Producing method of polishing composition and producing method of composition for rinse

Abstract

To provide a producing method of a novel polishing composition capable of reducing coarse particles and also capable of suppressing generation of defects, and a producing method of a novel rinsing composition.SOLUTION: A method for producing a polishing composition, comprising: preparing an abrasive particle dispersion containing abrasive particles and water, and obtaining a first liquid by filtering the abrasive particle dispersion; preparing one or more chemical component-containing aqueous solutions containing chemical components and water, and either filtering the aqueous solution in the case of a single kind or filtering a mixture X containing one or more of the aqueous solutions to obtain a second liquid; mixing the first liquid and the second liquid to obtain a third liquid; and filtering the third liquid.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polishing composition and a method for producing a rinse composition. [Background technology]

[0002] In the manufacture of semiconductor devices, a chemical mechanical polishing (CMP) process is sometimes performed to planarize the surface of a substrate having a metal wiring film, a barrier metal, an insulating film, etc., using a polishing slurry containing abrasive particles (e.g., silica, alumina, etc.).

[0003] In recent years, semiconductor devices have become increasingly miniaturized due to the increasing integration density of integrated circuits, and the demands for higher surface quality have been increasing for semiconductor substrates and magnetic disks. Various polishing compositions for CMP have been proposed to improve surface quality. For example, Patent Document 1 provides a polishing composition that has been subjected to precision filtration using a filter such as a depth filter or pleated filter in order to efficiently and economically remove agglomerates of primary abrasive particles or coarse primary abrasive particles contained in the polishing composition. It is claimed that such a polishing composition reduces the surface roughness of the polished object after polishing and significantly reduces nanoscratches (e.g., Patent Document 1). In the examples of the same document, a polishing composition is prepared by filtering a colloidal silica slurry as an abrasive, followed by the addition of an acid component or the like to adjust the pH.

[0004] On the other hand, in the CMP process, metal components derived from the abrasive particles used in the CMP process, the polished metal wiring film, and / or the barrier metal tend to remain on the surface of the semiconductor substrate after polishing. Because these residues can short-circuit between wirings and affect the electrical properties of the semiconductor, a cleaning process is conventionally performed to remove these residues from the surface of the semiconductor substrate.

[0005] For example, Patent Document 2 provides a method for cleaning a semiconductor substrate, which includes a cleaning step of cleaning a semiconductor substrate that has been subjected to chemical mechanical polishing using a specific cleaning solution. This document discloses that the cleaning solution may contain coarse particles, but that the content of coarse particles is preferably low, and that a purification process such as filtering can be used as a method for removing the coarse particles. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-075975 [Patent Document 2] Patent No. 7340614 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the present inventors have found that conventional methods are insufficient for producing a polishing composition that reduces coarse particles, and for producing a rinse composition that reduces coarse particles. Furthermore, the presence of many defects on a semiconductor substrate can affect the characteristics of the semiconductor.

[0008] Therefore, an object of the present invention is to provide a method for producing a novel polishing composition and a novel method for producing a rinsing composition, which can reduce coarse particles and suppress the occurrence of defects. [Means for solving the problem]

[0009] One aspect of the present invention is a method for producing a polishing composition, comprising the steps of preparing an abrasive dispersion containing abrasive grains and water and filtering the abrasive dispersion to obtain a first liquid; preparing one or more chemical component-containing aqueous solutions containing chemical components and water, and filtering the solution if only one solution is used, or filtering a mixture X containing one or more of the chemical component-containing aqueous solutions, to obtain a second liquid; and mixing the first liquid and the second liquid to obtain a third liquid and filtering the third liquid.

[0010] One aspect of the present invention is a method for producing a rinse composition, comprising the steps of: preparing one or more water-soluble polymer-containing liquids containing a water-soluble polymer and water, and filtering the liquid if one type is used, or filtering a mixture Y thereof if two or more types are used, to obtain liquid A; preparing one or more chemical component-containing aqueous solutions containing a chemical component and water, and filtering the liquid if one type is used, or filtering a mixture Z containing one or more of the chemical component-containing aqueous solutions, to obtain liquid B; and mixing liquid A and liquid B to obtain liquid C, and filtering liquid C. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a novel method for producing a polishing composition and a novel method for producing a rinsing composition, which can reduce coarse particles and suppress the occurrence of defects. DETAILED DESCRIPTION OF THE INVENTION

[0012] In this specification, "X to Y" refers to the range of values ​​between X and Y, including the upper and lower limits of the preceding and following values. When multiple "X to Y" are used, such as "X1 to Y1" or "X2 to Y2," the disclosure of each value as an upper limit, the disclosure of each value as a lower limit, and combinations of these upper and lower limits are all disclosed (i.e., they constitute legitimate grounds for amendment). Specifically, amendments to X1 or greater, amendments to Y2 or less, amendments to X1 or less, amendments to Y2 or greater, amendments between X1 and X2, and amendments between X1 and Y2 must all be deemed legitimate. Unless otherwise specified, all operations and measurements of physical properties are performed at room temperature (20-25°C) and a relative humidity of 40-50% RH. The concentrations described herein may be concentrations at the point of use (POU) or concentrations before dilution to the POU concentration. The dilution ratio may be 2 to 10 times, or 2 to 5 times. Furthermore, when features or aspects of the present disclosure are described in terms of a Markush group, those skilled in the art will recognize that the present disclosure is thereby described in terms of any individual component or subgroup of components of the Markush group. Furthermore, all combinations of embodiments and descriptions disclosed herein should be understood to be disclosed in this application, and thus should be understood to be grounds for amendment. Furthermore, when the content or concentration of each component is described, it may refer to the total amount when two or more components are included.

[0013] <Method for producing polishing composition> One aspect of the present invention is a method for producing a polishing composition, comprising the steps of preparing an abrasive dispersion containing abrasive grains and water and filtering the abrasive dispersion to obtain a first liquid, preparing one or more chemical component-containing aqueous solutions containing chemical components and water, and filtering the solution if only one solution is used, or filtering a mixture X containing one or more of the chemical component-containing aqueous solutions to obtain a second liquid, and mixing the first and second liquids to obtain a third liquid and filtering the third liquid. This aspect provides a novel method for producing a polishing composition that can reduce coarse particles and suppress the occurrence of defects.

[0014] [Step of obtaining first liquid] The method includes preparing an abrasive dispersion containing abrasive grains and water, and filtering the abrasive dispersion to obtain a first liquid.

[0015] (abrasive dispersion liquid) The abrasive dispersion contains abrasive grains and water. The abrasive grains have the function of mechanically polishing an object to be polished. The abrasive grains are insoluble in water.

[0016] The abrasive grains may be inorganic particles, organic particles, or organic-inorganic composite particles. Specific examples of inorganic particles include particles made of metal oxides such as silica, alumina, ceria, and titania, silicon nitride particles, silicon carbide particles, and boron nitride particles. Specific examples of organic particles include polymethyl methacrylate (PMMA) particles. The abrasive grains may be used alone or in combination. Furthermore, the abrasive grains may be commercially available or synthetic. Among these abrasive grains, silica is preferred, and colloidal silica is particularly preferred. Therefore, according to one embodiment of the present invention, the abrasive grains contain silica. Furthermore, according to another embodiment of the present invention, the abrasive grains contain colloidal silica.

[0017] According to one embodiment of the present invention, 85% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or more of the particles constituting the abrasive grains are made of silica (particularly colloidal silica) (upper limit 100% by mass).

[0018] The shape of the abrasive grains is not particularly limited and may be spherical or non-spherical. Specific examples of non-spherical shapes include polygonal prisms such as triangular prisms and square prisms, cylinders, bale-shaped cylinders in which the center is more bulging than the ends, doughnut-shaped discs with a central hole, plate-shaped discs, cocoon-shaped discs with a central constriction, associative spheres in which multiple particles are integrated, confetti-shaped discs with multiple protrusions on the surface, and rugby ball-shaped discs, and are not particularly limited.

[0019] When colloidal silica is used as the abrasive grains, the surface of the colloidal silica may be surface-modified with a silane coupling agent or the like.

[0020] Examples of methods for surface-modifying colloidal silica with a silane coupling agent include the following immobilization methods. For example, the method described in "Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups," Chem. Commun. 246-247 (2003) can be used. Specifically, colloidal silica with sulfonic acid immobilized on its surface can be obtained by coupling a silane coupling agent containing a thiol group, such as 3-mercaptopropyltrimethoxysilane, to colloidal silica and then oxidizing the thiol group with hydrogen peroxide. Alternatively, the method described in "Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel," Chemistry Letters, 3, 228-229 (2000) can be used. Specifically, colloidal silica with carboxylic acid immobilized on its surface can be obtained by coupling a silane coupling agent containing a photoreactive 2-nitrobenzyl ester to colloidal silica and then irradiating the resulting mixture with light.

[0021] Although the above is a colloidal silica having an anionic group (anion-modified colloidal silica), colloidal silica having a cationic group (cation-modified colloidal silica) may also be used. Examples of colloidal silica having a cationic group include colloidal silica having an amino group fixed to its surface. Examples of methods for producing such colloidal silica having a cationic group include a method described in JP 2005-162533 A in which a silane coupling agent having an amino group, such as aminoethyltrimethoxysilane, aminopropyltrimethoxysilane, aminoethyltriethoxysilane, aminopropyltriethoxysilane, aminopropyldimethylethoxysilane, aminopropylmethyldiethoxysilane, or aminobutyltriethoxysilane, is fixed to the surface of colloidal silica. This method allows for the production of colloidal silica having an amino group fixed to its surface.

[0022] The size of the abrasive grains is not particularly limited. For example, the average primary particle diameter of the abrasive grains is 5 nm or more, 10 nm or more, or 15 nm or more. The average primary particle diameter of the abrasive grains is 120 nm or less, 80 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, or 19 nm or less. The average primary particle diameter of the abrasive grains can be calculated, for example, based on the specific surface area (SA) of the abrasive grains calculated by the BET method, assuming that the abrasive grains are spherical. In this specification, the average primary particle diameter of the abrasive grains is a value measured by the method described in the Examples.

[0023] The average secondary particle diameter of the abrasive grains may be, for example, 16 nm or more, 20 nm or more, or 24 nm or more. The average secondary particle diameter of the abrasive grains may be 250 nm or less, 200 nm or less, 150 nm or less, 100 nm or less, 50 nm or less, or 30 nm or less. The average secondary particle diameter of the abrasive grains can be measured, for example, by dynamic light scattering, such as laser diffraction scattering. In this specification, the average secondary particle diameter of the abrasive grains is measured by the method described in the Examples.

[0024] The average degree of association of the abrasive grains may be 5.0 or less, 4.0 or less, or 3.0 or less. As the average degree of association of the abrasive grains decreases, defects can be further reduced. The average degree of association of the abrasive grains may also be 1.0 or more, 1.5 or more, or 2.0 or more. This average degree of association is obtained by dividing the average secondary particle size of the abrasive grains by the average primary particle size. As the average degree of association of the abrasive grains increases, there is an advantageous effect of improving the polishing rate of the object to be polished with the polishing composition.

[0025] The upper limit of the aspect ratio of the abrasive grains is not particularly limited, but may be less than 2.0, 1.8 or less, or 1.5 or less. Within this range, defects on the surface of the object to be polished can be further reduced. The aspect ratio is the average value obtained by taking the smallest rectangle circumscribing the image of the abrasive grains using a scanning electron microscope and dividing the length of the long side of the rectangle by the length of the short side of the same rectangle, and can be determined using general image analysis software. The lower limit of the aspect ratio of the abrasive grains in the polishing composition is not particularly limited, but is preferably 1.0 or more.

[0026] In the particle size distribution of abrasive grains measured by laser diffraction scattering, the ratio of the particle diameter (D90) when the cumulative particle mass from the fine particle side reaches 90% of the total particle mass to the particle diameter (D10) when the cumulative particle mass from the fine particle side reaches 10% of the total particle mass of all particles is not particularly limited, but the lower limit of D90 / D10 can be 1.1 or more, 1.2 or more, 1.3 or more, 2.0 or more, or 2.5 or more. Furthermore, in the particle size distribution of abrasive grains measured by laser diffraction scattering, the ratio of the particle diameter (D90) when the cumulative particle mass from the fine particle side reaches 90% of the total particle mass to the particle diameter (D10) when the cumulative particle mass from the fine particle side reaches 10% of the total particle mass of all particles is not particularly limited, but the upper limit of D90 / D10 can be 5.0 or less, 4.5 or less, 4.0 or less, or 3.0 or less. Within these ranges, defects on the surface of the object to be polished can be further reduced.

[0027] The size of the abrasive grains (average primary particle diameter, average secondary particle diameter, aspect ratio, D90 / D10, etc.) can be appropriately controlled by selecting the manufacturing method of the abrasive grains, etc.

[0028] The content (concentration) of the abrasive grains is not particularly limited, but according to one embodiment of the present invention, it is 5% by mass or more, 10% by mass or more, or 15% by mass or more, based on the total mass of the abrasive grain dispersion. The content (concentration) of the abrasive grains is not particularly limited, but it is 40% by mass or less, 30% by mass or less, or 25% by mass or less, based on the total mass of the abrasive grain dispersion. When the polishing composition contains two or more types of abrasive grains, the content of the abrasive grains refers to the total amount of these.

[0029] (Filtering of abrasive dispersion liquid) The material of the filter for filtering the abrasive dispersion is not particularly limited, and examples thereof include resins such as polycarbonate, cellulose mixed ester, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer, polycarbonate, polyethersulfone, cellulose acetate, nitrocellulose, regenerated cellulose, polyamide, triacetyl cellulose, polypropylene, polyvinyl chloride (PVC), nylon, nylon 66, polysulfone, polyester, polypropylene / polyethylene, acrylic copolymer, polycarbonate, polylactic acid, polycaprolactone, polyglycolic acid, polydioxanone, polyhydroxybutyrate, polybutadiene, polyurethane, polystyrene (PS), polymethyl methacrylate, polycarbonate, glass, metal, etc. Among these, polypropylene is preferred from the standpoints of cost and high resistance to chemicals.

[0030] The pore size of the filter is not particularly limited, but is preferably 0.03 μm or more, 0.04 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.5 μm or more, 1.0 μm or more, 1.5 μm or more, 2.1 μm or more, 2.5 μm or more, or 2.8 μm or more. A pore size of 2.1 μm or more, 2.5 μm or more, or 2.8 μm or more is particularly preferred because it provides a high filtration rate. The pore size of the filter may also be 10.0 μm or less, 8.0 μm or less, 5.0 μm or less, 4.0 μm or less, or 3.0 μm or less. Within these upper limits, aggregates formed in the abrasive dispersion can be efficiently removed.

[0031] The filter form is not particularly limited, and filters having various structures, shapes, and functions can be appropriately used. Specific examples include pleated, depth, depth-pleated, membrane, and adsorption filters. The filter structure is not particularly limited, and may be a bag-type filter or a hollow cylindrical cartridge filter. The cartridge filter may be a gasket type or a ring type.

[0032] The diameter of the filter (for example, the diameter of a membrane filter) can be appropriately determined depending on the production scale.

[0033] The filtration method may be natural filtration under normal pressure, suction filtration, pressure filtration, or centrifugal filtration, but pressure filtration is preferred in view of productivity.

[0034] The filtering speed is preferably 100 to 300,000 ml / min (m), 100 to 10,000 ml / min (m), or 100 to 1,000 ml / min (m).

[0035] The filtering time is preferably 1 to 100 minutes, 3 to 50 minutes, or 5 to 30 minutes.

[0036] The filter used in this step may be a commercially available product, such as 43L-SLS-030-EF (manufactured by ROKI TECHNO CORPORATION).

[0037] In this way, the abrasive dispersion liquid is filtered to obtain the first liquid.

[0038] [Step of obtaining second liquid] The method includes preparing one or more chemical component-containing aqueous solutions containing the chemical component and water, and filtering the solution if only one solution is used, or filtering a mixture X containing the one or more chemical component-containing aqueous solutions to obtain the second liquid.

[0039] (Aqueous solution containing chemical components) The chemical component-containing aqueous solution contains a chemical component and water. The chemical component has the effect of chemically polishing the object to be polished. In this specification, the chemical component is a concept that excludes abrasive grains, water-soluble polymers, and non-aqueous additives that are liquid at 25°C. As such a chemical component, components commonly used in the art can be used without particular limitation.

[0040] One or more types of chemical component-containing aqueous solutions are prepared. If one type of chemical component-containing aqueous solution is prepared, the second liquid is obtained by filtering that one type of chemical component-containing aqueous solution. If a mixture X containing one or more chemical component-containing aqueous solutions is prepared, the second liquid is obtained by filtering that mixture X.

[0041] There are no limitations on the method for preparing mixture X, as long as it contains an aqueous solution containing one or more chemical components.

[0042] For example, mixture X may be prepared by mixing two or more aqueous solutions containing chemical components together.

[0043] Alternatively, mixture X may be prepared by first preparing an aqueous solution containing one kind of chemical component, and then mixing the aqueous solution containing the one kind of chemical component with at least one selected from the group consisting of a chemical component (not in the form of an aqueous solution), a water-soluble polymer, and a non-aqueous additive that is liquid at 25°C.

[0044] Alternatively, mixture X may be prepared by simply mixing a chemical component (not in the form of an aqueous solution), at least one selected from the group consisting of a chemical component (not in the form of an aqueous solution), a non-aqueous additive that is liquid at 25°C, and a water-soluble polymer, with water. In this case, one or more aqueous solutions containing the chemical component and water are also prepared at the same time as preparing mixture X.

[0045] According to one embodiment of the present invention, examples of the chemical component include organic acids, inorganic acids, organic acid salts, inorganic acid salts, sugars, basic compounds, etc. Examples of salts include alkali metal salts such as sodium and potassium, and ammonium salts.

[0046] Examples of organic acids include citric acid, maleic acid, malic acid, glycolic acid, succinic acid, itaconic acid, malonic acid, iminodiacetic acid, gluconic acid, lactic acid, mandelic acid, tartaric acid, formic acid, acetic acid, propionic acid, butyric acid, adipic acid, oxalic acid, valeric acid, enanthic acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, crotonic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, methacrylic acid, and glycerin. Organic carboxylic acids such as phthalic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tartronic acid, glyceric acid, hydroxybutyric acid, hydroxyacetic acid, hydroxybenzoic acid, salicylic acid, isocitric acid, methylenesuccinic acid, gallic acid, ascorbic acid, nitroacetic acid, oxaloacetic acid, chloroacetic acid, dichloroacetic acid, and trichloroacetic acid; glycine, alanine, glutamic acid, aspartic acid, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, phenylalanine, tryptophan, tyrosine, proline, and cysteine. Amino acids such as sucrine, glutamine, asparagine, lysine, and arginine; nicotinic acid; picric acid; picolinic acid; phytic acid; 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxil Examples of organic phosphonic acids include hydroxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, and aminopoly(methylenephosphonic acid); and organic sulfonic acids such as xylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, aminoethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, sulfosuccinic acid, 10-camphorsulfonic acid, isethionic acid, and taurine.

[0047] Examples of inorganic acids include phosphoric acid (orthophosphoric acid), nitric acid, sulfuric acid, hydrochloric acid, boric acid, sulfamic acid, phosphinic acid, phosphonic acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid, carbonic acid, hydrofluoric acid, sulfurous acid, thiosulfuric acid, chloric acid, perchloric acid, chlorous acid, hydroiodic acid, periodic acid, iodic acid, hydrobromic acid, perbromic acid, bromic acid, chromic acid, and nitrous acid.

[0048] Examples of sugars include tetroses such as erythrose, threose, and erythrulose; pentoses such as ribose, arabinose, xylose, lyxose, xylulose, and ribulose; monosaccharides such as hexoses such as allose, altrose, glucose, mannose, glucose, idose, galactose, talose, fructose, sorbose, psicose, and tagatose; and oligosaccharides such as maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, turanose, trehalose, saccharose, mannitrose, cellotriose, gentianose, raffinose, melezitose, cerotetrose, and stachyose. Other sugars may also be residues such as heptose, deoxysugars, aminosugars such as N-methyl-D-glucamine, thiosugars, selenosugars, aldonic acids, uronic acids, sugar acids, ketoaldonic acids, anhydrosugars, unsaturated sugars, sugar esters, sugar ethers, glycosides, etc.; polysaccharides such as starch, glycogen, cellulose, chitin, chitosan, etc.; or hydrolyzed versions of these.

[0049] Specific examples of basic compounds include alkali metal hydroxides or salts, quaternary ammonium hydroxides or salts, ammonia, amines, etc. Examples of alkali metals include potassium and sodium. Examples of salts include carbonates, bicarbonates, sulfates, acetates, etc. Examples of quaternary ammonium compounds include tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc. Examples of quaternary ammonium hydroxide compounds include quaternary ammonium hydroxides or salts thereof, specific examples of which include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. Examples of amines include 2-amino-2-ethyl-1,3-propanediol, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-(β-aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, anhydrous piperazine, piperazine hexahydrate, 1-(2-aminoethyl)piperazine, N-methylpiperazine, guanidine, etc. These basic compounds may be used singly or in combination of two or more.

[0050] According to one embodiment of the present invention, the chemical component is an alcohol (eg, methanol, ethanol).

[0051] According to one embodiment of the present invention, the concentration of the chemical component in the chemical component-containing aqueous solution may be 0.1 to 20% by mass, 0.2 to 15% by mass, or 0.5 to 12% by mass. When two or more chemical components are prepared, the concentrations of the chemical components in the chemical component-containing aqueous solution may be the same or at least some of the chemical components may be different.

[0052] According to one embodiment of the present invention, the chemical component used in preparing one or more of the chemical component-containing aqueous solutions is in a solid form at 25°C. The present inventors have found that when a chemical component-containing aqueous solution containing a chemical component in a solid form at 25°C and water is used to prepare a polishing composition, the desired effects of the present invention cannot be achieved even if the abrasive dispersion is filtered and / or filtered immediately before the final polishing composition is prepared (filtering the third liquid). The present inventors speculate that this is because the chemical component in a solid form at 25°C remains incompletely dissolved in the chemical component-containing aqueous solution. This is particularly evident when preparing mixture X. By filtering the chemical component-containing aqueous solution (particularly mixture X) in this manner, the desired effects of the present invention can be achieved more efficiently.

[0053] According to one embodiment of the present invention, when two or more types of aqueous solutions containing chemical components are prepared, one or more of them are filtered in advance before producing the mixture X. That is, according to one embodiment of the present invention, two or more types of aqueous solutions containing chemical components are prepared, and one or more of them are filtered in advance before mixing to obtain the mixture X. According to such an embodiment, higher quality can be obtained.

[0054] According to one embodiment of the present invention, the chemical components used in preparing one or more of the chemical component-containing aqueous solutions are in a liquid form at 25° C. According to another embodiment of the present invention, a chemical component in a liquid form at 25° C. is prepared, and the chemical component is mixed with the chemical component-containing aqueous solution without pre-filtering to obtain the mixture X. This embodiment has the effect of improving productivity while ensuring quality.

[0055] (Water-soluble polymer-containing liquid) The water-soluble polymer mainly functions to protect the object to be polished and as a wetting agent. Therefore, a water-soluble polymer may be added to a polishing composition. That is, a method for producing a polishing composition according to one embodiment of the present invention includes preparing at least one water-soluble polymer-containing liquid containing a water-soluble polymer and water, and using the prepared liquid to prepare a polishing composition. According to one embodiment of the present invention, at least one water-soluble polymer-containing liquid containing a water-soluble polymer and water is prepared, and the water-soluble polymer-containing liquid is further mixed with the chemical component-containing aqueous solution to obtain the mixture X.

[0056] In this specification, a water-soluble polymer is a polymer that is in a solid form (powder form) at 25°C and can be dissolved in water to become liquid. A water-soluble polymer-containing solution can be prepared by dissolving the water-soluble polymer in water. Here, "water-soluble" means that the solubility in water (25°C) is 1 g / 100 mL or more, and "polymer" refers to a (co)polymer having repeating units in its molecular structure and a weight-average molecular weight (Mw) of 1,000 or more. In this specification, the "weight-average molecular weight" can be the value of the weight-average molecular weight (polyethylene glycol equivalent) measured by gel permeation chromatography (GPC). The weight-average molecular weight can be measured using the following equipment and conditions: GPC equipment: Shimadzu Corporation Model: Prominence + ELSD detector (ELSD-LTII) Column: VP-ODS (Shimadzu Corporation) Mobile phase A:MeOH B: 1% aqueous solution of acetic acid Flow rate: 1mL / min Detector: ELSD temp. 40℃, Gain 8, N2GAS 350kPa Oven temperature: 40°C Injection volume: 40μL.

[0057] As described above, when there is only one type of chemical component-containing aqueous solution, it is sufficient to filter that solution or the mixture X containing the chemical component-containing aqueous solution, but when a water-soluble polymer-containing liquid is also used to prepare the mixture X and higher quality is desired, a step of filtering the water-soluble polymer-containing liquid beforehand is included to obtain the mixture X. One or more types of water-soluble polymer-containing liquid may be prepared.

[0058] The water-soluble polymer may contain at least one functional group selected from cationic, anionic, and nonionic groups in the molecule. Specific examples of water-soluble polymers include those containing hydroxyl, carboxyl, acyloxy, sulfo, quaternary ammonium, heterocyclic, vinyl, and polyoxyalkylene structures in the molecule. Suitable examples include nitrogen-containing polymers, polyvinyl alcohol (polyvinyl alcohol with a saponification degree of 70 mol% or higher), and cellulose derivatives. The term "cellulose derivative" refers to a water-soluble cellulose derivative in which at least one hydroxyl group of water-insoluble cellulose is substituted with a substituent. Here, cellulose is a linear polymer of multiple β-glucose molecules via glycosidic bonds, and the cellulose structural unit has hydroxyl groups at the C2, C3, and C6 positions. Because the hydroxyl groups form strong hydrogen bonds both intramolecularly and intermolecularly, cellulose is generally insoluble in water and organic solvents. However, by substituting at least a portion of the hydroxyl groups of cellulose with a substituent and breaking at least a portion of the hydrogen bonds, the cellulose derivative can be made water-soluble.

[0059] More specifically, examples of the polymer include cellulose derivatives, imine derivatives such as poly(N-acylalkyleneimine), polyvinyl alcohol, polyvinylpyrrolidone, copolymers containing polyvinylpyrrolidone as part of their structure, polyvinylcaprolactam, copolymers containing polyvinylcaprolactam as part of their structure, polyoxyethylene, polymers containing oxyalkylene units, polymers of these having multiple types of structures such as diblock, triblock, random, and alternating structures, and polyether-modified silicones.

[0060] Among them, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, or polymers containing oxyalkylene units are preferred from the viewpoint of their excellent hydrophilicity. Specific examples of cellulose derivatives include cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and carboxymethyl cellulose, as well as pullulan. Among cellulose derivatives, hydroxyethyl cellulose is preferred from the viewpoint of its high ability to impart wettability to the polished surface and its excellent cleaning properties.

[0061] In one embodiment of the present invention, the weight-average molecular weight of the water-soluble polymer may be 1,000 to 3,000,000, 2,000 to 2,000,000, or 3,000 to 1,500,000. When two or more water-soluble polymers are prepared, the weight-average molecular weights of the water-soluble polymers may be the same or at least some may be different.

[0062] According to one embodiment of the present invention, the concentration of the water-soluble polymer in the water-soluble polymer-containing solution may be 0.1 to 10% by mass, 0.2 to 5% by mass, or 0.5 to 2% by mass. When two or more water-soluble polymers are prepared, the concentrations of the water-soluble polymers may be the same or at least some may be different.

[0063] According to one embodiment of the present invention, the water-soluble polymer present in at least one of the water-soluble polymer-containing liquids has a radius of gyration of 10 nm or more, 50 nm or more, 80 nm or more, or 100 nm or more. According to one embodiment of the present invention, the water-soluble polymer present in at least one of the water-soluble polymer-containing liquids has a radius of gyration of 300 nm or less, 250 nm or less, 200 nm or less, or 180 nm or less. In this specification, the radius of gyration can be calculated using the measurement method described in the Examples. When two or more water-soluble polymers are prepared, the radii of gyration of the water-soluble polymers in the water-soluble polymer-containing liquids may be the same or at least partially different.

[0064] (Non-aqueous additive that is liquid at 25°C) In order to impart certain properties to the polishing composition, a non-aqueous additive that is liquid at 25° C. may be added. The non-aqueous additive that is liquid at 25° C. has an oxyalkylene unit and is in a liquid form at 25° C. even if it is not dissolved in water.

[0065] Examples of compounds containing oxyalkylene units include ethylene glycol, propylene glycol, polyethylene glycol (polyethylene oxide (PEO)), polypropylene glycol (propylene oxide (PO)), block copolymers of ethylene oxide (EO) and propylene oxide (PO), and random copolymers of EO and PO. The block copolymers of EO and PO may be diblock copolymers or triblock copolymers containing a polyethylene oxide (PEO) block and a polypropylene oxide (PPO) block. Examples of triblock copolymers include PEO-PPO-PEO triblock copolymers and PPO-PEO-PPO triblock copolymers. PEO-PPO-PEO triblock copolymers are generally preferred. In block or random copolymers of EO and PO, the molar ratio of EO to PO (EO / PO) constituting the copolymer is preferably greater than 1, more preferably 2 or greater, and even more preferably 3 or greater (e.g., 5 or greater), from the viewpoint of water solubility and the like. Two or more nonaqueous additives that are liquid at 25°C may be used in combination.

[0066] In one embodiment of the present invention, the weight average molecular weight of the nonaqueous additive that is liquid at 25°C is preferably 50 to 5,000, more preferably 120 to 2,000, and even more preferably 150 to 1,000.

[0067] According to one embodiment of the present invention, a non-aqueous additive liquid at 25°C is prepared and mixed with the chemical component-containing aqueous solution without prior filtering to obtain the mixture X. This embodiment has the effect of improving productivity while ensuring quality. That is, one of the features of the present invention is that a chemical component-containing aqueous solution (containing mixture X) is prepared by mixing a chemical component (particularly a chemical component in a solid form at 25°C) with water, and then filtering the resulting solution. However, non-aqueous additives that are liquid at 25°C (e.g., polyethylene glycol) are not filtered because there is no risk of bleeding of undissolved components. In this way, when producing a polishing composition, rather than randomly filtering all components, selective filtering based on a clear technical concept can provide a production method that can ensure both quality and productivity.

[0068] The mass ratio of each component for obtaining mixture X may vary depending on the properties of the desired polishing composition, but for example, when mixture X is prepared by mixing an aqueous solution of an organic carboxylic acid such as maleic acid, an aqueous solution of an organic sulfonic acid such as xylene sulfonic acid, an aqueous solution of an amino sugar such as N-methyl-D-glucamine, and a non-aqueous additive such as polyethylene glycol, the mixing mass ratios are preferably 2-25:2-25:35-55:15-35, or 10-20:10-20:35-50:20-30, respectively. The values ​​are selected so that the total is 100.

[0069] Furthermore, for example, when the mixture X is prepared by mixing an aqueous solution of an organic carboxylic acid such as maleic acid, a compound containing an oxyalkylene unit, and a powdered organic carboxylic acid (not in the form of an aqueous solution) (e.g., iminodiacetic acid), the mixing mass ratio is preferably 60-90:5-20:1-10, or 70-88:7-15:1-5, etc. The values ​​are selected so that the total is 100.

[0070] The material of the filter used to filter at least one of the chemical component-containing aqueous solution and mixture X is not particularly limited, and examples thereof include resins such as polycarbonate, cellulose mixed ester, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer, polycarbonate, polyethersulfone, cellulose acetate, nitrocellulose, regenerated cellulose, polyamide, triacetyl cellulose, polypropylene, polyvinyl chloride (PVC), nylon, nylon 66, polysulfone, polyester, polypropylene / polyethylene, acrylic copolymer, polycarbonate, polylactic acid, polycaprolactone, polyglycolic acid, polydioxanone, polyhydroxybutyrate, polybutadiene, polyurethane, polystyrene (PS), polymethyl methacrylate, and polycarbonate, as well as glass and metal. Among these, nylon and nylon 66 are preferred from the standpoints of cost and resistance to chemicals.

[0071] The pore size of the filter is not particularly limited, but is preferably 0.03 μm or more, 0.04 μm or more, 0.05 μm or more, or 0.1 μm or more. The pore size of the filter may be 10.0 μm or less, 8.0 μm or less, 5.0 μm or less, 4.0 μm or less, 3.0 μm or less, 2.5 μm or less, 2.1 μm or less, 1.5 μm or less, 1.2 μm or less, 0.9 μm or less, 0.7 μm or less, 0.5 μm or less, or 0.3 μm or less. In particular, a pore size of 0.7 μm or less, 0.5 μm or less, or 0.3 μm or less can efficiently remove aggregates that may form in at least one of the chemical component-containing aqueous solution and mixture X.

[0072] The filter form is not particularly limited, and filters having various structures, shapes, and functions can be appropriately used. Specific examples include pleated, depth, depth-pleated, membrane, and adsorption filters. The filter structure is not particularly limited, and may be a bag-type filter or a hollow cylindrical cartridge filter. The cartridge filter may be a gasket type or a ring type.

[0073] The filtration method may be natural filtration under normal pressure, suction filtration, pressure filtration, or centrifugal filtration, but pressure filtration is preferred in view of productivity.

[0074] The filtering speed is preferably 100 to 300,000 ml / min (m), 100 to 10,000 ml / min (m), or 100 to 1,000 ml / min (m).

[0075] The filtering time is preferably 1 to 100 minutes, 3 to 50 minutes, or 5 to 30 minutes.

[0076] In this step, a commercially available filter can also be used. Examples of commercially available filters that can be used in this step include Ultipleats (registered trademark) P-Nylon 66 and Ultipore (registered trademark) N66, both manufactured by Nippon Pall Co., Ltd.

[0077] In this way, the second liquid is obtained.

[0078] [Step of obtaining the third liquid and filtering the third liquid] The third liquid can be obtained by mixing the first and second liquids. In this case, water can be mixed in addition to the first and second liquids. In one embodiment of the present invention, the mixing mass ratio of the first liquid, the second liquid, and water may be, for example, 100-500:10-200:400-800, or 250-350:50-150:500-700, or 20-70:80-300:630-900, or 30-60:80-200:710-890, although this may vary depending on the properties of the polishing composition desired. These values ​​are selected so that the total is 1000. The mixing mass ratio of the first liquid, the second liquid, and water may be, for example, 20-80:50-300:620-930, or 30-60:80-300:700-890. The values ​​are chosen so that they add up to 1000.

[0079] The mixing method is not particularly limited, and the composition can be prepared using, for example, a well-known mixing device such as a propeller mixer, an ultrasonic disperser, a homomixer, etc. The polishing composition may be mixed simultaneously or in any order.

[0080] In this step, the polishing composition can be produced by filtering the third liquid.

[0081] In a preferred embodiment of the present invention, the third liquid is filtered by first filtering the abrasive dispersion as described above, followed by filtering similar to that performed on at least one of the chemical component-containing aqueous solution and mixture X. This embodiment allows the intended effects of the present invention to be efficiently achieved. Of course, the descriptions of filtering the abrasive dispersion and filtering the chemical component-containing aqueous solution and mixture X can also be applied to this step. It is preferable to use a lower filtration rate than that used in filtering at least one of the chemical component-containing aqueous solution and mixture X. According to one embodiment of the present invention, the ratio of the filtration rate (ml / min) used in filtering at least one of the chemical component-containing aqueous solution and mixture X to the filtration rate (ml / min) used in filtering at least one of the chemical component-containing aqueous solution and mixture X used in this step is preferably 0.1 to 10, or 0.5 to 5.

[0082] The polishing composition thus produced may have a number of coarse particles having a particle diameter of more than 0.15 μm per ml of the polishing composition of 1,000,000 or less, 8,000,000 or less, 5,000,000 or less, 2,000,000 or less, 1,500,000 or less, 1,000,000 or less, or 500,000 or less. The method for measuring coarse particles is the method described in the Examples.

[0083] The polishing composition of the present invention may be a one-component type or a multi-component type such as a two-component type. The polishing composition of the present invention may also be prepared by diluting the stock solution of the polishing composition, for example, 10 times or more, with a diluent such as water.

[0084] [Application of polishing composition] The polishing composition obtained as described above can be suitably used for polishing an object to be polished.The object to be polished is not particularly limited, but includes metals such as silicon, polysilicon, aluminum, nickel, tungsten, copper, tantalum, titanium, stainless steel, or semiconductor wafers, or alloys thereof; glassy materials such as quartz glass, aluminosilicate glass, and glassy carbon; ceramic materials such as alumina, silica, sapphire, silicon nitride, tantalum nitride, and titanium carbide; compound semiconductor wafer materials such as silicon carbide, gallium nitride, and gallium arsenide; and resin materials such as polyimide resin.In addition, the shape of the object to be polished is not particularly limited.For example, it can be suitably used for polishing an object to be polished that has a flat surface, such as a plate or polyhedron.

[0085] The object to be polished is polished using a polishing apparatus. As the polishing apparatus, a general polishing apparatus can be used, which is equipped with a holder for holding the object to be polished, a motor capable of changing the rotation speed, etc., and a polishing platen to which a polishing pad (polishing cloth) can be attached. As the polishing pad, general nonwoven fabric, polyurethane, porous fluororesin, etc. can be used without any particular restrictions. The polishing pad is preferably provided with grooves to allow the polishing composition to accumulate. Regarding the polishing conditions, for example, the rotation speed of the polishing platen is 10 rpm (0.17 s -1 ) or more 500rpm(8.3s -1 ) or less is preferable. The pressure (polishing pressure) applied to the object to be polished is preferably 0.5 psi (3.4 kPa) or more and 10 psi (68.9 kPa) or less. The method of supplying the polishing composition to the polishing pad is not particularly limited, and for example, a method of continuously supplying it using a pump or the like is used. There is no limit to the amount of supply, but it is preferable that the surface of the polishing pad is always covered with the polishing composition.

[0086] After polishing, the substrate is washed in running water, and then dried using a spin dryer or the like to remove any adhering water droplets, thereby obtaining a polished object.

[0087] According to one embodiment of the present invention, the number of defects (greater than 0.1 μm) on a polished object (e.g., polished polysilicon) is 250 or less, 200 or less, 170 or less, 150 or less, 130 or less, or 100 or less. In reality, the number is about 10 or more.

[0088] <Rinse composition> One aspect of the present invention is a method for producing a rinse composition, comprising the steps of preparing one or more water-soluble polymer-containing liquids containing a water-soluble polymer and water, and filtering the liquid if one type is used, or filtering a mixture Y if two or more types are used, to obtain Solution A; preparing one or more chemical component-containing aqueous solutions containing a chemical component and water, and filtering the liquid if one type is used, or filtering a mixture Z containing one or more of the chemical component-containing aqueous solutions, to obtain Solution B; and mixing Solution A and Solution B to obtain Solution C and filtering Solution C. This aspect also enables the production of a novel rinse composition that can reduce coarse particles and suppress the occurrence of defects.

[0089] [Process for obtaining solution A] One or more water-soluble polymer-containing liquids containing a water-soluble polymer and water are prepared, and if one liquid is prepared, the liquid is filtered. If two or more liquids are prepared, the mixture Y is filtered to obtain liquid A. The water-soluble polymer mainly functions to protect the polished object and to act as a wetting agent. In the above method for producing a polishing composition, the water-soluble polymer is an optional component, but is an essential component in the rinse composition. By using a rinse composition containing a water-soluble polymer as a post-CMP composition, it becomes easier to remove foreign matter from the surface of the polished object that has been polished by the polishing object.

[0090] In one embodiment of the present invention, the weight-average molecular weight of the water-soluble polymer may be 1,000 to 3,000,000, 2,000 to 2,000,000, or 3,000 to 1,500,000. When two or more water-soluble polymers are prepared, the weight-average molecular weights of the water-soluble polymers may be the same or at least some may be different.

[0091] According to one embodiment of the present invention, the concentration of the water-soluble polymer in the water-soluble polymer-containing solution may be 0.1 to 5 mass %, 0.3 to 3 mass %, or 0.5 to 2 mass %. When two or more water-soluble polymers are prepared, the concentrations of the water-soluble polymers in the water-soluble polymer-containing solution may be the same or at least some of them may be different.

[0092] According to one embodiment of the present invention, the water-soluble polymer present in at least one of the water-soluble polymer-containing solutions has a radius of gyration of 10 nm or more, 50 nm or more, 80 nm or more, or 100 nm or more. Thus, the present invention exhibits particularly remarkable effects when a significantly large water-soluble polymer is contained in the composition. According to one embodiment of the present invention, the water-soluble polymer present in at least one of the water-soluble polymer-containing solutions has a radius of gyration of 300 nm or less, 250 nm or less, 200 nm or less, or 180 nm or less. The radius of gyration can be calculated using the measurement method described in the Examples. When two or more water-soluble polymers are prepared, the radii of gyration of the water-soluble polymers in the water-soluble polymer-containing solution may be the same or at least partially different.

[0093] For other explanations about the "water-soluble polymer" and "water-soluble polymer-containing liquid" applied to the rinse composition, the explanations given in <Method for manufacturing a polishing composition> apply, except for the explanations given in this section.

[0094] In this process, one or more types of water-soluble polymer-containing liquids containing a water-soluble polymer and water are prepared, and if one type is used, the liquid is filtered. If two or more types are used, the mixture Y is filtered to obtain liquid A.

[0095] The material of the filter for filtering at least one of the water-soluble polymer-containing liquid and the mixture Y is not particularly limited, and examples thereof include resins such as polycarbonate, cellulose mixed esters, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer, polycarbonate, polyethersulfone, cellulose acetate, nitrocellulose, regenerated cellulose, polyamide, triacetyl cellulose, polypropylene, polyvinyl chloride (PVC), nylon, nylon 66, polysulfone, polyester, polypropylene / polyethylene, acrylic copolymer, polycarbonate, polylactic acid, polycaprolactone, polyglycolic acid, polydioxanone, polyhydroxybutyrate, polybutadiene, polyurethane, polystyrene (PS), polymethyl methacrylate, and polycarbonate, as well as glass and metal. Among these, nylon and nylon 66 are preferred from the standpoints of cost and resistance to chemicals.

[0096] The pore size of the filter is not particularly limited, but is preferably 0.03 μm or more, 0.04 μm or more, 0.05 μm or more, or 0.1 μm or more. The pore size of the filter may be 10.0 μm or less, 8.0 μm or less, 5.0 μm or less, 4.0 μm or less, 3.0 μm or less, 2.5 μm or less, 2.1 μm or less, 1.5 μm or less, 1.2 μm or less, 0.9 μm or less, 0.7 μm or less, 0.5 μm or less, or 0.3 μm or less. In particular, a pore size of 0.7 μm or less, 0.5 μm or less, or 0.3 μm or less can efficiently remove aggregates that may form in at least one of the water-soluble polymer-containing liquid and mixture Y.

[0097] The filter form is not particularly limited, and filters having various structures, shapes, and functions can be appropriately used. Specific examples include pleated, depth, depth-pleated, membrane, and adsorption filters. The filter structure is not particularly limited, and may be a bag-type filter or a hollow cylindrical cartridge filter. The cartridge filter may be a gasket type or a ring type.

[0098] The filtration method may be natural filtration under normal pressure, suction filtration, pressure filtration, or centrifugal filtration, but pressure filtration is preferred in view of productivity.

[0099] The filtering speed is preferably 30 to 100,000 ml / min (m), 50 to 50,000 ml / min (m), or 80 to 100,000 ml / min (m).

[0100] The filtering time is preferably 1 to 100 minutes, 3 to 50 minutes, or 5 to 30 minutes.

[0101] In this step, a commercially available filter can also be used. Examples of commercially available filters that can be used in this step include Ultipleats (registered trademark) P-Nylon 66 and Ultipore (registered trademark) N66, both manufactured by Nippon Pall Co., Ltd.

[0102] [Step for obtaining solution B] One or more kinds of chemical component-containing aqueous solutions containing the chemical component and water are prepared, and if only one kind is prepared, the solution is filtered, or a mixture Z containing one or more of the chemical component-containing aqueous solutions is filtered to obtain liquid B.

[0103] (Aqueous solution containing chemical components) The chemical component-containing aqueous solution contains a chemical component and water. The chemical component may have the effect of treating the surface of the polished object and suppressing the occurrence of defects. In this specification, the chemical component is a concept that excludes abrasive grains, water-soluble polymers, and non-aqueous additives that are liquid at 25°C. As such a chemical component, components commonly used in the art may be used without particular limitation.

[0104] There are no limitations on the method for preparing mixture Z, as long as it contains an aqueous solution containing one or more chemical components.

[0105] For example, mixture Z may be prepared by mixing two or more aqueous solutions containing chemical components together.

[0106] Alternatively, mixture Z may be prepared by first preparing an aqueous solution containing one type of chemical component, and then mixing the aqueous solution containing the one type of chemical component with at least one selected from the group consisting of chemical components (not in the form of an aqueous solution) and non-aqueous additives that are liquid at 25°C.

[0107] Alternatively, mixture Z may be prepared by simply mixing a chemical component (not in the form of an aqueous solution), at least one selected from the group consisting of a chemical component (not in the form of an aqueous solution) and a non-aqueous additive that is liquid at 25°C, and water. In this case, at the same time as preparing mixture Z, one or more aqueous solutions containing the chemical component and water are also prepared.

[0108] The mass ratio of each component for obtaining mixture Z may vary depending on the desired properties of the rinse composition. For example, when mixing an organic carboxylic acid such as iminodiacetic acid with an amine such as 2-amino-2-ethyl-1,3-propanediol, the mixing mass ratio is preferably 26-46:54-74, or 30-40:60-70. These values ​​are selected so that the total is 100. According to one embodiment of the present invention, the total mass of the chemical components in mixture Z is preferably 3-15% by mass, or 5-10% by mass.

[0109] According to one embodiment of the present invention, the chemical component used in preparing one or more of the chemical component-containing aqueous solutions is in a solid form at 25°C. The present inventors have found that when a chemical component-containing aqueous solution containing a chemical component in a solid form at 25°C and water is used to prepare a rinse composition, the desired effects of the present invention cannot be achieved even if the solution is filtered immediately before being used as the final rinse composition (filtering liquid C). The present inventors speculate that this is because the chemical component in a solid form at 25°C remains incompletely dissolved in the chemical component-containing aqueous solution. This is particularly evident when preparing mixture Z. By filtering the chemical component-containing aqueous solution (particularly mixture Z) in this manner, the desired effects of the present invention can be achieved more efficiently.

[0110] According to one embodiment of the present invention, the chemical components used in preparing one or more of the chemical component-containing aqueous solutions are in a liquid form at 25° C. According to another embodiment of the present invention, a chemical component in a liquid form at 25° C. is prepared, and the chemical component is mixed with the chemical component-containing aqueous solution without pre-filtering to obtain the mixture Z. This embodiment has the effect of improving productivity while ensuring quality.

[0111] According to one embodiment of the present invention, the concentration of the chemical component in the chemical component-containing aqueous solution may be 0.1 to 20% by mass, 0.2 to 15% by mass, or 0.5 to 12% by mass. When two or more types of chemical component-containing aqueous solutions are prepared, the concentrations of the chemical components in the respective chemical component-containing aqueous solutions may be the same or at least partially different.

[0112] With respect to the "chemical component-containing aqueous solution" to be mixed into the rinse composition, the explanation given in <Method for producing polishing composition> is applicable except for the explanation given in this section.

[0113] (Non-aqueous additive that is liquid at 25°C) Non-aqueous additives that are liquid at 25°C may also be added to rinse compositions in order to impart certain properties to the compositions.

[0114] According to one embodiment of the present invention, a nonaqueous additive in a liquid state at 25°C is prepared, and the nonaqueous additive is mixed with the chemical component-containing aqueous solution without prior filtering to obtain the mixture Z. This embodiment has the effect of improving productivity while ensuring quality. In this way, when producing a rinse composition, rather than randomly filtering all components, the components to be filtered are selected based on a clear technical concept, thereby providing a production method that can ensure both quality and productivity.

[0115] In one embodiment of the present invention, the weight average molecular weight of the nonaqueous additive that is liquid at 25°C is preferably 50 to 5,000, more preferably 120 to 2,000, and even more preferably 150 to 1,000.

[0116] With respect to the "non-aqueous additive that is liquid at 25°C" that is mixed into the rinse composition, the explanation given in <Method for manufacturing polishing composition> is applicable, except for the explanation given in this section.

[0117] The explanation for filtering at least one of the chemical component-containing aqueous solution and mixture Z is the same as the explanation for filtering at least one of the water-soluble polymer-containing liquid and mixture Y. However, the filtration rate for filtering at least one of the chemical component-containing aqueous solution and mixture Z is preferably faster than the filtration rate employed for filtering at least one of the water-soluble polymer-containing liquid and mixture Y. According to one embodiment of the present invention, the filtration rate for filtering at least one of the chemical component-containing aqueous solution and mixture Z is preferably 100 to 300,000 ml / min (m), 100 to 100,000 ml / min (m), or 100 to 10,000 ml / min (m).

[0118] [Step of obtaining solution C and filtering the solution C] Liquid C can be obtained by mixing Liquid A and Liquid B. In this case, water can be mixed in addition to Liquid A and Liquid B. In one embodiment of the present invention, the mixing mass ratio of Liquid A, Liquid B, and water is preferably, for example, 1-20:50-200:800-920, or 5-15:70-150:800-900, although this may vary depending on the properties of the desired polishing composition. The values ​​are selected so that the total is 1,000. The mixing method is not particularly limited, and the mixture can be prepared using, for example, a well-known mixing device such as a propeller agitator, an ultrasonic disperser, a homomixer, etc. The components of the rinse composition may be mixed simultaneously or in any order.

[0119] In this step, a rinse composition can be produced by filtering Liquid C. The explanation for filtering Liquid C is the same as that for filtering at least one of the water-soluble polymer-containing liquid and mixture Y. However, the filtration rate for filtering Liquid C is preferably faster than the rate used for filtering at least one of the water-soluble polymer-containing liquid and mixture Y, and is preferably slower than the filtration rate for filtering at least one of the chemical component-containing aqueous solution and mixture Z. According to one embodiment of the present invention, the filtration rate for filtering Liquid C is preferably 100 to 300,000 ml / min (m), 100 to 100,000 ml / min (m), or 100 to 10,000 ml / min (m).

[0120] The rinse composition produced in this manner may have a number of coarse particles having a particle diameter of more than 0.15 μm per ml of the rinse composition of not more than 1,200,000, not more than 1,000,000, not more than 800,000, or not more than 600,000. The method for measuring coarse particles is the method described in the Examples.

[0121] In one embodiment of the present invention, the rinsing composition contains less than 0.1% by weight, less than 0.01% by weight, or less than 0.001% by weight. In one embodiment of the present invention, the rinsing composition is substantially free of abrasive grains. By "substantially free of abrasive grains," we mean that the rinsing composition contains no abrasive grains, or if it contains abrasive grains, the concentration is less than 0.0001% by weight. In one embodiment of the present invention, the rinsing composition does not contain abrasive grains.

[0122] The rinse composition of the present invention may be a one-component type or a multi-component type such as a two-component type. The polishing composition of the present invention may also be prepared by diluting the stock solution of the rinse composition with a diluent such as water, for example, 10 times or more.

[0123] [Application of rinse composition] The rinse composition of the present invention is preferably used in a rinse treatment for removing foreign matter that may be present on the surface of a polished object obtained by polishing the object with the polishing composition. The description of such an object to be polished is the same as that given in <Method for producing a polishing composition>.

[0124] The polishing composition may or may not be one obtained by the method for producing a polishing composition of the present invention. The latter polishing composition will be described below.

[0125] As the polishing composition, a general one can be used without any limitation.

[0126] According to one embodiment of the present invention, the polishing composition contains abrasive grains and water, and may optionally contain at least one selected from the group consisting of chemical components, water-soluble polymers, and non-aqueous additives that are liquid at 25°C.

[0127] According to one embodiment of the present invention, the content (concentration) of the abrasive grains in the polishing composition is, for example, 0.1 to 20 mass%, 0.3 to 15 mass%, or 0.5 to 10 mass%. When the polishing composition contains two or more types of abrasive grains, the content of the abrasive grains refers to the total amount of these. According to one embodiment of the present invention, the content (concentration) of the chemical component in the polishing composition is, for example, 0.1 to 10 mass%, 0.3 to 0.5 mass%, or 0.5 to 3 mass%. When the polishing composition contains two or more types of chemical components, the content of the chemical components refers to the total amount of these. According to one embodiment of the present invention, the content (concentration) of the water-soluble polymer in the polishing composition is, for example, 0.0001 to 10 mass%, 0.001 to 5 mass%, or 0.01 to 1 mass%. When the polishing composition contains two or more types of water-soluble polymers, the content of the water-soluble polymers refers to the total amount of these. According to one embodiment of the present invention, the content (concentration) of the nonaqueous additive that is liquid at 25° C. in the polishing composition is, for example, 0.0001 to 3 mass%, 0.001 to 1 mass%, or 0.01 to 0.5 mass%. When the polishing composition contains two or more nonaqueous additives, the content of the nonaqueous additives that are liquid at 25° C. refers to the total amount thereof.

[0128] The abrasive grains may be inorganic particles, organic particles, or organic-inorganic composite particles. Specific examples of inorganic particles include particles made of metal oxides such as silica, alumina, ceria, and titania, silicon nitride particles, silicon carbide particles, and boron nitride particles. Specific examples of organic particles include polymethyl methacrylate (PMMA) particles. The abrasive grains may be used alone or in combination. Furthermore, the abrasive grains may be commercially available or synthetic. Among these abrasive grains, silica is preferred, and colloidal silica is particularly preferred.

[0129] According to one embodiment of the present invention, 85% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or more of the particles constituting the abrasive grains are made of silica (particularly colloidal silica) (upper limit 100% by mass).

[0130] The shape of the abrasive grains is not particularly limited and may be spherical or non-spherical. Specific examples of non-spherical shapes include polygonal prisms such as triangular prisms and square prisms, cylinders, bale-shaped cylinders in which the center is more bulging than the ends, doughnut-shaped discs with a central hole, plate-shaped discs, cocoon-shaped discs with a central constriction, associative spheres in which multiple particles are integrated, confetti-shaped discs with multiple protrusions on the surface, and rugby ball-shaped discs, and are not particularly limited.

[0131] When colloidal silica is used as the abrasive grains, the surface of the colloidal silica may be surface-modified with a silane coupling agent or the like.

[0132] Examples of methods for surface-modifying colloidal silica with a silane coupling agent include the following immobilization methods. For example, the method described in "Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups," Chem. Commun. 246-247 (2003) can be used. Specifically, colloidal silica with sulfonic acid immobilized on its surface can be obtained by coupling a silane coupling agent containing a thiol group, such as 3-mercaptopropyltrimethoxysilane, to colloidal silica and then oxidizing the thiol group with hydrogen peroxide. Alternatively, the method described in "Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel," Chemistry Letters, 3, 228-229 (2000) can be used. Specifically, colloidal silica with carboxylic acid immobilized on its surface can be obtained by coupling a silane coupling agent containing a photoreactive 2-nitrobenzyl ester to colloidal silica and then irradiating the resulting mixture with light.

[0133] Although the above is a colloidal silica having an anionic group (anion-modified colloidal silica), colloidal silica having a cationic group (cation-modified colloidal silica) may also be used. Examples of colloidal silica having a cationic group include colloidal silica having an amino group fixed to its surface. Examples of methods for producing such colloidal silica having a cationic group include a method described in JP 2005-162533 A in which a silane coupling agent having an amino group, such as aminoethyltrimethoxysilane, aminopropyltrimethoxysilane, aminoethyltriethoxysilane, aminopropyltriethoxysilane, aminopropyldimethylethoxysilane, aminopropylmethyldiethoxysilane, or aminobutyltriethoxysilane, is fixed to the surface of colloidal silica. This method allows for the production of colloidal silica having an amino group fixed to its surface.

[0134] The size of the abrasive grains is not particularly limited. For example, the average primary particle diameter of the abrasive grains is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 15 nm or more. The average primary particle diameter of the abrasive grains is preferably 120 nm or less, more preferably 80 nm or less, and even more preferably 50 nm or less. That is, the average primary particle diameter of the abrasive grains is preferably 5 nm or more and 120 nm or less, more preferably 10 nm or more and 80 nm or less, and even more preferably 15 nm or more and 50 nm or less. The average primary particle diameter of the abrasive grains can be calculated, for example, based on the specific surface area (SA) of the abrasive grains calculated by the BET method, assuming that the abrasive grains are spherical. In this specification, the average primary particle diameter of the abrasive grains is the value measured by the method described in the Examples.

[0135] The average secondary particle diameter of the abrasive grains is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The average secondary particle diameter of the abrasive grains is preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. That is, the average secondary particle diameter of the abrasive grains is preferably 30 nm or more and 250 nm or less, more preferably 40 nm or more and 200 nm or less, and even more preferably 50 nm or more and 150 nm or less. The average secondary particle diameter of the abrasive grains can be measured, for example, by dynamic light scattering, typified by laser diffraction scattering. In this specification, the average secondary particle diameter of the abrasive grains is the value measured by the method described in the Examples.

[0136] The average degree of association of the abrasive grains is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. As the average degree of association of the abrasive grains decreases, defects can be further reduced. The average degree of association of the abrasive grains is also preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 2.0 or more. This average degree of association is obtained by dividing the average secondary particle diameter of the abrasive grains by the average primary particle diameter. As the average degree of association of the abrasive grains increases, there is an advantageous effect of improving the polishing rate of the object to be polished with the polishing composition.

[0137] The upper limit of the aspect ratio of the abrasive grains is not particularly limited, but is preferably less than 2.0, more preferably 1.8 or less, and even more preferably 1.5 or less.Within this range, defects on the surface of the object to be polished can be further reduced.The aspect ratio is the average value obtained by taking the smallest rectangle that circumscribes the image of the abrasive grains using a scanning electron microscope, and dividing the length of the long side of the rectangle by the length of the short side of the same rectangle, and can be determined using general image analysis software.The lower limit of the aspect ratio of the abrasive grains in the polishing composition is not particularly limited, but is preferably 1.0 or more.

[0138] In the particle size distribution of abrasive grains determined by laser diffraction scattering, the ratio of the particle diameter (D90) when the cumulative particle mass from the fine particle side reaches 90% of the total particle mass to the particle diameter (D10) when the cumulative particle mass from the fine particle side reaches 10% of the total particle mass of all particles is not particularly limited, but the lower limit of D90 / D10 is preferably 1.1 or more, more preferably 1.2 or more, and even more preferably 1.3 or more. In addition, in the particle size distribution of abrasive grains determined by laser diffraction scattering, the ratio of the particle diameter (D90) when the cumulative particle mass from the fine particle side reaches 90% of the total particle mass to the particle diameter (D10) when the cumulative particle mass from the fine particle side reaches 10% of the total particle mass of all particles is not particularly limited, but the upper limit of D90 / D10 is preferably 2.0 or less. Within this range, defects on the surface of the object to be polished can be further reduced.

[0139] The size of the abrasive grains (average primary particle diameter, average secondary particle diameter, aspect ratio, D90 / D10, etc.) can be appropriately controlled by selecting the manufacturing method of the abrasive grains, etc.

[0140] The chemical component has the function of chemically polishing the object to be polished. In this specification, the chemical component is a concept excluding abrasive grains, water-soluble polymers, and non-aqueous additives that are liquid at 25°C. As such chemical components, components commonly used in the art may be used without particular limitation. One or more types of chemical component-containing aqueous solutions may be prepared.

[0141] According to one embodiment of the present invention, the chemical component may be an organic acid, an inorganic acid, an organic acid salt, an inorganic acid salt, a sugar, etc. Examples of the salt include alkali metal salts such as sodium and potassium, and ammonium salts.

[0142] Examples of organic acids include citric acid, maleic acid, malic acid, glycolic acid, succinic acid, itaconic acid, malonic acid, iminodiacetic acid, gluconic acid, lactic acid, mandelic acid, tartaric acid, formic acid, acetic acid, propionic acid, butyric acid, adipic acid, oxalic acid, valeric acid, enanthic acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, crotonic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, methacrylic acid, and glycerin. Organic carboxylic acids such as phthalic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tartronic acid, glyceric acid, hydroxybutyric acid, hydroxyacetic acid, hydroxybenzoic acid, salicylic acid, isocitric acid, methylenesuccinic acid, gallic acid, ascorbic acid, nitroacetic acid, oxaloacetic acid, chloroacetic acid, dichloroacetic acid, and trichloroacetic acid; glycine, alanine, glutamic acid, aspartic acid, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, phenylalanine, tryptophan, tyrosine, proline, and cysteine. Amino acids such as sucrine, glutamine, asparagine, lysine, and arginine; nicotinic acid; picric acid; picolinic acid; phytic acid; 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxil Examples of organic phosphonic acids include hydroxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, and aminopoly(methylenephosphonic acid); and organic sulfonic acids such as xylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, aminoethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 2-naphthalenesulfonic acid, sulfosuccinic acid, 10-camphorsulfonic acid, isethionic acid, and taurine.

[0143] Examples of inorganic acids include phosphoric acid (orthophosphoric acid), nitric acid, sulfuric acid, hydrochloric acid, boric acid, sulfamic acid, phosphinic acid, phosphonic acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid, carbonic acid, hydrofluoric acid, sulfurous acid, thiosulfuric acid, chloric acid, perchloric acid, chlorous acid, hydroiodic acid, periodic acid, iodic acid, hydrobromic acid, perbromic acid, bromic acid, chromic acid, and nitrous acid.

[0144] Examples of sugars include tetroses such as erythrose, threose, and erythrulose; pentoses such as ribose, arabinose, xylose, lyxose, xylulose, and ribulose; monosaccharides such as hexoses such as allose, altrose, glucose, mannose, glucose, idose, galactose, talose, fructose, sorbose, psicose, and tagatose; and oligosaccharides such as maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, turanose, trehalose, saccharose, mannitrose, cellotriose, gentianose, raffinose, melezitose, cerotetrose, and stachyose. Other sugars such as residues of heptose, deoxy sugar, thio sugar, seleno sugar, aldonic sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar, unsaturated sugar, sugar ester, sugar ether, glycoside, etc. may also be used, as well as polysaccharides such as starch, glycogen, cellulose, chitin, chitosan, etc., or their hydrolyzed products.

[0145] Specific examples of basic compounds include alkali metal hydroxides or salts, quaternary ammonium hydroxides or salts, ammonia, amines, etc. Examples of alkali metals include potassium and sodium. Examples of salts include carbonates, bicarbonates, sulfates, acetates, etc. Examples of quaternary ammonium include tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc.

[0146] The quaternary ammonium hydroxide compound includes quaternary ammonium hydroxide or a salt thereof, and specific examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide.

[0147] Specific examples of the amine include 2-amino-2-ethyl-1,3-propanediol, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-(β-aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, anhydrous piperazine, piperazine hexahydrate, 1-(2-aminoethyl)piperazine, N-methylpiperazine, guanidine, etc. These basic compounds may be used alone or in combination of two or more.

[0148] According to one embodiment of the present invention, the chemical components are in solid form at 25°C.

[0149] The water-soluble polymer mainly functions to protect the object to be polished and as a wetting agent, and therefore is sometimes added to the polishing composition.

[0150] In this specification, a water-soluble polymer is a polymer that is in a solid form (powder form) at 25°C and can be dissolved in water to become a liquid. A water-soluble polymer-containing liquid can be prepared by dissolving the water-soluble polymer in water. Here, "water-soluble" means that the solubility in water (25°C) is 1 g / 100 mL or more, and "polymer" refers to a (co)polymer that has repeating units in its molecular structure and a weight-average molecular weight (Mw) of 1,000 or more.

[0151] The water-soluble polymer may contain at least one functional group selected from cationic, anionic, and nonionic groups in the molecule. Specific examples of water-soluble polymers include those containing hydroxyl, carboxyl, acyloxy, sulfo, quaternary ammonium, heterocyclic, vinyl, and polyoxyalkylene structures in the molecule. Suitable examples include nitrogen-containing polymers, polyvinyl alcohol (polyvinyl alcohol with a saponification degree of 70 mol% or higher), and cellulose derivatives. The term "cellulose derivative" refers to a water-soluble cellulose derivative in which at least one hydroxyl group of water-insoluble cellulose is substituted with a substituent. Here, cellulose is a linear polymer of multiple β-glucose molecules via glycosidic bonds, and the cellulose structural unit has hydroxyl groups at the C2, C3, and C6 positions. Because the hydroxyl groups form strong hydrogen bonds both intramolecularly and intermolecularly, cellulose is generally insoluble in water and organic solvents. However, by substituting at least a portion of the hydroxyl groups of cellulose with a substituent and breaking at least a portion of the hydrogen bonds, the cellulose derivative can be made water-soluble.

[0152] More specifically, examples of the polymer include cellulose derivatives, imine derivatives such as poly(N-acylalkyleneimine), polyvinyl alcohol, polyvinylpyrrolidone, copolymers containing polyvinylpyrrolidone as part of their structure, polyvinylcaprolactam, copolymers containing polyvinylcaprolactam as part of their structure, polyoxyethylene, polymers containing oxyalkylene units, polymers of these having multiple types of structures such as diblock, triblock, random, and alternating structures, and polyether-modified silicones.

[0153] Among them, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, or polymers containing oxyalkylene units are preferred from the viewpoint of their excellent hydrophilicity. Specific examples of cellulose derivatives include cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and carboxymethyl cellulose, as well as pullulan. Among cellulose derivatives, hydroxyethyl cellulose is preferred from the viewpoint of its high ability to impart wettability to the polished surface and its excellent cleaning properties.

[0154] In one embodiment of the present invention, the weight-average molecular weight of the water-soluble polymer is preferably 1,000 to 3,000,000, more preferably 2,000 to 1,000,000, even more preferably 3,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 8,000 to 50,000. When two or more water-soluble polymers are prepared, the weight-average molecular weights of the water-soluble polymers may be the same or at least some may be different.

[0155] A non-aqueous additive that is liquid at 25°C refers to an additive that is in a liquid form at 25°C even if it is not dissolved in water.

[0156] According to one embodiment of the present invention, the nonaqueous additive liquid at 25°C contains an oxyalkylene unit. Examples of compounds containing an oxyalkylene unit include ethylene glycol, propylene glycol, polyethylene glycol (polyethylene oxide (PEO)), polypropylene glycol (propylene oxide (PO)), block copolymers of ethylene oxide (EO) and propylene oxide (PO), and random copolymers of EO and PO. The block copolymer of EO and PO may be a diblock copolymer or triblock copolymer containing a polyethylene oxide (PEO) block and a polypropylene oxide (PPO) block. Examples of the triblock copolymer include PEO-PPO-PEO triblock copolymers and PPO-PEO-PPO triblock copolymers. Generally, PEO-PPO-PEO triblock copolymers are more preferred. In block or random copolymers of EO and PO, the molar ratio of EO to PO (EO / PO) constituting the copolymer is preferably greater than 1, more preferably 2 or greater, and even more preferably 3 or greater (e.g., 5 or greater), from the viewpoint of water solubility and the like.

[0157] In one embodiment of the present invention, the weight average molecular weight of the nonaqueous additive that is liquid at 25°C is preferably 50 to 5,000, more preferably 120 to 2,000, and even more preferably 150 to 1,000.

[0158] According to one embodiment of the present invention, the non-aqueous additive that is liquid at 25° C. includes alcohol (for example, methanol, ethanol).

[0159] A polished object can be obtained by polishing the object with the polishing composition described above. A rinse treatment is performed by applying the rinse composition of the present invention to the polished object. In one embodiment of the present invention, the rinse treatment can be performed on a polishing table (platen) equipped with a polishing pad. The rinse composition is then brought into direct contact with the polished object. As a result, foreign matter on the surface of the polished object is removed by the frictional force (physical action) of the polishing pad and the chemical action of the rinse composition. Among foreign matter, particles and organic residues are particularly easily removed by physical action. Therefore, a preferred rinse treatment utilizes friction with the polishing pad on the polishing table (platen) to effectively remove particles and organic residues. In other words, a rinse treatment using a rinse composition is preferably a treatment that reduces residues on the surface of the polished object using a polishing pad.

[0160] Specifically, for example, the rinsing treatment can be carried out by placing the polished surface of the object to be polished on the polishing table (platen) of the polishing device, bringing the polishing pad into contact with the polished object to be polished, and supplying a rinsing composition to the contact area while sliding the polished object to be polished and the polishing pad relative to each other.

[0161] As the polishing device, a general polishing device can be used, which is equipped with a holder for holding the object to be polished, a motor whose rotation speed can be changed, and a polishing platen to which a polishing pad (polishing cloth) can be attached.

[0162] The polishing pad may be made of any material, including general nonwoven fabric, polyurethane, porous fluororesin, etc. The polishing pad is preferably provided with grooves to allow the rinse composition to accumulate.

[0163] There are no particular restrictions on the rinse polishing conditions. For example, the rotation speed of the polishing table and the head (carrier) are 10 rpm (0.17 s -1 ) or more 100rpm(1.67s -1) or less, and the pressure (polishing pressure) applied to the polished object is preferably 0.5 psi (3.4 kPa) or more and 10 psi (68.9 kPa) or less. The method of supplying the rinsing composition to the polishing pad is not particularly limited, and for example, a method of continuously supplying it using a pump or the like (flowing it over) is used. There is no limit to the amount of supply, but it is preferable that the surface of the polishing pad is always covered with the rinsing composition, and it is preferably 10 mL / min or more and 5000 mL / min or less. The rinsing time is also not particularly limited, but it is preferably 5 seconds or more and 180 seconds or less.

[0164] According to one embodiment of the present invention, the number of defects (greater than 0.1 μm) on a rinsed object (e.g., rinsed polysilicon) is 170 or less, 150 or less, 130 or less, or 100 or less. In reality, it is about 10 or more.

[0165] The present invention encompasses the following aspects and configurations: 1. A process of preparing an abrasive dispersion containing abrasive grains and water, and filtering the abrasive dispersion to obtain a first liquid; a process of preparing one or more chemical component-containing aqueous solutions containing a chemical component and water, and filtering the solution if only one solution is used, or filtering a mixture X containing one or more of the chemical component-containing aqueous solutions, to obtain a second liquid; and a process of mixing the first liquid and the second liquid to obtain a third liquid, and filtering the third liquid. A method for producing a polishing composition comprising the steps of:

[0166] 2. The manufacturing method described in 1, wherein the abrasive grains contain silica.

[0167] 3. The manufacturing method according to 1. or 2., wherein the abrasive grains contain colloidal silica.

[0168] 4. The manufacturing method according to any one of 1. to 3., wherein the chemical component used in preparing one or more of the chemical component-containing aqueous solutions is in a solid form at 25°C.

[0169] 5. The manufacturing method according to any one of 1. to 4., wherein the mixture X is obtained by preparing two or more aqueous solutions containing the chemical components and filtering one or more of them before the mixing.

[0170] 6. The manufacturing method according to any one of 1. to 5., wherein the number of coarse particles having a particle diameter of more than 0.15 μm is 1,000,000 or less per 1 ml of the polishing composition.

[0171] 7. The manufacturing method according to any one of 1. to 6., in which at least one water-soluble polymer-containing liquid containing a water-soluble polymer and water is prepared, and the mixture X is obtained by further mixing the water-soluble polymer-containing liquid with the chemical component-containing aqueous solution.

[0172] 8. The manufacturing method according to 7., wherein the mixture X is obtained by filtering the water-soluble polymer-containing liquid before the mixing.

[0173] 9. The production method according to any one of 1. to 8., wherein a liquid non-aqueous additive is prepared at 25°C, and the mixture X is obtained by mixing the non-aqueous additive with the chemical component-containing aqueous solution without filtering the non-aqueous additive in advance.

[0174] 10. A method for producing a rinse composition, comprising the steps of preparing one or more water-soluble polymer-containing liquids containing a water-soluble polymer and water, and filtering the liquid if one type is used, or filtering a mixture Y if two or more types are used, to obtain liquid A; preparing one or more chemical component-containing aqueous solutions containing a chemical component and water, and filtering the liquid if one type is used, or filtering a mixture Z of one or more of the chemical component-containing aqueous solutions, to obtain liquid B; and mixing liquid A and liquid B to obtain liquid C, and filtering liquid C.

[0175] 11. The manufacturing method according to 10, wherein a liquid non-aqueous additive is prepared at 25°C, and the non-aqueous additive is mixed with the chemical component-containing aqueous solution without prior filtering to obtain the mixture Z.

[0176] 12. The manufacturing method described in 10. or 11., wherein the water-soluble polymer present in at least one of the water-soluble polymer-containing liquids has a radius of gyration of 10 nm or more.

[0177] 13. The manufacturing method according to any one of items 10 to 12, wherein the number of coarse particles having a particle diameter of more than 0.15 μm is 1,000,000 or less per 1 ml of the rinse composition.

[0178] 14. The manufacturing method according to any one of items 10 to 13, wherein the rinsing composition is substantially free of abrasive grains. [Example]

[0179] The present invention will be described in more detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. In the following, unless otherwise specified, the operations were carried out under the conditions of room temperature (25°C) and relative humidity of 40 to 50% RH.

[0180] <Ingredient preparation> 1) An aqueous dispersion of colloidal silica (colloidal silica concentration 20% by mass; average primary particle size of abrasive grains 12 nm; average secondary particle size of abrasive grains 25 nm, D90 / D10: 3.1) was prepared as the abrasive grain dispersion. The average primary particle size of the abrasive grains was calculated from the specific surface area of ​​the abrasive grains measured by the BET method using a Micromeritics Flow Sorb II 2300 and the density of the abrasive grains. The average secondary particle size of the abrasive grains was measured using a Nikkiso Co., Ltd. dynamic light scattering particle size distribution analyzer UPA-UT151.

[0181] 2) As the aqueous solution containing the chemical component, an aqueous maleic acid solution (maleic acid concentration: 10% by mass) was prepared. Note that the maleic acid was in a solid form (powder) at 25°C.

[0182] 3) An N-methyl-D-glucamine aqueous solution (N-methyl-D-glucamine concentration 10% by mass) was prepared as a chemical component-containing aqueous solution. Note that N-methyl-D-glucamine is in a solid form (powder) at 25°C.

[0183] 4) As the aqueous solution containing the chemical component, an aqueous solution of m-xylene sulfonic acid (m-xylene sulfonic acid concentration: 10% by mass) was prepared. Note that m-xylene sulfonic acid is in a solid form (powder) at 25°C.

[0184] 5) Polyethylene glycol (weight average molecular weight 200) was prepared as a non-aqueous additive that was liquid at 25°C.

[0185] 6) Iminodiacetic acid was prepared as a chemical component. Note that iminodiacetic acid is in solid form (powder) at 25°C.

[0186] 7) 2-amino-2-ethyl-1,3-propanediol was prepared as a chemical component. Note that 2-amino-2-ethyl-1,3-propanediol is in liquid form at 25°C.

[0187] 8) A hydroxyethyl cellulose-containing solution (hydroxyethyl cellulose concentration: 1% by mass; radius of gyration of hydroxyethyl cellulose present in the hydroxyethyl cellulose-containing solution: 140 nm; weight-average molecular weight of hydroxyethyl cellulose: 1,400,000) was prepared as a water-soluble polymer-containing solution. The radius of gyration was measured by first preparing an aqueous solution with a water-soluble polymer concentration in the range of 0.1 to 1 mg / mL. For each sample, measurements were taken every 10 degrees at angles ranging from 20 to 150 degrees using a DLS-8000 light scattering photometer (Otsuka Electronics Co., Ltd.). The radius of gyration (nm) was calculated by one-concentration plot analysis.

[0188] <Preparation of Polishing Composition> Example 1 The aqueous dispersion of colloidal silica prepared in 1) above was filtered by pressure filtration using a 1-inch cartridge filter (made of polypropylene (depth type)) (manufactured by ROKI TECHNO Co., Ltd.) with a pore size of 3.0 μm at a filtration rate of 500 ml / m for 10 minutes to obtain a first liquid.

[0189] The aqueous maleic acid solution, the aqueous N-methyl-D-glucamine solution, and the aqueous m-xylene sulfonic acid solution prepared in 2), 3), and 4), respectively, were filtered for 10 minutes at a filtration rate of 500 ml / m using a 1-inch cartridge filter (Ultipore (registered trademark) N66 (pleated type), made of nylon 66, manufactured by Nippon Pall Corporation) with a pore size of 0.2 μm, to prepare filtered aqueous maleic acid solutions, filtered aqueous N-methyl-D-glucamine solutions, and filtered aqueous m-xylene sulfonic acid solutions.

[0190] A filtered aqueous solution of maleic acid; A filtered N-methyl-D-glucamine aqueous solution; A filtered aqueous solution of m-xylene sulfonic acid; 5) The polyethylene glycol prepared in The above were mixed in a mass ratio of 15:15:45:25 to obtain a mixture X, and the mixture X was filtered by pressure filtration using a 1-inch cartridge filter (Ultipore (registered trademark) N66 (pleated type), made of nylon 66, manufactured by Nippon Pall Corporation) with a pore size of 0.2 μm at a filtration rate of 500 ml / m for 10 minutes to obtain a second liquid.

[0191] The first liquid, the second liquid, and water were mixed in a mass ratio of 300:100:600 to obtain a third liquid. The third liquid was then pressure-filtered using a 1-inch cartridge filter (made of polypropylene (depth type)) with a pore size of 3.0 μm (manufactured by Roki Techno Co., Ltd.) at a filtration rate of 500 ml / m for 10 minutes, and the resulting liquid was further pressure-filtered using a 1-inch cartridge filter (Ultipore (registered trademark) N66 (pleated type), made of nylon 66, manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.2 μm at a filtration rate of 200 ml / m for 10 minutes to obtain a composition. Water was then added to the composition so that its mass was three times that of the original mass (i.e., it was diluted three times with water), thereby obtaining a polishing composition.

[0192] Example 2 In Example 1, a polishing composition was obtained in the same manner as in Example 1, except that the polyethylene glycol prepared in 5) was further filtered by pressure filtration using a 1-inch cartridge filter (Ultipore (registered trademark) N66 (pleated type), made of nylon 66, manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.2 μm at a filtration rate of 200 ml / m for 10 minutes.

[0193] Example 3 The aqueous dispersion of colloidal silica prepared in 1) above was filtered by pressure filtration using a 1-inch cartridge filter (made of polypropylene (depth type)) (manufactured by ROKI TECHNO Co., Ltd.) with a pore size of 3.0 μm at a filtration rate of 500 ml / m for 10 minutes to obtain a first liquid.

[0194] Prepared in 2), 5), and 6) above an aqueous maleic acid solution; Polyethylene glycol (weight average molecular weight 200), Iminodiacetic acid, The above was mixed with water in a mass ratio of 86:10:4 to obtain a mixture X having a total mass concentration of 10 mass %, and the mixture X was filtered by pressure filtration using a 1-inch cartridge filter (Ultipore (registered trademark) N66 (pleated type), made of nylon 66, manufactured by Nippon Pall Corporation) with a pore size of 0.2 μm at a filtration rate of 500 ml / m for 10 minutes to obtain a second liquid.

[0195] The above-mentioned first liquid, the above-mentioned second liquid and water were mixed in a mass ratio of 50:100:850 to obtain a third liquid, which was then filtered by pressure filtration for 10 minutes at a filtration rate of 500 ml / m using a 1-inch cartridge filter (manufactured by Roki Techno Co., Ltd.) with a pore size of 3.0 μm. The resulting liquid was then further filtered by pressure filtration for 10 minutes at a filtration rate of 200 ml / m using a 1-inch cartridge filter (Ultipore (registered trademark) N66 (pleated type), made of nylon 66, manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.2 μm, to obtain a polishing composition.

[0196] Example 5 A polishing composition was obtained in the same manner as in Example 1, except that the m-xylene sulfonic acid aqueous solution prepared in 4) above was used instead of the filtered m-xylene sulfonic acid aqueous solution in Example 1.

[0197] Example 6 A polishing composition was obtained in the same manner as in Example 1, except that the N-methyl-D-glucamine aqueous solution prepared in 3) above was used instead of the filtered N-methyl-D-glucamine aqueous solution in Example 1.

[0198] Example 7 In Example 1, a polishing composition was obtained in the same manner as in Example 1, except that the N-methyl-D-glucamine aqueous solution prepared in 3) above was used instead of the filtered N-methyl-D-glucamine aqueous solution, and the m-xylene sulfonic acid aqueous solution prepared in 4) above was used instead of the filtered m-xylene sulfonic acid aqueous solution.

[0199] (Comparative Example 1) In Example 1, a polishing composition was obtained in the same manner as in Example 1, except that the maleic acid aqueous solution, N-methyl-D-glucamine aqueous solution, and m-xylene sulfonic acid aqueous solution prepared in 2), 3), and 4) above, respectively, were not filtered, and the third liquid was not filtered.

[0200] (Comparative Example 2) A polishing composition was obtained in the same manner as in Example 1, except that only mixture X was subjected to the filtering described in Example 1.

[0201] (Comparative Example 3) A polishing composition was obtained in the same manner as in Example 1, except that the filtering described in Example 1 was carried out only on the third liquid.

[0202] Comparative Example 4 A polishing composition was obtained in the same manner as in Example 1, except that no filtering was carried out.

[0203] (Comparative Example 5) In Example 1, the maleic acid aqueous solution, N-methyl-D-glucamine aqueous solution, and m-xylene sulfonic acid aqueous solution prepared in 2), 3), and 4), respectively, were not filtered, and mixture X was also not filtered. Except for this, the polishing composition was obtained in the same manner as in Example 1.

[0204] (Comparative Example 9) In Example 1, the aqueous dispersion of colloidal silica prepared in 1) above was filtered by pressure filtration using a 1-inch cartridge filter (made of polypropylene (depth type)) (manufactured by ROKI TECHNO Co., Ltd.) with a pore size of 3.0 μm at a filtration rate of 500 ml / m for 180 minutes, but no other filtering was performed. The same procedure as in Example 1 was repeated to obtain a polishing composition.

[0205] (Comparative Example 10) In Example 1, the polishing composition was obtained in the same manner as in Example 1, except that the aqueous dispersion of colloidal silica prepared in 1) above was not filtered, the mixture X was not filtered, and the third liquid was not filtered.

[0206] <Preparation of Rinse Composition> Example 4 The hydroxyethyl cellulose-containing solution prepared in 8) above was filtered by pressure filtration using a 1-inch cartridge filter (Ultipore (registered trademark) N66 (pleated type), made of nylon 66, manufactured by Nippon Pall Corporation) with a pore size of 0.2 μm at a filtration rate of 100 ml / m for 10 minutes to obtain solution A.

[0207] Iminodiacetic acid and 2-amino-2-ethyl-1,3-propanediol prepared in steps 6) and 7) above, respectively, were mixed in a mass ratio of 36:64 with water to obtain an aqueous solution (mixture Z) with a total mass concentration of 7%, and mixture Z was filtered by pressure filtration using a 1-inch cartridge filter with a pore size of 0.2 μm (Ultipore (registered trademark) N66 (pleated type), made of nylon 66, manufactured by Nippon Pall Co., Ltd.) at a filtration rate of 500 ml / m for 10 minutes to obtain solution B.

[0208] The above-mentioned solution A, the above-mentioned solution B, and water were mixed in a mass ratio of 10:100:890 to obtain solution C, which was then further filtered by pressure filtration using a 1-inch cartridge filter with a pore size of 0.2 μm (Ultipore (registered trademark) N66 (pleated type), made of nylon 66, manufactured by Nippon Pall Corporation) at a filtration rate of 200 ml / m for 10 minutes to obtain a rinse composition.

[0209] (Comparative Example 6) A rinse composition was obtained in the same manner as in Example 4, except that the hydroxyethyl cellulose-containing liquid prepared in the above 8) was not filtered.

[0210] (Comparative Example 7) In Example 4, a rinse composition was obtained in the same manner as in Example 4, except that the mixture Z was not filtered.

[0211] (Comparative Example 8) In Example 4, a rinse composition was obtained in the same manner as in Example 4, except that the liquid C was not filtered.

[0212] <Measurement of the number of coarse particles> The number of coarse particles having a size exceeding 0.15 μm per unit volume (1 mL) present in the polishing compositions and rinse compositions obtained in each of the examples and comparative examples was measured using a liquid particle counter (LPC, Liquid Particle Counter, AccuSizer (registered trademark) FX-nano, manufactured by Nippon Integris Co., Ltd.). The measurement was performed three times (n = 3), the average value of n = 3 was determined, and the decimal part was rounded off.

[0213] <Measurement of defects> As a polishing object, a silicon wafer (200 mm, blanket wafer) having a 5000 Å thick polysilicon film formed on its surface was prepared.

[0214] <Evaluation of the polishing composition> <CMP process> Using each of the polishing compositions prepared in Examples 1 to 3, 5 to 7, or Comparative Examples 1 to 5, 9, and 10, polishing treatment was performed under the following conditions.

[0215] - Polishing apparatus and polishing conditions - Polishing object: 200 mm polysilicon wafer Polishing apparatus: Single-sided polishing apparatus for 200 mm wafers Polishing pad: Foamed polyurethane pad (hardness 90) Polishing pressure: 2.3 psi (1 psi = 6894.76 Pa, the same applies hereinafter) Rotational speed of the polishing platen: 93 rpm Supply of the polishing composition: Pouring Supply amount of the polishing composition: 100 mL / min Head rotation speed: 87 rpm Polishing time: 60 seconds.

[0216] ≪Rinse polishing process≫ Following the above CMP process, a rinse polishing treatment was performed on the polysilicon substrate after being polished in the same process using GLANZOX 3500 manufactured by Fujimi Incorporated.

[0217] - Rinse polishing apparatus and rinse polishing conditions - Rinse polishing apparatus: Single-sided polishing apparatus for 200 mm wafers Polishing pad: Foamed polyurethane pad (hardness 90) Polishing pressure: 1.5 psi Polishing platen rotation speed: 88 rpm Supply of rinse composition: Pouring Supply rate of rinse composition: 100 mL / min Head rotation speed: 85 rpm Rinse polishing time: 10 seconds.

[0218] <Evaluation of rinse composition> <CMP process> Using PLANERLITE 6103 manufactured by Fujimi Incorporated, polishing treatments were performed under the following conditions respectively.

[0219] - Polishing apparatus and polishing conditions - Object to be polished: 200 mm polysilicon wafer Polishing apparatus: Single-sided polishing apparatus for 200 mm wafers Polishing pad: Foamed polyurethane pad (hardness 90) Polishing pressure: 2.3 psi (1 psi = 6894.76 Pa, the same hereinafter) Polishing platen rotation speed: 93 rpm Supply of polishing composition: Pouring Supply rate of polishing composition: 100 mL / min Head rotation speed: 87 rpm Polishing time: 60 seconds.

[0220] <Rinse polishing process> Following the above CMP step, the polysilicon substrates polished in the step were subjected to a rinse polishing treatment using each of the rinse compositions prepared in Example 4 or Comparative Examples 6 to 8.

[0221] - Rinse polishing equipment and rinse polishing conditions - Rinse polishing machine: Single-sided polishing machine for 200mm wafers Polishing pad: Polyurethane foam pad (hardness 90) Grinding pressure: 1.5psi Polishing platen rotation speed: 88 rpm Supply of rinse composition: free-flowing Rinse composition supply rate: 100 mL / min Head rotation speed: 85 rpm Rinse polishing time: 10 seconds.

[0222] The surface of the object to be polished obtained by the above cleaning was examined for defects of 0.1 μm or larger on the entire surface of the object to be polished (excluding the outer 5 mm area) using a defect detection device (wafer inspection device) called "Surfscan SP2" manufactured by KLA-TENCOR Corporation.

[0223] The above is summarized in Table 1.

[0224] [Table 1]

[0225] [Table 2]

[0226] The polishing compositions and rinsing compositions of the Examples were able to reduce coarse particles and suppress defects.

[0227] The results of Example 2 are interesting. Although Example 2 involved more filtering than Example 1, the quality results of both were almost the same. In other words, Example 2 required more time for the filtering operation of the non-aqueous additive, and in that sense, it was evaluated as having a slight decrease in productivity. Thus, when producing a polishing composition, it is important to select the components to be filtered based on a clear technical concept, rather than blindly filtering all components.

[0228] The results of Comparative Example 9 are also interesting. The number of coarse particles in the polishing composition of Comparative Example 9 is at the same level as that of Example 7, but the latter has more suppressed defects. This suggests that the number of coarse particles and the number of defects do not necessarily correlate, and that the process of the present invention produces a heterogeneous effect of suppressing defects.

Claims

1. preparing an abrasive dispersion containing abrasive grains and water, and filtering the abrasive dispersion to obtain a first liquid; a step of preparing one or more chemical component-containing aqueous solutions containing a chemical component and water, and filtering the solution if only one solution is used, or filtering a mixture X containing the one or more chemical component-containing aqueous solutions, to obtain a second liquid; mixing the first liquid and the second liquid to obtain a third liquid, and filtering the third liquid; A method for producing a polishing composition comprising the steps of:

2. The method of claim 1 , wherein the abrasive grains comprise silica.

3. The method of claim 1 , wherein the abrasive grains comprise colloidal silica.

4. The method according to claim 1 , wherein the chemical components used in preparing one or more of the chemical component-containing aqueous solutions are in a solid form at 25° C.

5. The method for producing the mixture X according to claim 1 , further comprising the steps of preparing two or more kinds of aqueous solutions containing the chemical components and filtering one or more of the aqueous solutions before the mixing.

6. 2. The manufacturing method according to claim 1, wherein the number of coarse particles having a particle diameter of more than 0.15 μm is 1,000,000 or less per ml of the polishing composition.

7. 2. The method according to claim 1, wherein the mixture X is obtained by preparing a non-aqueous additive in a liquid state at 25°C and mixing the non-aqueous additive with the chemical component-containing aqueous solution without filtering the non-aqueous additive in advance.

8. a step of preparing one or more kinds of water-soluble polymer-containing liquids containing a water-soluble polymer and water, and filtering the water-soluble polymer-containing liquid if one kind is used, or filtering a mixture Y thereof if two or more kinds are used, to obtain a liquid A; a step of preparing one or more chemical component-containing aqueous solutions containing a chemical component and water, and filtering the solution if only one solution is used, or filtering a mixture Z containing the one or more chemical component-containing aqueous solutions to obtain a solution B; mixing the solution A and the solution B to obtain a solution C, and filtering the solution C; A method for producing a rinse composition comprising the steps of:

9. The method according to claim 8 , wherein the water-soluble polymer present in at least one of the water-soluble polymer-containing liquids has a radius of gyration of 10 nm or more.

10. The method according to claim 9, wherein the number of coarse particles having a particle diameter of more than 0.15 μm is 1,000,000 or less per ml of the rinse composition.

11. The method of claim 8 , wherein the rinsing composition is substantially free of abrasive particles.

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