphate ester surfactant) Examples of the phosphate ester surfactant include alkyl phosphate ester, polyoxyalkylene alkyl ether phosphate ester, and salts thereof. Phosphate ester and polyoxyalkylene alkyl ether phosphate ester usually include both monoester and diester, but monoester or diester can be used alone. Examples of the salt of the phosphate ester surfactant include sodium salt, potassium salt, ammonium salt, and organic amine salt.

[0061] Examples of the phosphate ester surfactant include the compounds described in paragraphs

[0012] to

[0019] of JP-A-2011-040502, the contents of which are incorporated herein by reference.

[0062] The anionic surfactant may be used alone or in combination of two or more. The content of the anionic surfactant is preferably 0.001 to 8.0% by mass, more preferably 0.005 to 5.0% by mass, and even more preferably 0.01 to 3.0% by mass, relative to the total mass of the treatment liquid. Furthermore, the mass ratio of the content of the hydroxyl group-containing carboxylic acid relative to the total solids content of the treatment liquid is preferably 0.0001 to 1.0, more preferably 0.001 to 0.1.

[0063] [Water] The treatment liquid may contain water as a solvent. The type of water used in the treatment liquid may be any type that does not adversely affect the semiconductor substrate, and distilled water, deionized water (DI: De Ionized) water, and pure water (ultrapure water) can be used. Pure water (ultrapure water) is preferred because it contains almost no impurities and has less impact on the semiconductor substrate during the semiconductor substrate manufacturing process. The water content is preferably 1.0 mass% or more, more preferably 30.0 mass% or more, even more preferably 60.0 mass% or more, and particularly preferably 80.0 mass% or more, relative to the total mass of the treatment liquid. The upper limit of the water content is preferably 99.99 mass% or less, more preferably 99.9 mass% or less, even more preferably 99.0 mass% or less, and particularly preferably 97.0 mass% or less, relative to the total mass of the treatment liquid.

[0064] [Other Components] The treatment solution of the present invention may contain components other than those described above. Examples of other components include a pH adjuster, an organic solvent, a preservative (antibacterial agent), a reducing agent, and dissolved gases. It is also preferable that the treatment solution of the present invention does not contain a quaternary ammonium salt. The other components will be described below.

[0065] <pH Adjuster> The treatment liquid of the present invention may contain a pH adjuster to adjust and maintain the pH of the treatment liquid of the present invention. The pH adjuster is a basic compound or an acidic compound that is different from the components contained in the treatment liquid of the present invention described above. However, it is permissible to adjust the pH of the treatment liquid of the present invention by adjusting the amount of each component that can be contained in the treatment liquid of the present invention.

[0066] The basic compound is a compound that exhibits basicity (pH greater than 7.0) in an aqueous solution, and examples of the basic inorganic compound include amine compounds such as tris(hydroxymethyl)aminomethane, ammonia, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides.

[0067] The acidic compound as a pH adjuster is a compound that exhibits acidity (pH less than 7.0) in an aqueous solution, and examples of the acidic inorganic compound include hydrochloric acid, nitric acid, nitrous acid, sulfurous acid, phosphoric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and hexafluorophosphoric acid. The acidic compound as a pH adjuster may be a salt of an acidic compound, as long as it becomes an acid or an acid ion (anion) in an aqueous solution.

[0068] The content of the pH adjuster can be selected depending on the types and amounts of other components and the desired pH of the treatment liquid. For example, the content of the pH adjuster is preferably 0.0001 to 10% by mass, more preferably 0.001 to 8% by mass, and even more preferably 0.001 to 0.1% by mass, relative to the total mass of the treatment liquid.

[0069] <Organic Solvent> The treatment liquid of the present invention may contain an organic solvent. Examples of the organic solvent include known organic solvents, such as alcohol-based solvents, glycol-based solvents, glycol ether-based solvents, and ketone-based solvents. The organic solvent is preferably miscible with water at any ratio. Examples of the organic solvent that can be used include the compounds exemplified in paragraphs

[0135] to

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

[0070] <Preservatives> The treatment solution of the present invention may contain a preservative. The preservative is a compound different from the components contained in the treatment solution of the present invention described above. Examples of preservatives include benzoic acid, sodium benzoate, salicylic acid, propionic acid, isopropyl parahydroxybenzoate, isobutyl parahydroxybenzoate, ethyl parahydroxybenzoate, methyl parahydroxybenzoate, butyl parahydroxybenzoate, propyl parahydroxybenzoate, sodium sulfite, sodium hyposulfite, potassium metabisulfite, sorbic acid, potassium sorbate, sodium dehydroacetate, thujaplicin, Aralia udo extract, Styrax japonica extract, Artemisia capillaris extract, oolong tea extract, milt protein extract, enzymatically hydrolyzed Job's tears extract, tea catechins, apple polyphenols, pectin hydrolysates, chitosan, lysozyme, and ε-polylysine. Among these, benzoic acid, sorbic acid, salicylic acid, and propionic acid are preferred as preservatives.

[0071] The content of the preservative is preferably from 0.0001 to 10.0% by mass, more preferably from 0.0001 to 1.0% by mass, and even more preferably from 0.0001 to 0.1% by mass, based on the total mass of the treatment liquid.

[0072] <Reducing Agent> The treatment liquid of the present invention may contain a reducing agent. The reducing agent has a reducing action and reduces OH contained in the treatment liquid. － A reducing agent is a compound that has the function of reducing ions or dissolved oxygen, and is also called an oxygen scavenger. The reducing agent functions as an anticorrosive agent that improves the corrosion prevention performance of the treatment solution. The reducing agent used in the treatment solution is not particularly limited, and examples thereof include ascorbic acid compounds, catechol compounds, hydroxylamine compounds, hydrazide compounds, and reducing sulfur compounds. Specific examples of ascorbic acid compounds, catechol compounds, hydroxylamine compounds, hydrazide compounds, and reducing sulfur compounds include the compounds described in paragraphs

[0084] to

[0093] of WO 2021 / 131452, the contents of which are incorporated herein by reference.

[0073] <Dissolved Gas> The treatment solution of the present invention may contain a dissolved gas. By setting the concentration of the dissolved gas in the treatment solution within an appropriate range, it is possible to improve residue removability. The concentration of the dissolved gas is preferably 0.01 to 10 mg / L relative to the total volume of the treatment solution of the present invention. In terms of achieving a more excellent residue removal effect, the concentration of the dissolved gas is preferably 0.05 mg / L or more, and more preferably 0.1 mg / L or more, relative to the total volume of the treatment solution of the present invention. On the other hand, in terms of achieving a more excellent storage stability, the concentration is preferably 7 mg / L or less, more preferably 4 mg / L or less, and even more preferably 1.5 mg / L or less, relative to the total volume of the treatment solution of the present invention.

[0074] The dissolved gas is not particularly limited, but is preferably clean air. In this specification, "clean air" refers to air of Class 8 or lower (Class 8 or lower) in ISO standard ISO 14644-1:2015. The concentration of dissolved gas in the treatment liquid is determined by the following criteria: oxygen gas (O ２ gas), nitrogen gas (N ２ gas), and carbon dioxide gas (CO ２ The concentrations of oxygen gas, nitrogen gas, and carbon dioxide gas can be measured using the processing method described in paragraph

[0020] of WO 2020 / 194978, the contents of which are incorporated herein by reference.

[0075] The concentration of dissolved gas can be controlled by known methods. For example, the methods described in paragraphs

[0019] ,

[0052] to

[0056] , and

[0060] to

[0062] of WO 2020 / 194978 can be referred to, and the contents of these can be incorporated herein.

[0076] <Abrasive Particles> The treatment liquid preferably does not substantially contain abrasive particles. Abrasive particles refer to particles contained in the polishing liquid used in the polishing process of semiconductor substrates, and have an average primary particle diameter of 5 nm or more. Examples of the abrasive particles include inorganic solids such as silica (including colloidal silica and fumed silica), alumina, zirconia, ceria, titania, germania, manganese oxide, and silicon carbide; and organic solids such as polystyrene, polyacrylic resin, and polyvinyl chloride. "Substantially free of abrasive particles" means that the content of abrasive particles is less than 0.1% by mass, preferably 0.01% by mass or less, and more preferably 0.001% by mass or less, based on the total mass of the treatment liquid. The lower limit is not particularly limited and is 0% by mass. The content of abrasive particles can be measured using a commercially available measuring device that uses a laser light source for light scattering liquid particle measurement. The average primary particle diameter of particles such as abrasive particles is determined by measuring the particle diameters (circle-equivalent diameters) of 1,000 randomly selected primary particles from an image acquired using a transmission electron microscope TEM2010 (accelerating voltage 200 kV) manufactured by JEOL Ltd., and then calculating the arithmetic mean of the particle diameters. The circle-equivalent diameter is the diameter of a perfect circle having the same projected area as the projected area of ​​the particle observed. Examples of methods for removing abrasive particles from the treatment solution include purification processes such as filtering.

[0077] [Physical Properties of Treatment Solution] <pH> The pH of the treatment solution is not particularly limited as long as it is 0.1 to 7.0, but is preferably 0.1 to 6.0, and more preferably 1.0 to 4.0. When the treatment solution of the present invention is applied to an object having a copper surface that has been subjected to chemical mechanical polishing, the pH of the treatment solution is preferably within the above range. When the treatment solution of the present invention is applied to an object having a tungsten surface that has been subjected to chemical mechanical polishing, the pH of the treatment solution is preferably 3.0 to 7.0, and more preferably 5.0 to 7.0. The pH of the treatment solution can be measured using a known pH meter according to a method in accordance with JIS Z8802-1984. The pH measurement temperature is 25°C.

[0078] <Metal Content> The content (measured as ion concentration) of metals (e.g., metal elements Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) contained as impurities in the treatment solution is preferably 5 mass ppm or less, more preferably 1 mass ppm or less. In particular, the content of sodium atoms in the treatment solution is preferably 1 mass ppm or less relative to the total mass of the treatment solution. Since it is expected that treatment solutions of even higher purity will be required in the manufacture of cutting-edge semiconductor devices, the content of the above metals is more preferably lower than 1 mass ppm, that is, more preferably on the order of ppb by mass or less, particularly preferably 100 mass ppb or less, and most preferably less than 10 mass ppb. The lower limit is preferably 0.

[0079] Examples of methods for reducing the metal content include purification treatments such as distillation and filtration using an ion exchange resin or a filter at the stage of raw materials used in producing the treatment liquid or at the stage after the production of the treatment liquid. Another method for reducing the metal content includes using a container that is less likely to leach out impurities, as described below, as a container for containing the raw materials or the produced treatment liquid. Another method includes lining the inner wall of a pipe with a fluororesin to prevent metal components from leaching out from the pipe during production of the treatment liquid.

[0080] <Insoluble Particles> The treatment liquid preferably contains substantially no insoluble particles. The term "insoluble particles" refers to particles of inorganic solids, organic solids, and the like that ultimately exist as particles without dissolving in the treatment liquid. The term "substantially free of insoluble particles" refers to a measurement composition obtained by diluting the treatment liquid 10,000 times with a solvent contained in the treatment liquid, and the number of particles with a particle size of 40 nm or more contained in 1 mL of the measurement composition is 40,000 or less. The number of particles contained in the measurement composition can be measured in the liquid phase using a commercially available particle counter. Commercially available particle counters include those manufactured by Rion and PMS. A representative example of the former is the KS-19F, and a representative example of the latter is the UltraChem 40. To measure larger coarse particles, devices such as the KS-42 series and the LiQuilaz II S series can be used. Examples of insoluble particles include particles of inorganic solids such as silica (including colloidal silica and fumed silica), alumina, zirconia, ceria, titania, germania, manganese oxide, and silicon carbide; and particles of organic solids such as polystyrene, polyacrylic resin, and polyvinyl chloride. Methods for removing insoluble particles from the treatment liquid include, for example, purification treatments such as filtering.

[0081] <Coarse Particles> The treatment liquid may contain coarse particles, but the content thereof is preferably low. Coarse particles refer to particles having a diameter (particle size) of 1 μm or more when the particle shape is considered to be a sphere. The coarse particles contained in the treatment liquid include particles such as dust, dirt, organic solids, and inorganic solids contained as impurities in the raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids brought in as contaminants during the preparation of the treatment liquid, and which ultimately exist as particles without dissolving in the treatment liquid.

[0082] The content of coarse particles in the treatment liquid is preferably 100 or less, more preferably 50 or less, particles with a particle size of 1 μm or more per mL of treatment liquid. The lower limit is preferably 0 or more, more preferably 0.01 or more, per mL of treatment liquid. The content of coarse particles present in the treatment liquid can be measured in the liquid phase using a commercially available measuring device that uses a laser as a light source for light scattering liquid particle measurement. Methods for removing coarse particles include, for example, purification processes such as filtering, which will be described later.

[0083] [Method for Producing Treatment Liquid] The treatment liquid can be produced by a known method, which will be described in detail below.

[0084] [Liquid Preparation Step] The treatment liquid can be produced, for example, by mixing the above-mentioned components. As a method for preparing the treatment liquid, for example, an anionic polymer, a phosphonic acid compound, a hydroxyl group-containing carboxylic acid, and optionally optional components are sequentially added to a container containing purified pure water, and then the mixture is stirred and mixed, and a pH adjuster is added as needed to adjust the pH of the mixture, thereby preparing the treatment liquid. When adding each component to a container, they may be added all at once, or may be added in portions over several times.

[0085] The stirring device and stirring method used to prepare the treatment solution may be a known device such as a stirrer or disperser. Examples of the stirrer include an industrial mixer, a portable stirrer, a mechanical stirrer, and a magnetic stirrer. Examples of the disperser include an industrial disperser, a homogenizer, an ultrasonic disperser, and a bead mill.

[0086] The mixing of the components in the preparation step of the treatment solution, the purification treatment described below, and storage of the produced treatment solution are preferably carried out at 40° C. or lower, more preferably at 30° C. or lower. The lower limit is preferably 5° C. or higher, more preferably 10° C. or higher. By preparing, treating, and / or storing the treatment solution within the above temperature range, the performance can be maintained stably for a long period of time.

[0087] <Purification> It is preferable to perform a purification treatment in advance on one or more of the raw materials used to prepare the treatment solution. Examples of purification treatment include known methods such as distillation, ion exchange, and filtration. The degree of purification is preferably such that the raw material has a purity of 99% by mass or more, and more preferably such that the raw solution has a purity of 99.9% by mass or more. The upper limit is preferably 99.9999% by mass or less.

[0088] Examples of purification methods include passing the raw material through an ion exchange resin or a reverse osmosis membrane (RO membrane), reprecipitation, distillation of the raw material, and filtering. A combination of the above purification methods may be used as the purification method. For example, the raw material may be subjected to primary purification by passing it through an RO membrane, and then subjected to secondary purification by passing it through a purification device consisting of a cation exchange resin, an anion exchange resin, or a mixed-bed ion exchange resin. Furthermore, the purification process may be performed multiple times.

[0089] The filter used for filtering is not particularly limited as long as it is one that has been conventionally used for filtering purposes. Examples include filters made of fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyallylsulfone (PAS), and polyolefin resins (including high-density or ultra-high molecular weight) such as polyethylene and polypropylene (PP). Among these materials, materials selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesins (including PTFE and PFA), and polyamide resins (including nylon) are preferred, and fluororesin filters are more preferred. Filtering raw materials using filters made of these materials can effectively remove highly polar foreign matter that is likely to cause defects.

[0090] <Container> The treatment liquid (including the diluted treatment liquid described below) can be filled into any container for storage, transport and use, as long as corrosiveness and other factors do not pose a problem.

[0091] As a container, a container with a high degree of cleanliness within the container for semiconductor applications and that suppresses the elution of impurities from the inner wall of the container's storage section into each liquid is preferred. Examples of such containers include various containers commercially available as containers for semiconductor processing liquids, such as the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited to these. In addition, the containers exemplified in paragraphs

[0121] to

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

[0092] The interior of these containers is preferably washed before filling with the treatment liquid. The liquid used for washing is preferably one that has a reduced amount of metal impurities. After production, the treatment liquid may be bottled in a container such as a gallon bottle or a coated bottle, and then transported and stored.

[0093] To prevent changes in the components of the treatment solution during storage, the container may be filled with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. A gas with a low water content is particularly preferred. The treatment solution may be transported and stored at room temperature, or the temperature may be controlled to a range of -20°C to 20°C to prevent deterioration.

[0094] <Clean Room> It is preferable that all of the manufacturing of the treatment liquid, handling including opening and cleaning of containers, filling of the treatment liquid, treatment analysis, and measurement are carried out in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferable that the clean room meets any of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably ISO Class 1 or ISO Class 2, and even more preferably ISO Class 1.

[0095] [Dilution Step] The treatment liquid may be subjected to a dilution step in which the concentrated solution is diluted with a diluent such as water, and then the diluted treatment liquid (diluted treatment liquid) may be used to treat an object. In other words, the treatment liquid may be diluted with a diluent containing water before use. Note that the concentrated solution and the diluted treatment liquid are also forms of the treatment liquid of the present invention as long as they satisfy the requirements of the present invention.

[0096] It is preferable to perform a purification treatment beforehand on the diluted solution used in the dilution step. It is also more preferable to perform a purification treatment on the diluted treated solution obtained by the dilution step. Examples of the purification treatment include the ion component reduction treatment using an ion exchange resin or an RO membrane, etc., and the removal of foreign matter using filtering, which are described as purification treatments for the treated solution above. It is preferable to perform either of these treatments.

[0097] The dilution ratio of the treatment liquid in the dilution step may be adjusted as appropriate depending on the type and content of each component and the object to be treated, but the ratio of the diluted treatment liquid to the treatment liquid before dilution (dilution factor) is preferably 10 to 10,000 times, more preferably 10 to 1,000 times, and even more preferably 10 to 300 times, in terms of mass ratio or volume ratio (volume ratio at 23° C.). Furthermore, in terms of superior residue removal properties, the diluted liquid preferably contains water, and more preferably is water.

[0098] The change in pH before and after dilution (the difference between the pH of the treatment liquid before dilution and the pH of the diluted treatment liquid) is preferably 2.0 or less, more preferably 1.8 or less, and even more preferably 1.5 or less. The pH of the treatment liquid before dilution and the pH of the diluted treatment liquid are each preferably in the preferred embodiment described above.

[0099] The specific method for the dilution step of diluting the treatment liquid may be similar to that used in the above-mentioned treatment liquid preparation step. The stirring device and stirring method used in the dilution step may also be similar to those used in the above-mentioned treatment liquid preparation step, using the known stirring device.

[0100] [Use of Treatment Liquid] The treatment liquid of the present invention is preferably used for cleaning an object that has been subjected to chemical mechanical polishing (CMP). As described above, when using the treatment liquid, the treatment liquid may be diluted.

[0101] <Subject> The subject of the treatment liquid includes, for example, a subject having a metal, such as a semiconductor substrate having a metal. When the semiconductor substrate has a metal, the metal may be present on the front and back surfaces, side surfaces, or in grooves of the semiconductor substrate. When the semiconductor substrate has a metal, the metal may be present not only on the surface of the semiconductor substrate, but also on the semiconductor substrate via another layer.

[0102] Examples of metals include at least one metal M selected from the group consisting of copper (Cu), cobalt (Co), ruthenium (Ru), aluminum (Al), tungsten (W), titanium (Ti), tantalum (Ta), chromium (Cr), hafnium (Hf), osmium (Os), platinum (Pt), nickel (Ni), manganese (Mn), iron (Fe), zirconium (Zr), molybdenum (Mo), palladium (Pd), lanthanum (La), and iridium (Ir). Cu, Co, or Ru is preferred, and Cu or Co is more preferred. In other words, the target object is preferably an object containing at least one metal selected from the group consisting of Cu and Co. The treatment solution of the present invention can be suitably used for cleaning the copper surface of the target object when the target object has a copper surface that has been subjected to chemical mechanical polishing.

[0103] The metal may be any substance containing a metal (metal atom), and examples thereof include a simple substance of the metal M and an alloy containing the metal M.

[0104] The object to be treated with the treatment liquid may include, for example, a semiconductor substrate, a metal wiring film, a barrier metal, and an insulating film.

[0105] Examples of wafers constituting semiconductor substrates include wafers made of silicon-based materials such as silicon (Si) wafers, silicon carbide (SiC) wafers, silicon-containing resin wafers (glass epoxy wafers), gallium nitride (GaN), gallium phosphide (GaP) wafers, gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers. Examples of silicon wafers include n-type silicon wafers doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb)), and p-type silicon wafers doped with trivalent atoms (e.g., boron (B) and gallium (Ga)). Examples of silicon in silicon wafers include amorphous silicon, single crystal silicon, polycrystalline silicon, and polysilicon. Among these, wafers made of silicon-based materials such as silicon wafers, silicon carbide wafers, and silicon-containing resin wafers (glass epoxy wafers) are preferred.

[0106] The insulating film may be, for example, a silicon oxide film (e.g., silicon dioxide (SiO ２ ) film and tetraethyl orthosilicate (Si(OC ２ H ５ ) ４ ) film (TEOS film), silicon nitride film (e.g., silicon nitride (Si ３ N ４ ) and silicon carbide nitride (SiNC), and low dielectric constant (Low-k) films (for example, carbon-doped silicon oxide (SiOC) films and silicon carbide (SiC) films), and low dielectric constant (Low-k) films are preferred.

[0107] The metal wiring film is preferably a copper-containing film, a cobalt-containing film, or a ruthenium-containing film. Examples of the copper-containing film include a wiring film made only of metallic copper (copper wiring film) and a wiring film made of an alloy of metallic copper and other metals (copper alloy wiring film). Examples of the copper alloy wiring film include a wiring film made of an alloy of copper and one or more metals selected from Al, Ti, Cr, Mn, Ta, and W. More specifically, examples include a copper-aluminum alloy wiring film (CuAl alloy wiring film), a copper-titanium alloy wiring film (CuTi alloy wiring film), a copper-chromium alloy wiring film (CuCr alloy wiring film), a copper-manganese alloy wiring film (CuMn alloy wiring film), a copper-tantalum alloy wiring film (CuTa alloy wiring film), and a copper-tungsten alloy wiring film (CuW alloy wiring film).

[0108] Examples of the cobalt-containing film include a metal film made only of metallic cobalt (cobalt metal film) and a metal film made of an alloy of metallic cobalt and other metals (cobalt alloy metal film). Examples of the cobalt alloy metal film include a metal film made of an alloy of cobalt and one or more metals selected from Ti, Cr, Fe, Ni, Mo, Pd, Ta, and W. More specifically, examples of the metal film include a cobalt-titanium alloy metal film (CoTi alloy metal film), a cobalt-chromium alloy metal film (CoCr alloy metal film), a cobalt-iron alloy metal film (CoFe alloy metal film), a cobalt-nickel alloy metal film (CoNi alloy metal film), a cobalt-molybdenum alloy metal film (CoMo alloy metal film), a cobalt-palladium alloy metal film (CoPd alloy metal film), a cobalt-tantalum alloy metal film (CoTa alloy metal film), and a cobalt-tungsten alloy metal film (CoW alloy metal film).

[0109] Examples of ruthenium-containing films include metal films made only of ruthenium metal (ruthenium metal films) and metal films made of alloys made of ruthenium metal and other metals (ruthenium alloy metal films).

[0110] The method for forming the insulating film, copper-containing film, cobalt-containing film, and ruthenium-containing film on the wafer constituting the semiconductor substrate is not particularly limited as long as it is a method commonly used in this field. For example, the insulating film forming method includes a method in which a silicon oxide film is formed on the wafer constituting the semiconductor substrate by heat treatment in the presence of oxygen gas, and then a silicon nitride film is formed by chemical vapor deposition (CVD) by injecting silane and ammonia gas. For example, the copper-containing film, cobalt-containing film, and ruthenium-containing film forming method includes a method in which a circuit is formed on the wafer having the insulating film by a known method such as resist, and then a copper-containing film, cobalt-containing film, and ruthenium-containing film are formed by plating and CVD.

[0111] <CMP Treatment> The object is an object that has been subjected to CMP treatment (preferably, an object having a metal that has been subjected to CMP treatment). CMP treatment is a treatment that flattens the surface of a semiconductor substrate having, for example, a metal wiring film, a barrier metal, and an insulating film, by a combined action of chemical action and mechanical polishing using a polishing slurry containing polishing particles (abrasive grains).

[0112] <Subject Subjected to Pad Cleaning Treatment> The surface of the subject may be subjected to a pad cleaning treatment after CMP treatment. Pad cleaning treatment is a treatment that uses a pad to reduce residues present on the surface of the treated area. Specifically, the surface of the subject that has been subjected to CMP treatment is brought into contact with a pad, and the subject and the pad are slid relative to each other while a pad cleaning composition is supplied to the contact area. As a result, residues on the surface of the subject are removed by the frictional force of the pad and the chemical action of the pad cleaning composition.

[0113] The pad is not particularly limited and can be appropriately selected depending on the type of object, the type of residue to be removed, and the device to be used. The pad may be a polishing pad used in CMP processing, or a buff pad such as a foam polyurethane buff pad, a nonwoven fabric buff pad, a suede buff pad, or a sponge buff pad. The pad cleaning process using a pad includes a process called buff cleaning or buff polishing.

[0114] As the pad cleaning composition, a known cleaning composition can be used depending on the type of object and the type and amount of residue to be removed. Examples of components contained in the pad cleaning composition include ammonium fluoride (NH ４ F), 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), a water-soluble polymer such as polyvinyl alcohol, a dispersion medium such as water, and an acid such as nitric acid. The pad cleaning composition does not contain abrasive particles.

[0115] The apparatus and conditions used in the pad cleaning treatment can be appropriately selected from known apparatus and conditions depending on the type of object and the type and amount of residue to be removed. For example, the treatment method described in paragraphs

[0085] to

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

[0116] In one embodiment of the pad cleaning treatment, a pad cleaning treatment is preferably performed on an object using the treatment liquid of the present invention as a pad cleaning composition. The treatment liquid used in the pad cleaning treatment may be a diluted treatment liquid.

[0117] The pad cleaning process may be performed only once or may be performed two or more times. For example, after the CMP process, a pad cleaning process using a polishing pad and a pad cleaning process using a buffing pad may be performed.

[0118] [Method for Treating an Object] The method for treating an object of the present invention is not particularly limited as long as it includes a step of contacting the object with the treatment liquid of the present invention (contact step). For example, the treatment method can be used to clean a semiconductor substrate that has been subjected to CMP treatment. The method for cleaning a semiconductor substrate preferably includes a step of applying the diluted treatment liquid obtained in the dilution step to a semiconductor substrate that has been subjected to CMP treatment to clean the substrate.

[0119] The method for contacting the object with the treatment liquid is not particularly limited, and examples include immersing the object in the treatment liquid contained in a tank, spraying the treatment liquid onto the object, pouring the treatment liquid onto the object, and combinations thereof. The above method may be appropriately selected depending on the purpose. Furthermore, the above method may appropriately adopt a method typically used in this field. For example, scrubbing, in which a cleaning member such as a brush is physically brought into contact with the surface of the object while supplying the treatment liquid to remove residue, or a spin (drop) method, in which the treatment liquid is dropped onto the rotating object, may be used. In the immersion method, ultrasonic treatment is preferably performed on the object immersed in the treatment liquid, as this can further reduce impurities remaining on the surface of the object.

[0120] In the contacting step, the object may be contacted with the treatment solution only once or may be contacted two or more times. When the object is contacted two or more times, the same method may be repeated or different methods may be combined.

[0121] The contacting step may be performed by either a single wafer method or a batch method. The single wafer method generally involves treating objects one by one, while the batch method generally involves treating multiple objects simultaneously.

[0122] The temperature of the treatment liquid is not particularly limited as long as it is a temperature that is normally used in this field. Generally, the treatment is performed at room temperature (about 25°C), but the temperature can be selected as desired to improve residue removal and suppress damage to components. For example, the temperature of the treatment liquid is preferably 10 to 60°C, and more preferably 15 to 50°C.

[0123] The contact time between the object and the treatment liquid can be changed as appropriate depending on the type and content of the components contained in the treatment liquid, etc. In practice, it is preferably 10 seconds to 2 minutes, more preferably 20 seconds to 1 minute 30 seconds, and even more preferably 30 seconds to 1 minute.

[0124] The amount (feed rate) of the treatment liquid supplied in the contact step is preferably 50 to 5,000 mL / min, more preferably 500 to 2,000 mL / min.

[0125] In the contact step, a mechanical stirring method may be used to further enhance the residue removal ability of the treatment liquid. Examples of the mechanical stirring method include a method of circulating the treatment liquid over the semiconductor substrate, a method of passing or spraying the treatment liquid over the semiconductor substrate, and a method of stirring the treatment liquid with ultrasonic waves or megasonics.

[0126] Furthermore, after the contacting step, a step of contacting the object with a rinse liquid (hereinafter also referred to as a "rinsing step") may be carried out. By carrying out the rinsing step, the object obtained in the contacting step can be washed with the rinse liquid, and residues can be efficiently removed. The rinsing step is preferably carried out consecutively after the cleaning step of the object, and is a step of rinsing the object with the rinse liquid. The rinsing step may be carried out using the mechanical stirring method described above.

[0127] Rinse solvents include, for example, water (preferably deionized (DI) water), methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Aqueous rinse solutions having a pH greater than 8.0 (such as dilute aqueous ammonium hydroxide) may also be utilized.

[0128] The method of contacting the object with the rinse liquid can be the same as the method of contacting the object with the treatment liquid described above. The contact time between the object and the rinse liquid can be appropriately changed depending on the type and content of each component contained in the treatment liquid, and the object and purpose of use of the treatment liquid. In practice, the contact time is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and even more preferably 30 to 60 seconds.

[0129] The rinsing step may be followed by a drying step for drying the object, such as a spin drying method, a method of passing a dry gas over the semiconductor substrate, a method of heating the substrate with a heating means such as a hot plate or an infrared lamp, a Marangoni drying method, a Rotagoni drying method, an IPA (isopropyl alcohol) drying method, or any combination thereof.

[0130] [Method for Manufacturing a Semiconductor Device] The above-described method for processing an object can be suitably applied to a method for manufacturing a semiconductor device. The above-described cleaning method may be performed in combination with other processes performed on a substrate, either before or after the other processes. The above-described cleaning method may be incorporated into other processes during its implementation, or the cleaning method may be incorporated into other processes. Examples of other processes include processes for forming structures such as metal wiring, gate structures, source structures, drain structures, insulating films, ferromagnetic layers, and non-magnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and modification), resist formation processes, exposure processes, removal processes, heat treatment processes, cleaning processes, and inspection processes.

[0131] The above processing method may be performed at any stage of a back end process (BEOL: Back end of the line), a middle process (MOL: Middle of the line), or a front end process (FEOL: Front end of the line), and is preferably performed in a front end process or a middle process.

[0132] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0133] In the following examples, the pH of the treatment solution was measured at 25°C using a pH meter (Horiba, Ltd., model "F-74") in accordance with JIS Z8802-1984. In addition, in producing the treatment solutions of the examples and comparative examples, handling of containers, preparation, filling, storage and analytical measurements of the treatment solutions were all carried out in a clean room meeting ISO class 2 or lower.

[0134] [Raw materials for treatment solution] The following compounds were used to produce the treatment solution. Note that all of the components used in the examples were classified as semiconductor grade or equivalent high purity grade.

[0135] [Hydroxyl-containing carboxylic acids] Citric acid Malic acid Tartaric acid

[0136] [Phosphonic acid compounds] HEDP NTMP EDTMP

[0137] [Anionic polymers] PA: Polyacrylic acid (Mw (weight average molecular weight): 6000) PB: Polystyrene sulfonic acid (Mw: 75000) PC: Polyvinyl sulfonic acid (Mw: 8000) PD: Poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (Mw: 6000) PE: 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer (Mw: 8500) PF: Polycarboxylic acid polyalkylene glycol graft compound (Mw: 3000, AQUALIC PM-303B, manufactured by Nippon Shokubai Co., Ltd.) PG: Polyvinyl phosphonic acid (Mw: 24000)

[0138] [Anionic surfactants] SA: Dodecylbenzenesulfonic acid SB: Naphthalenesulfonic acid formalin condensate (Mw: 2000) SC: C12-C14 alkyldiphenyletherdisulfonic acid SD: Laurylsulfonic acid SE: Trideceth-4 carboxylic acid

[0139] [Other ingredients] Oxalic acid

[0140] [pH adjuster, ultrapure water] As a pH adjuster, potassium hydroxide (KOH) and sulfuric acid (H ２SO ４ The contents of potassium hydroxide and sulfuric acid were 2 mass % or less relative to the total mass of each treatment solution. Ultrapure water (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used when preparing the treatment solutions.

[0141] [Production of Treatment Solution] Next, the production method of each treatment solution of the Examples and Comparative Examples will be described using Example 1 as an example. Citric acid, HEDP, PA, and SA were each added to ultrapure water so that the content of each component was the blending ratio shown in each table, and then a pH adjuster was added so that the pH of the mixed solution was 1.4. The content of ultrapure water is the remainder of the treatment solution, minus the content of each component used in preparing the treatment solution other than ultrapure water. The resulting mixed solution was thoroughly stirred to prepare the treatment solution of Example 1. Each treatment solution of the Examples and Comparative Examples, having the composition shown in the table below, was prepared according to the production method of the treatment solution of Example 1.

[0142] [Evaluation] Subsequently, the following evaluations were carried out using each of the treatment liquids of the Examples and Comparative Examples produced by the above-mentioned methods.

[0143] [Evaluation of Organic Residue Removability on Wafers Having a Copper (Cu) Film] The organic residue removability (number of defects) when cleaning a semiconductor substrate that had been subjected to chemical mechanical polishing was evaluated. Using a FREX300S-II (polishing apparatus, manufactured by Ebara Corporation), a wafer (12 inches in diameter) having a Cu film on its surface was polished using polishing liquid 1 as the polishing liquid under conditions of an in-plane average polishing pressure of 105 hPa, a polishing liquid supply rate of 200 mL / min, and a polishing time of 30 seconds. Next, the wafer subjected to the above polishing treatment was further polished using polishing liquid 2 as the polishing liquid under conditions of an in-plane average polishing pressure of 70 hPa, a polishing liquid supply rate of 200 mL / min, and a polishing time of 60 seconds. The resulting CMP-treated wafer was scrubbed for 1 minute using a 100-fold diluted sample (diluted with pure water) of the treatment liquid adjusted to room temperature (23°C), and then dried. The compositions of the polishing solutions 1 and 2 are as follows: Polishing Solution 1 (pH 7.0): Colloidal silica (PL3, manufactured by Fuso Chemical Co., Ltd.) 0.1 mass %; Glycine 1.0 mass %; 3-amino-1,2,4-triazole 0.2 mass %; Benzotriazole (BTA) 30 mass ppm; Hydrogen peroxide 1.0 mass %; pH adjuster (ammonia and nitric acid); Water; Balance Polishing Solution 2 (pH 10.5): Colloidal silica (PL3, manufactured by Fuso Chemical Co., Ltd.) 6.0 mass %; Citric acid 1.0 mass %; Alkyl alkoxylate surfactant 100 mass ppm; BTA 0.2 mass %; Hydrogen peroxide 1.0 mass %; pH adjuster (potassium hydroxide and nitric acid); Water; Balance

[0144] Next, using a defect detection device (Surfscan SP5 manufactured by KLA Corporation), the number of detected signal intensities corresponding to defects having a length of 0.036 μm or more (total number of defects) was counted on the polished surface of the obtained wafer. Subsequently, images of 100 random defects were observed using a SemVision G5 (manufactured by Applied Materials), and the number of organic residues in the 100 defects was counted to estimate the proportion of defects derived from organic matter. The number of organic residues was calculated by multiplying the "total number of defects" by the "proportion of organic matter," and evaluated based on the following evaluation criteria. A rating of A is most preferable, and a rating of C or higher is practically preferable.

[0145] (Evaluation Criteria) A: The number of organic residues per wafer is less than 20. B: The number of organic residues per wafer is 20 or more but less than 50. C: The number of organic residues per wafer is 50 or more but less than 100. D: The number of organic residues per wafer is 100 or more.

[0146] [Evaluation of Removability of Organic Residue on Wafer Having Tungsten (W) Film] The removability of organic residue on the wafer having a W film was evaluated in the same manner as in the evaluation method and evaluation criteria described in [Evaluation of Removability of Organic Residue on Wafer Having Copper (Cu) Film] above, except that the wafer (diameter 12 inches) having a Cu film on its surface was changed to a wafer (diameter 12 inches) having a W film on its surface and the pH of the polishing solutions 1 and 2 was changed to 4.0.

[0147] [Evaluation of Corrosion Inhibition Performance] 2 × 2 cm copper coupon wafers were prepared, and the corrosion inhibition performance of the treatment solution for Cu was evaluated using these. The wafers were immersed for 30 minutes at room temperature (25 ° C.) in each treatment solution and each treatment solution that had been left to stand at room temperature (25 ° C.) for 6 months. The film thickness of the resulting wafers was then measured, and the etching rate (Å / min) was calculated from the difference in film thickness before and after the immersion treatment. The lower the etching rate, the better the corrosion inhibition performance, and in practical terms, an etching rate of 1.0 Å / min or less is preferable.

[0148] [Results] Tables 1 and 2 show the composition of each treatment solution used in the examples and comparative examples, as well as the evaluation results of each treatment solution. Table 1 (continued) is a continuation of Table 1. The same applies to Table 2. For example, in Example 1, a treatment solution having a composition of 20% by mass of citric acid, 0.5% by mass of HEDP, 0.1% by mass of PA, and 0.07% by mass of SA, with a pH of 1.4 and 2.5 before and after dilution, respectively, was used. As a result of the evaluation, the organic residue removability was rated "A," and the copper etching rate immediately after preparation and after storage at room temperature for 6 months was 0.3 Å / min. In the table, the values ​​in the "Content (wt%)" column indicate the content (mass%) of each component relative to the total mass of the treatment solution. The values ​​in the "pH" column indicate the pH of each treatment solution prepared in the above [Production of Treatment Solution], and the values ​​in the "pH after Dilution" column indicate the pH of the diluted sample of each treatment solution used in the above [Evaluation of Organic Residue Removability]. The numerical values ​​in the "Ratio" column indicate the content ratio (mass ratio) of each component. The numerical value in the "Phosphonic Acid / Polymer" column indicates the mass ratio of the phosphonic acid compound content to the anionic polymer content. The numerical value in the "Carboxylic Acid / Polymer" column indicates the mass ratio of the hydroxyl group-containing carboxylic acid content to the anionic polymer content. The numerical value in the "Polymer / Total Solids" column indicates the mass ratio of the anionic polymer content to the total solids content of the treatment liquid.

[0149]

[0150]

[0151]

[0152]

[0153] The results in the table confirm that the treatment solution of the present invention, when applied to an object having a copper surface that has been subjected to chemical mechanical polishing, causes little copper corrosion and is excellent at removing organic residues from the copper surface. Furthermore, it was confirmed that the treatment solution of the present invention, when applied to an object having a tungsten surface that has been subjected to chemical mechanical polishing, also exhibits excellent removability of organic residues from the tungsten surface. Furthermore, a comparison of Examples 1 to 7 and the like confirmed that when the mass ratio of the hydroxyl group-containing carboxylic acid content to the anionic polymer content was 10 or more, the organic residue removal ability was superior, and when it was 100 or more, the organic residue removal ability was even superior. A comparison of Examples 1 to 4 and the like confirmed that when the mass ratio of the anionic polymer content to the total solids content of the treatment solution was 0.1 or less, the organic residue removal ability was superior, and when the mass ratio of the anionic polymer content to the total solids content of the treatment solution was 0.0001 or more, the organic residue removal ability was even superior and copper corrosion was reduced. Comparison of Examples 8 to 16 and the like confirmed that, when the anionic polymer did not have a repeating unit derived from an acrylamide-based monomer, even when a copper-containing object was treated with a treatment solution that had been stored at room temperature for six months, there was little change in the properties of the treatment solution over time and little corrosion of copper.

Claims

1. A treatment solution used in a semiconductor manufacturing process, comprising: an anionic polymer; a phosphonic acid compound; and a hydroxyl group-containing carboxylic acid, wherein the mass ratio of the content of the phosphonic acid compound to the content of the anionic polymer is 0.1 to 1000; and the pH is 0.1 to 7.

0.

2. The treatment solution according to claim 1, wherein the hydroxyl group-containing carboxylic acid is selected from the group consisting of citric acid, malic acid, tartaric acid, glycolic acid, lactic acid, tartronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ-hydroxybutyric acid, citramalic acid, isocitric acid, leucic acid, mevalonic acid, pantoic acid, ricinoleic acid, ricineraidic acid, cerebronic acid, quinic acid, shikimic acid, salicylic acid, creosote acid, vanillic acid, syringic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orselliic acid, gallic acid, mandelic acid, benzilic acid, atrolactic acid, mellitic acid, phloretic acid, coumaric acid, umbellic acid, caffeic acid, ferulic acid, and sinapic acid.

3. The treatment solution according to claim 1, wherein the phosphonic acid compound is selected from the group consisting of etidronic acid, nitrilotris(methylene phosphonic acid), ethylenediaminetetramethylene phosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid.

4. The treatment solution according to claim 1, wherein the anionic polymer is selected from the group consisting of polyacrylic acid, polystyrenesulfonic acid, polyvinylsulfonic acid, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, polyvinylphosphonic acid, poly(N-vinylacetamide), and styrenesulfonic acid-acrylic acid-vinylphosphonic acid copolymer.

5. The treatment liquid according to claim 1, wherein the anionic polymer does not have any repeating units derived from an acrylamide monomer.

6. The treatment liquid according to claim 1, wherein the mass ratio of the content of said hydroxyl group-containing carboxylic acid to the content of said anionic polymer is 10 or more.

7. The treatment liquid according to claim 1, wherein the mass ratio of the content of said hydroxyl group-containing carboxylic acid to the content of said anionic polymer is 100 or more.

8. The treatment liquid according to claim 1, wherein the mass ratio of the content of said anionic polymer to the total solid content of said treatment liquid is from 0.0001 to 0.

1.

9. The treatment liquid according to claim 1, further comprising an anionic surfactant selected from the group consisting of sulfonic acid surfactants, carboxylic acid surfactants, and phosphate ester surfactants.

10. The treatment liquid according to claim 9, wherein the anionic surfactant is a sulfonic acid surfactant having an alkyl chain with six or more carbon atoms.

11. The treatment liquid according to claim 1, which is used for cleaning an object that has been subjected to a chemical mechanical polishing process.

12. The treatment solution according to claim 11, wherein the object has a copper surface that has been subjected to a chemical mechanical polishing process and the treatment solution is used to clean the copper surface.

13. The treatment solution according to claim 1, which is diluted with a diluent containing water.

14. The processing solution according to claim 1, which does not contain a quaternary ammonium salt.

15. A method for treating an object, comprising a step of contacting the object which has been subjected to chemical mechanical polishing treatment with the treatment liquid according to any one of claims 1 to 14.

16. A method for manufacturing a semiconductor device, comprising the method for processing an object according to claim 15.

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