Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B24—GRINDING; POLISHING
  • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
  • B24B37/00—Lapping machines or devices; Accessories
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09G—POLISHING COMPOSITIONS; SKI WAXES
  • C09G1/00—Polishing compositions
  • C09G1/02—Polishing compositions containing abrasives or grinding agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/14—Anti-slip materials; Abrasives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
  • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

• the present disclosure relates to a polishing liquid composition for silicon oxide films containing cerium oxide particles, a method for manufacturing a semiconductor substrate using the same, and a method for polishing a substrate.
• a chemical mechanical polishing (CMP) technique is a technique in which the surface of a substrate to be polished and a polishing pad are brought into contact with each other, and a polishing liquid is supplied to the contact area between the substrate and the polishing pad. This is a technique for chemically reacting uneven portions on the surface of the substrate to be polished and mechanically removing and flattening the substrate by moving the substrate.
• CMP chemical mechanical polishing
• the polishing selectivity of the polishing stopper film eg, silicon nitride film
• the film to be polished eg, silicon oxide film
• improved polishing selectivity that is, the film to be polished is harder to polish than the film to be polished
• Patent Document 1 discloses a polishing liquid for chemical mechanical polishing containing ceria particles having an average aspect ratio of 1.5 or more and an anionic polymer such as polyacrylic acid.
• This document discloses a nitrogen-containing heteroaromatic ring compound, 4-pyrone, etc. as optional components.
• Patent Document 2 discloses a copolymer having abrasive grains such as ceria, a structural unit derived from a styrene compound and a structural unit derived from at least one selected from acrylic acid and maleic acid,
• a polishing liquid comprising:
• the present disclosure in one aspect, contains cerium oxide particles (component A), a water-soluble anionic polymer (component B), an unsaturated cyclic compound (component C), and an aqueous medium, Component B has an aromatic group in the molecule, Component C relates to a polishing liquid composition for silicon oxide films having a functional group represented by the following formula (I) or (II) in the cyclic skeleton.
• Y represents OM 1 or SM 2
• M 1 and M 2 are the same or different and represent an alkali metal ion, an alkaline earth metal ion, an organic cation, ammonium (NH 4 + ) or a hydrogen atom.
• M 3 represents an alkali metal ion, an alkaline earth metal ion, an organic cation, ammonium (NH 4 + ) or a hydrogen atom.
• the present disclosure in one aspect, relates to a method for manufacturing a semiconductor substrate, including the step of polishing a film-to-be-polished using the polishing liquid composition of the present disclosure.
• the present disclosure includes a step of polishing a film-to-be-polished using the polishing composition of the present disclosure, wherein the film-to-be-polished is a silicon oxide film formed in the process of manufacturing a semiconductor substrate. Regarding the method.
• the present disclosure provides a polishing liquid composition for silicon oxide films that can improve the flatness of the substrate surface after polishing while ensuring the polishing rate, and a method for manufacturing and polishing a semiconductor substrate using the same.
• the present disclosure in one aspect, contains cerium oxide particles (component A), a water-soluble anionic polymer (component B), an unsaturated cyclic compound (component C), and an aqueous medium, Component B has an aromatic group in the molecule, Component C has a functional group represented by the above formula (I) or Formula (II) in the cyclic skeleton, a polishing composition for silicon oxide films ( hereinafter, also referred to as "the polishing composition of the present disclosure”).
• a polishing liquid composition for a silicon oxide film that can improve the flatness of the substrate surface after polishing while ensuring the polishing rate.
• Component C can be adsorbed to the silicon oxide film or cerium oxide particles by the functional group represented by the above formula (I) or formula (II) in the cyclic skeleton, and when a high stress is applied, , can be desorbed.
• Component C can form a protective film by being adsorbed on the silicon oxide film or cerium oxide particles in concave portions to which a load is less likely to be applied, and desorbs from convex portions to which a high load is applied, thereby securing the polishing speed of convex portions.
• dishing can be suppressed.
• Component B is thought to improve the strength of the protective film formed by Component C, suppress the polishing rate of concave portions, and improve the flatness of the surface of the substrate after polishing. be done.
• the present disclosure may not be construed as being limited to these mechanisms.
• the polishing composition of the present disclosure contains cerium oxide (hereinafter also referred to as "ceria”) particles (hereinafter also simply referred to as "component A”) as abrasive grains.
• ceria cerium oxide
• component A positively charged ceria or negatively charged ceria can be used.
• ESA method Electrokinetic Sonic Amplitude
• the surface potential can be measured using, for example, "Zeta Probe” (manufactured by Kyowa Interface Science Co., Ltd.), and specifically by the method described in Examples.
• Component A may be of one type or a combination of two or more types.
• component A examples include colloidal ceria, amorphous ceria, and ceria-coated silica.
• Colloidal ceria can be obtained by a build-up process, for example, by the method described in Examples 1 to 4 of JP-A-2010-505735.
• amorphous ceria examples include pulverized ceria.
• An embodiment of the pulverized ceria includes, for example, calcined and pulverized ceria obtained by calcining and pulverizing a cerium compound such as cerium carbonate or cerium nitrate.
• ground ceria examples include, for example, single crystal ground ceria obtained by wet grinding ceria particles in the presence of an inorganic acid or an organic acid.
• inorganic acids used during wet pulverization include nitric acid
• organic acids include organic acids having a carboxyl group.
• polycarboxylates such as ammonium polyacrylate, At least one selected from picolinic acid, glutamic acid, aspartic acid, aminobenzoic acid and p-hydroxybenzoic acid can be mentioned.
• ceria-coated silica for example, at least a part of the silica particle surface is granular by the method described in Examples 1 to 14 of JP-A-2015-63451 or Examples 1-4 of JP-A-2013-119131.
• Composite particles having a structure coated with ceria can be mentioned, and the composite particles can be obtained, for example, by depositing ceria on silica particles.
• the shape of component A includes, for example, a substantially spherical shape, a polyhedral shape, and a raspberry shape.
• the average primary particle size of component A is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, and even more preferably 30 nm or more, from the viewpoint of improving the polishing rate. It is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, still more preferably 100 nm or less, even more preferably 80 nm or less, and even more preferably 60 nm or less.
• the average primary particle size of component A is calculated using the BET specific surface area S (m 2 /g) calculated by the BET (nitrogen adsorption) method. The BET specific surface area can be measured by the method described in Examples.
• the content of component A in the polishing composition of the present disclosure is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and 0.05% by mass, from the viewpoint of improving the polishing rate and flatness. % or more is more preferable, 0.1% by mass or more is still more preferable, and 0.15% by mass or more is even more preferable, and from the viewpoint of suppressing the occurrence of polishing scratches, it is preferably 6% by mass or less, and 3% by mass or less. More preferably, 1% by mass or less is even more preferable, and 0.7% by mass or less is even more preferable.
• the content of component A is preferably 0.001% by mass or more and 6% by mass or less, more preferably 0.01% by mass or more and 6% by mass or less, and 0.05% by mass or more and 3% by mass or less. is more preferable, 0.1% by mass or more and 1% by mass or less is even more preferable, and 0.15% by mass or more and 0.7% by mass or less is even more preferable.
• component A is a combination of two or more, the content of component A refers to the total content thereof.
• the polishing composition of the present disclosure contains a water-soluble anionic polymer (hereinafter also simply referred to as "component B").
• Component B is a water-soluble anionic polymer having aromatic groups in the molecule.
• the aromatic group is preferably a group containing an aromatic ring from the viewpoint of improving the polishing rate and flatness. Examples of aromatic rings include benzene rings and naphthalene rings.
• component B is considered to be able to suppress the dishing rate during overpolishing while ensuring the polishing rate of the silicon oxide film, and improve the flatness of the substrate surface after polishing.
• dishing refers to a dish-shaped depression that is caused by excessive polishing of the concave portion.
• water-soluble refers to dissolving in the polishing composition of the present disclosure, preferably having a solubility of 0.5 g/100 mL or more in water (20° C.), more preferably 2 g/ It refers to having a solubility of 100 mL or more.
• Component B may be one type or a combination of two or more types.
• Component B is a water-soluble anionic condensate having a benzene ring or naphthalene ring in the main chain (“Component B1” and “Component B2” below) from the viewpoint of improving polishing rate and flatness. ), and a copolymer containing a styrene-derived structural unit and a monomer-derived structural unit having an anionic group (hereinafter "component B3").
• Component B1 Water-soluble anionic condensate>
• Component B1 in one or more embodiments, is a water-soluble anionic condensate with benzene rings in the backbone.
• Component B1 is, in one or more embodiments, a monomer represented by the following formula (III) (hereinafter also referred to as “constituent monomer b11”) and a monomer represented by the following formula (IV) (hereinafter referred to as "constituent monomer b12”).
• Component B1 may be one kind or a combination of two or more kinds.
• the constituent monomer b11 is a monomer represented by the following formula (III).
• R 1 and R 2 are the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or -OM 5 .
• at least one of R 1 and R 2 is preferably —OM 5 and more preferably —OH from the viewpoint of polymerization reactivity.
• at least one of R 1 and R 2 is preferably a hydrogen atom from the viewpoint of improving polishing rate and flatness.
• M 4 and M 5 are the same or different and represent an alkali metal ion, an alkaline earth metal ion, an organic cation, ammonium (NH 4 + ) or a hydrogen atom.
• Organic cations include organic ammoniums, such as alkylammoniums such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and the like.
• M 4 is preferably at least one selected from alkali metal ions, ammonium (NH 4 + ) and hydrogen atoms, and sodium ions and potassium ions, from the viewpoint of improving the polishing rate and flatness. , ammonium (NH 4 + ) and a hydrogen atom are more preferable.
• M 5 is preferably at least one selected from alkali metal ions, ammonium (NH 4 + ) and hydrogen atoms, and sodium ions and potassium ions, from the viewpoint of improving the polishing rate and flatness. , ammonium (NH 4 + ) and a hydrogen atom are more preferred, and a hydrogen atom is even more preferred.
• the constituent monomer b11 is preferably hydroxybenzoic acid (HBA), dihydroxybenzoic acid (DHBA), or 4-hydroxybenzoic acid (4-HBA ), 2-hydroxybenzoic acid (2-HBA), 2,4-dihydroxybenzoic acid (2,4-HBA), 2,6-dihydroxybenzoic acid (2,6-HBA) are more preferred, and 4-hydroxybenzoic acid Acid (4-HBA) is more preferred.
• the constituent monomer b12 is a monomer represented by the following formula (IV).
• R 3 and R 4 are the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or -OM 6 .
• at least one of R 3 and R 4 is preferably —OM 6 , more preferably —OH, from the viewpoint of improving the polishing rate and flatness.
• at least one of R 3 and R 4 is preferably a hydrogen atom from the viewpoint of improving the polishing rate and flatness.
• X 1 represents -SO 3 M 7 or -PO 3 M 8 M 9 .
• X 1 is preferably —SO 3 M 7 from the viewpoint of dissolution stability.
• M 6 , M 7 , M 8 and M 9 are the same or different and represent alkali metal ions, alkaline earth metal ions, organic cations, ammonium (NH 4 + ) or hydrogen atoms.
• Organic cations include organic ammoniums, such as alkylammoniums such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and the like.
• M 6 is preferably at least one selected from alkali metal ions, ammonium (NH 4 + ) and hydrogen atoms from the viewpoint of improving the polishing rate and planarity, and is preferably sodium ion or potassium ion.
• M 7 , M 8 and M 9 are the same or different, and in one or a plurality of embodiments, at least selected from alkali metal ions, ammonium (NH 4 + ) and hydrogen atoms from the viewpoint of improving the polishing rate and planarity.
• alkali metal ions, ammonium (NH 4 + ) and hydrogen atoms from the viewpoint of improving the polishing rate and planarity.
• sodium ions, potassium ions, ammonium (NH 4 + ) and hydrogen atoms is more preferred.
• the constituent monomer b12 includes phenolsulfonic acid (PhS).
• the molar ratio (%) of the constituent monomers b11 to the total of the constituent monomers b11 and b12 in the component B1 is preferably more than 30%, more preferably 35% or more, from the viewpoint of improving the polishing rate and flatness. More preferably 40% or more, even more preferably more than 40%, even more preferably 42% or more, even more preferably 43% or more, even more preferably 44% or more, even more preferably 45% or more, 46% or more is even more preferred, and 48% or more is even more preferred.
• component B1 is preferably an anionic condensate containing a structure represented by the following formula (V) from the viewpoint of improving polishing rate and flatness.
• R 5 and R 6 are the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or -OM 11 .
• R 5 and R 6 are preferably hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms, more preferably hydrogen atoms, from the viewpoint of improving the polishing rate and flatness.
• M 10 and M 11 are the same or different and represent an alkali metal ion, an alkaline earth metal ion, an organic cation, ammonium (NH 4 + ) or a hydrogen atom.
• Organic cations include organic ammoniums, such as alkylammoniums such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and the like.
• M 10 is preferably at least one selected from alkali metal ions, ammonium (NH 4 + ) and hydrogen atoms from the viewpoint of improving polishing rate and planarity, and is preferably sodium ion or potassium ion. , ammonium (NH 4 + ) and a hydrogen atom are more preferable.
• M 11 is preferably at least one selected from alkali metal ions, ammonium (NH 4 + ) and hydrogen atoms from the viewpoint of improving polishing rate and planarity, and is preferably sodium ion, potassium ion. , ammonium (NH 4 + ) and a hydrogen atom are more preferred, and a hydrogen atom is even more preferred.
• X 2 represents —SO 3 M 12 or —PO 3 M 13 M 14 . In one or more embodiments, X 2 is preferably —SO 3 M 12 from the viewpoint of dissolution stability.
• M 12 , M 13 and M 14 are the same or different and represent an alkali metal ion, an alkaline earth metal ion, an organic cation, ammonium (NH 4 + ) or a hydrogen atom.
• Organic cations include organic ammoniums, such as alkylammoniums such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and the like.
• m is 0.8 or less, 0.75 or less, 0.7 or less, or 0.65 or less.
• component B1 examples include cocondensates of 4-hydroxybenzoic acid (4-HBA) and phenolsulfonic acid (PhS).
• Component B1 can be produced, for example, by polymerizing a monomer having constituent monomer b11 and constituent monomer b12 in the presence of formaldehyde by known means such as addition condensation. From the viewpoint of improving hydrolysis resistance and improving storage stability in an acidic polishing liquid, it is preferably produced by an addition condensation method.
• the content (mol%) of a certain structural unit in all the structural units constituting component B1 may be defined as the content (mol%) of a structural unit charged to the reaction vessel in all steps of the synthesis of component B1, depending on the synthesis conditions.
• the amount (mol %) of the compound for introducing the constitutional unit charged in the reaction tank, which accounts for the amount of the compound to be introduced, may be used.
• the composition ratio (molar ratio) of the two structural units, depending on the synthesis conditions may be You may use the compound amount ratio (molar ratio) for introducing said two constitutional units.
• Component B1 may have a structural unit derived from the constituent monomer b11 and a structural unit derived from the constituent monomer b12, or other constituent units not included in the constitution represented by formula (III).
• each structural unit constituting component B1 may be random, block, or graft.
• Component B2 Water-soluble anionic condensate>
• Component B2 in one or more embodiments, is a water-soluble anionic condensate with benzene or naphthalene rings in the backbone.
• component B2 is an anionic condensate containing a structural unit having an anionic group on the benzene ring or naphthalene ring of the main chain (hereinafter also simply referred to as "anionic structural unit").
• the anionic group in the anionic constitutional unit is, in one or more embodiments, -SO 3 M 12 or -PO 3 M 13 M 14 , M 12 , M 13 and M 14 being the same or different, an alkali metal ions, alkaline earth metal ions, organic cations, ammonium (NH 4 + ) or hydrogen atoms.
• at least one hydrogen atom of a benzene ring or a naphthalene ring constituting the main chain is a sulfonic acid group from the viewpoint of ensuring water solubility and suppressing the polishing speed and dishing speed of a silicon nitride film during overpolishing. It is preferred to have substituted structures.
• aromatic monomers from which anionic structural units are derived include at least one selected from phenolsulfonic acid, naphthalenesulfonic acid, and salts thereof.
• Component B2 may be one type or a combination of two or more types. Ingredient B2 is, in one or more embodiments, exclusive of ingredient B1. A combination of components B1 and B2 may also be used.
• Component B2 can further contain structural units other than anionic structural units.
• structural units other than anionic structural units may be represented by the following formula ( VI) (hereinafter also simply referred to as “structural unit b21”) and structural unit b22 represented by the following formula (VII) (hereinafter simply referred to as “structural unit b22”) At least one structural unit is included.
• the structural unit b21 is a structural unit represented by the following formula (VI).
• R 7 and R 8 are the same or different and represent a hydrogen atom or -OM 15
• M 15 is at least one selected from alkali metals, alkaline earth metals, organic cations, ammonium and hydrogen atoms
• R9 and R10 are the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group or -OM16
• M16 is an alkali metal, an alkaline earth metal, an organic cation, ammonium and a hydrogen atom
• X 3 is a bond, —CH 2 —, —S—, —SO 2 —, —C(CH 3 ) 2 —, or is.
• R 7 and R 8 are preferably —OH from the viewpoint of securing the polishing rate and suppressing the polishing rate and dishing rate of the silicon nitride film during overpolishing.
• R 9 and R 10 are preferably hydrogen atoms or alkyl groups, more preferably hydrogen atoms, from the viewpoint of securing the polishing rate.
• X 3 is preferably —SO 2 — from the viewpoint of securing the polishing speed and suppressing the polishing speed and dishing speed of the silicon nitride film during overpolishing.
• Examples of monomers forming the structural unit b21 include bis(4-hydroxyphenyl)sulfone (BisS) and bis(4-hydroxy-3-methylphenyl)sulfone (BSDM).
• the structural unit b22 is a structural unit represented by the following formula (VII).
• R 11 represents a hydrogen atom or -OM 17
• M 17 is at least one selected from alkali metals, alkaline earth metals, organic cations, ammonium and hydrogen atoms
• R 12 is a hydrogen atom.
• R 11 is preferably —OH from the viewpoint of securing the polishing rate and suppressing the polishing rate and dishing rate of the silicon nitride film during overpolishing
• R 12 is preferably a hydrogen atom or an alkyl group from the viewpoint of securing the polishing rate and suppressing the polishing rate and dishing rate of the silicon nitride film during overpolishing.
• Examples of monomers forming the structural unit b22 include p-cresol and phenol.
• Component B2 includes a condensate of an aromatic monomer having an aromatic ring and an anionic group, an anionic structural unit, and the like, from the viewpoint of securing the polishing rate and suppressing the polishing rate and dishing rate of a silicon nitride film during overpolishing.
• Examples include condensates containing structural units other than anionic structural units, and salts thereof. Salts include alkali metal ions such as sodium salts, ammonium salts, organic amine salts and the like.
• the condensate of an aromatic monomer having an aromatic ring and an anionic group or a salt thereof is selected from the viewpoints of securing the polishing rate and suppressing the polishing rate and dishing rate of a silicon nitride film during overpolishing.
• a condensate having a structure in which at least one hydrogen atom of the ring is substituted with a sulfonic acid group or a salt thereof is preferred, and at least one selected from phenolsulfonic acid, naphthalenesulfonic acid and salts thereof is more preferred.
• a condensate containing an anionic structural unit and a structural unit other than the anionic structural unit or a salt thereof from the viewpoint of securing the polishing rate and suppressing the polishing rate and dishing rate of the silicon nitride film during overpolishing, an anionic At least one selected from a condensate containing a structural unit and at least one structural unit selected from structural unit b21 and structural unit b22, and salts thereof, is preferred.
• component B2 examples include condensates of phenolsulfonic acid, condensates of naphthalenesulfonic acid, condensates of bis(4-hydroxyphenyl)sulfone (BisS) and phenolsulfonic acid, condensates of p-cresol and phenolsulfonic acid, At least one selected from condensates of bis(4-hydroxy-3-methylphenyl)sulfone (BSDM) and phenolsulfonic acid, and condensates of phenol and phenolsulfonic acid.
• BSDM bis(4-hydroxy-3-methylphenyl)sulfone
• component B2 is a condensate containing an anionic structural unit and at least one structural unit selected from structural unit b21 and structural unit b22, the anionic structural unit and the structural unit in all structural units of component B2
• the molar ratio to the unit b21 or the structural unit b22 is effective for suppressing the polishing rate and dishing rate of the silicon nitride film during overpolishing, From the viewpoint of sexuality, 100/0 to 50/50 is preferred, 99/1 to 60/40 is more preferred, and 98/2 to 70/30 is even more preferred.
• Component B2 may further have structural units other than the anionic structural units and structural units b21 and b22.
• Other structural units include benzenesulfonic acid, halogenated derivatives of benzenesulfonic acid, alkylbenzenesulfonic acid, halogenated derivatives of naphthalenesulfonic acid, alkylnaphthalenesulfonic acid, toluenesulfonic acid, and benzoic acid.
• Component B3 in one or more embodiments, is a copolymer containing structural units derived from styrene and monomers having an anionic group. From the viewpoint of improving the polishing rate and flatness, component B3 contains a structural unit derived from styrene (St) (hereinafter also referred to as “structural unit b31"), acrylic acid (AAc), methacrylic acid, maleic acid (MA), and A copolymer containing at least one monomer-derived structural unit (hereinafter also referred to as "structural unit b32") selected from these salts is preferred. Salts include alkali metal salts, alkaline earth metal salts, ammonium salts, organic ammonium salts and the like. Component B3 may be one type or a combination of two or more types.
• component B3 examples include at least one selected from styrene/acrylic acid copolymer (St/AAc) and styrene/maleic acid copolymer (St/MA).
• the content (mol%) of the structural unit b31 in all the structural units of the component B3 is preferably 3 or more, more preferably 5 or more, and still more preferably 8 or more from the viewpoint of suppressing dishing, and from the viewpoint of water solubility. , is preferably 80 or less, more preferably 70 or less, and even more preferably 50 or less.
• Component B3 may further contain structural units other than structural units b31 and b32.
• Other structural units include vinyl phosphoric acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and the like.
• Component B3 can be obtained, for example, by a known method such as solution polymerization of a monomer mixture containing styrene and at least one monomer selected from acrylic acid, methacrylic acid, maleic acid and salts thereof.
• Aromatic hydrocarbons such as toluene and xylene; alcohols such as ethanol and 2-propanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and diethylene glycol dimethyl ether; .
• a polymerization initiator used for polymerization a known radical initiator can be used, and examples thereof include ammonium persulfate.
• a chain transfer agent can be further used in the polymerization, and examples thereof include thiol chain transfer agents such as 2-mercaptoethanol and ⁇ -mercaptopropionic acid.
• thiol chain transfer agents such as 2-mercaptoethanol and ⁇ -mercaptopropionic acid.
• the content of each structural unit in all structural units of component B3 can be regarded as the ratio of the amount of each monomer used to the total amount of monomers used for polymerization.
• each structural unit constituting component B3 may be random, block, or graft.
• the weight average molecular weight of component B is preferably 1,500 or more, more preferably 4,000 or more, still more preferably 9,000 or more, from the viewpoint of dishing suppression, and preferably 100,000 or less from the viewpoint of polishing rate. , 80,000 or less is more preferable, and 50,000 or less is even more preferable. More specifically, the weight-average molecular weight of component B is preferably 1,500 or more and 100,000 or less, more preferably 4,000 or more and 80,000 or less, and even more preferably 9,000 or more and 50,000 or less. In the present disclosure, the weight average molecular weight is a value measured using gel permeation chromatography (GPC) under the conditions described in Examples.
• GPC gel permeation chromatography
• the weight-average molecular weight of component B1 is preferably 1,500 or more, more preferably 5,000 or more, still more preferably 9,000 or more, from the viewpoint of suppressing dishing. From the viewpoint of, 100,000 or less is preferable, 80,000 or less is more preferable, and 50,000 or less is still more preferable. More specifically, the weight average molecular weight of component B1 is preferably 1,500 or more and 100,000 or less, more preferably 4,000 or more and 80,000 or less, and even more preferably 9,000 or more and 50,000 or less. When component B is component B2, the weight average molecular weight of component B2 is preferably 1,500 or more, more preferably 2,000 or more, still more preferably 4,000 or more, from the viewpoint of suppressing dishing.
• the weight average molecular weight of component B2 is preferably 1,500 or more and 50,000 or less, more preferably 2,000 or more and 40,000 or less, and even more preferably 4,000 or more and 20,000 or less.
• the weight average molecular weight of component B3 is preferably 1,500 or more, more preferably 2,000 or more, still more preferably 3,000 or more, from the viewpoint of suppressing dishing.
• 100,000 or less is preferable, 50,000 or less is more preferable, and 30,000 or less is still more preferable.
• the weight average molecular weight of component B3 is preferably 1,500 or more and 100,000 or less, more preferably 2,000 or more and 50,000 or less, and even more preferably 3,000 or more and 30,000 or less.
• the content of component B in the polishing composition of the present disclosure is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.02% by mass or more. And, from the viewpoint of the polishing rate, it is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and still more preferably 0.1% by mass or less. More specifically, the content of component B is more preferably 0.005% by mass or more and 0.5% by mass or less, further preferably 0.01% by mass or more and 0.3% by mass or less, and 0.02% by mass. Above 0.1% by mass or less is more preferable. When component B is a combination of two or more, the content of component B refers to their total content.
• the mass ratio B/A of the content of component B to the content of component A in the polishing composition of the present disclosure is preferably 0.01 or more, and preferably 0.03 or more, from the viewpoint of improving polishing speed and improving flatness. is more preferably 0.05 or more, and from the same viewpoint, it is preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.2. More specifically, the mass ratio B/A is preferably 0.01 or more and 0.5 or less, more preferably 0.03 or more and 0.3 or less, and preferably 0.05 or more and 0.2 or less.
• the polishing composition of the present disclosure contains an unsaturated cyclic compound (hereinafter also simply referred to as "component C").
• Component C is an unsaturated cyclic compound having a functional group represented by the following formula (I) or formula (II) in the cyclic skeleton.
• Component C may be one type or a combination of two or more types.
• unsaturated rings contained in unsaturated cyclic compounds include unsaturated heterocycles.
• the unsaturated heterocyclic ring preferably has at least one nitrogen atom or one oxygen atom in the heterocyclic ring from the viewpoint of improving the polishing rate and flatness.
• Component C in one or more embodiments, is an unsaturated cyclic compound having a functional group represented by the following formula (I) in the cyclic skeleton.
• Y represents OM 1 or SM 2
• M 1 and M 2 are the same or different and represent an alkali metal ion, an alkaline earth metal ion, an organic cation, ammonium (NH 4 + ) or a hydrogen atom. indicates From the viewpoint of tautomerism, component C can also be said to be an unsaturated cyclic compound having a functional group represented by the following formula (I') in the cyclic skeleton.
• N-oxide compounds containing a nitrogen-containing heteroaromatic ring skeleton having a hydroxyl group and salts thereof (hereinafter also referred to as "component C1"), containing a nitrogen-containing heteroaromatic ring skeleton having a thiol group at the ortho position of the N-oxide group
• component C1 nitrogen-containing heteroaromatic ring skeleton having a hydroxyl group and salts thereof
• component C2 examples thereof include N-oxide compounds and salts thereof (hereinafter referred to as "component C2").
• an N-oxide compound refers to a compound having an N-oxide group (N ⁇ O group) in one or more embodiments.
• the N-oxide compound can have one or more N ⁇ O groups, and one N ⁇ O group is preferred from the standpoint of availability.
• Component C1 in one or more embodiments, is an N-oxide compound containing a nitrogen-containing heteroaromatic ring skeleton having a hydroxyl group ortho-positioned to the N-oxide group and a salt thereof.
• Examples of the above salts include alkali metal salts, alkaline earth metal salts, organic amine salts, ammonium salts and the like.
• Component C1 may be used singly or in combination of two or more.
• At least one nitrogen atom contained in the nitrogen-containing heteroaromatic skeleton of component C1 forms an N-oxide.
• the nitrogen-containing heteroaromatic ring contained in component C1 includes a monocyclic or bicyclic condensed ring.
• the number of nitrogen atoms in the nitrogen-containing heteroaromatic ring contained in component C1 is, in one or more embodiments, 1 to 3, preferably 1 or 2, and 1 from the viewpoint of improving the polishing rate. more preferred.
• the nitrogen-containing heteroaromatic ring skeleton contained in component C1 includes at least one selected from pyridine N-oxide skeletons, quinoline N-oxide skeletons, and the like.
• the pyridine N-oxide skeleton indicates a structure in which the nitrogen atoms contained in the pyridine ring form an N-oxide.
• a quinoline N-oxide skeleton indicates a structure in which a nitrogen atom contained in a quinoline ring forms an N-oxide.
• an N-oxide compound containing a pyridine ring having a hydroxy group at the ortho position of the N-oxide group of the pyridine ring, a hydroxy group at the ortho position of the N-oxide group of the quinoline ring and at least one selected from N-oxide compounds containing a quinoline ring having and salts thereof are preferred as component C1 from the viewpoints of improving the polishing speed and water solubility.
• component C1 examples include at least one selected from 2-hydroxypyridine N-oxide and salts thereof.
• Component C2 in one or more embodiments, is an N-oxide compound or a salt thereof containing a nitrogen-containing heteroaromatic ring skeleton having a thiol group at the ortho-position to the N-oxide group of the nitrogen-containing heteroaromatic ring skeleton.
• Examples of the above salts include alkali metal salts, alkaline earth metal salts, organic amine salts, ammonium salts and the like.
• Component C2 may be used singly or in combination of two or more.
• At least one nitrogen atom contained in the nitrogen-containing heteroaromatic skeleton of component C2 forms an N-oxide.
• the nitrogen-containing heteroaromatic ring contained in component C2 includes a monocyclic or bicyclic condensed ring.
• the number of nitrogen atoms in the nitrogen-containing heteroaromatic ring contained in component C2 is, in one or more embodiments, 1 to 3, preferably 1 or 2, and 1 from the viewpoint of improving the polishing rate. more preferred.
• the nitrogen-containing heteroaromatic ring skeleton contained in component C2 includes at least one selected from a pyridine N-oxide skeleton, a quinoline N-oxide skeleton, and the like.
• the pyridine N-oxide skeleton indicates a structure in which the nitrogen atoms contained in the pyridine ring form an N-oxide.
• a quinoline N-oxide skeleton indicates a structure in which a nitrogen atom contained in a quinoline ring forms an N-oxide.
• an N-oxide compound containing a pyridine ring having a thiol group (—SH) at the ortho position of the N-oxide group of the pyridine ring, ortho of the N-oxide group of the quinoline ring At least one selected from N-oxide compounds containing a quinoline ring having a thiol group (--SH) at the position and salts thereof.
• an N-oxide compound containing a pyridine ring having a thiol group (--SH) at the ortho-position to the N-oxide group of the pyridine ring or a salt thereof is preferable as component B2 from the viewpoint of improving the polishing rate.
• component C2 examples include 2-mercaptopyridine N-oxide or salts thereof.
• Component C in one or more embodiments, is an unsaturated cyclic compound having a functional group represented by the following formula (II) in the cyclic skeleton.
• M 3 represents an alkali metal ion, an alkaline earth metal ion, an organic cation, ammonium (NH 4 + ) or a hydrogen atom.
• the unsaturated cyclic compound having a functional group represented by formula (II) in the cyclic skeleton includes a keto group and an ortho
• a compound containing an oxygen-containing heterocyclic skeleton having a hydroxyl group at the position or a salt thereof (hereinafter also referred to as "component C3") can be mentioned.
• the above salts include alkali metal salts, alkaline earth metal salts, organic amine salts such as ethanolamine salts, and ammonium salts.
• Component C3 may be used singly or in combination of two or more.
• the oxygen-containing heterocyclic ring contained in component C3 includes, in one or more embodiments, a monocyclic or bicyclic condensed ring. In one or a plurality of embodiments, the number of oxygen atoms in the oxygen-containing heterocyclic ring contained in component C3 is preferably 1 from the viewpoint of improving the polishing rate.
• the oxygen-containing heterocyclic skeleton contained in component C3 includes, in one or more embodiments, a pyran skeleton.
• component C3 examples include maltol and ethyl maltol.
• the content of Component C in the polishing composition of the present disclosure is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, from the viewpoint of suppressing dishing. 0.0015% by mass or more is more preferable, and from the viewpoint of polishing rate, 0.1% by mass or less is preferable, 0.04% by mass or less is more preferable, and 0.015% by mass or less is even more preferable. More specifically, the content of Component C is preferably 0.0001% by mass or more and 0.1% by mass or less, more preferably 0.001% by mass or more and 0.04% by mass or less, and 0.0015% by mass or more. 0.015% by mass or less is more preferable. When component C is a combination of two or more, the content of component C refers to their total content.
• the mass ratio B/C of the content of component B to the content of component C in the polishing composition of the present disclosure is preferably 1 or more, and 2 or more from the viewpoint of polishing rate. More preferably, 3 or more is still more preferable, 5 or more is still more preferable, 8 or more is still more preferable, and from the viewpoint of suppressing dishing, 100 or less is preferable, 50 or less is more preferable, 30 or less is more preferable, and 25 or less is further preferable. preferable.
• the mass ratio B/C is preferably 1 or more and 100 or less, more preferably 2 or more and 100 or less, still more preferably 3 or more and 50 or less, even more preferably 5 or more and 30 or less, and further preferably 8 or more and 25 or less. preferable.
• the aqueous medium contained in the polishing composition of the present disclosure includes water such as distilled water, ion-exchanged water, pure water and ultrapure water, or a mixed solvent of water and a solvent.
• the solvent include water-miscible solvents (for example, alcohol such as ethanol).
• the aqueous medium is a mixed solvent of water and a solvent, the ratio of water to the entire mixed medium may not be particularly limited as long as the effects of the present disclosure are not hindered. , is preferably 95% by mass or more, more preferably 98% by mass or more.
• the aqueous medium is preferably water, more preferably ion-exchanged water or ultrapure water, and still more preferably ultrapure water.
• the content of the aqueous medium in the polishing composition of the present disclosure can be the remainder after removing component A, component B, component C, and optional components described later that are blended as necessary.
• the polishing composition of the present disclosure further contains other components such as a pH adjuster, a polymer other than component B, a surfactant, a thickener, a dispersant, an antirust agent, an antiseptic, and a basic substance. be able to.
• the polishing composition of the present disclosure is manufactured by a manufacturing method including, for example, a step of blending component A, component B, component C, an aqueous medium, and optionally the above optional components (other components) by a known method.
• the polishing composition of the present disclosure can be made by blending at least component A, component B, component C and an aqueous medium.
• "blending" includes mixing component A, component B, component C, an aqueous medium, and optionally the optional components (other components) described above simultaneously or in order. The order of mixing is not particularly limited.
• the blending can be performed using a mixer such as a homomixer, a homogenizer, an ultrasonic disperser, and a wet ball mill.
• the blending amount of each component in the method for producing the polishing composition of the present disclosure can be the same as the content of each component in the polishing composition of the present disclosure described above.
• Embodiments of the polishing composition of the present disclosure may be a so-called one-component type in which all components are premixed and supplied to the market, or a so-called two-component type in which they are mixed at the time of use.
• a two-part polishing composition is composed of a first liquid containing a component A and a second liquid containing a component B and a component C, and when used, the first liquid and the second liquid are mixed.
• the first liquid and the second liquid may be mixed before being supplied to the surface to be polished, or they may be separately supplied and mixed on the surface of the substrate to be polished.
• the first liquid and the second liquid can each contain the optional components described above as necessary.
• the pH of the polishing composition of the present disclosure is preferably 3.5 or higher, more preferably 4 or higher, still more preferably 5 or higher, from the viewpoint of improving the polishing rate, and preferably 9 or lower from the viewpoint of suppressing dishing. 8.5 or less is more preferable, and 8 or less is even more preferable. More specifically, the pH is preferably 3.5 or more and 9 or less, more preferably 4 or more and 8.5 or less, and even more preferably 5 or more and 8 or less.
• the pH of the polishing composition is a value at 25° C. and can be measured using a pH meter, specifically by the method described in Examples.
• the content of each component in the polishing composition refers to the content of each component at the time when the polishing composition is started to be used for polishing.
• the polishing composition of the present disclosure may be stored and supplied in a concentrated state to the extent that its stability is not impaired. In this case, it is preferable in that manufacturing and transportation costs can be reduced.
• This concentrated solution can be used in the polishing step after being appropriately diluted with the aforementioned aqueous medium, if necessary.
• the dilution ratio is preferably 5 to 100 times.
• the polishing composition of the present disclosure can be used in processes requiring polishing of silicon oxide films.
• the polishing composition of the present disclosure is used to polish a silicon oxide film in the step of forming an element isolation structure of a semiconductor substrate, and polish a silicon oxide film in the step of forming an interlayer insulating film. It can be suitably used for polishing a silicon oxide film in a process of forming an embedded metal wiring, or polishing a silicon oxide film in a process of forming an embedded capacitor.
• the polishing composition of the present disclosure can be suitably used for manufacturing a three-dimensional semiconductor device such as a three-dimensional NAND flash memory.
• the present disclosure relates to a kit for preparing the polishing composition of the present disclosure (hereinafter also referred to as “polishing composition kit of the present disclosure”).
• a polishing liquid kit of the present disclosure for example, an abrasive dispersion liquid (first liquid) containing component A and an aqueous medium and an additive aqueous solution (second liquid) containing component B and component C are mixed with each other.
• Polishing liquid kits two-pack type polishing liquid compositions, which are contained in an uncured state, are mixed at the time of use, and are diluted with an aqueous medium as necessary.
• the aqueous medium contained in the abrasive dispersion (first liquid) may be the entire amount or a part of the aqueous medium used for preparing the polishing composition.
• the additive aqueous solution (second liquid) may contain a part of the aqueous medium used for preparing the polishing composition.
• the abrasive dispersion (first liquid) and the additive aqueous solution (second liquid) may each contain optional components (other components) described above, if necessary.
• the abrasive grain dispersion liquid (first liquid) and the additive aqueous solution (second liquid) may be mixed before being supplied to the surface of the object to be polished, or they may be separately supplied to the surface to be polished. Mixing may occur on the surface of the substrate.
• the polishing liquid kit of the present disclosure it is possible to obtain a polishing liquid composition capable of improving the flatness of the substrate surface after polishing while ensuring the polishing rate of the silicon oxide film.
• a polishing method comprising the step of polishing a film-to-be-polished using the polishing composition of the present disclosure, wherein the film-to-be-polished is a silicon oxide film formed in the process of manufacturing a semiconductor substrate.
• a polishing method of the present disclosure By using the polishing method of the present disclosure, it is possible to improve the flatness of the substrate surface after polishing while ensuring the polishing speed of the silicon oxide film, so that the productivity of semiconductor substrates with improved quality can be improved. effect can be achieved.
• the specific polishing method and conditions can be the same as those of the semiconductor substrate manufacturing method of the present disclosure, which will be described later.
• a semiconductor substrate comprising a step of polishing a film-to-be-polished using the polishing composition of the present disclosure (hereinafter also referred to as “polishing step using the polishing composition of the present disclosure”). (hereinafter also referred to as “method for manufacturing a semiconductor substrate of the present disclosure”).
• the method for manufacturing a semiconductor substrate of the present disclosure includes, for example, a step of polishing the surface of the silicon oxide film opposite to the surface in contact with the silicon nitride film, for example, the uneven stepped surface of the silicon oxide film, using the polishing liquid composition of the present disclosure.
• the present invention relates to a method for manufacturing a semiconductor device, including According to the method for manufacturing a semiconductor device of the present disclosure, it is possible to improve the flatness of the surface of the substrate after polishing while ensuring the polishing rate of the silicon oxide film, so that it is possible to efficiently manufacture the semiconductor device. can be
• the uneven stepped surface of the silicon oxide film may be naturally formed corresponding to the uneven stepped surface of the lower layer of the silicon oxide film, for example, when the silicon oxide film is formed by a method such as chemical vapor deposition. Alternatively, it may be one obtained by forming an uneven pattern using a lithography method or the like.
• a silicon substrate is exposed to oxygen in an oxidation furnace to grow a silicon dioxide layer on its surface, and then a silicon nitride (Si A polishing stopper film such as a 3 N 4 ) film or a polysilicon film is formed by, for example, a CVD method (chemical vapor deposition method).
• a substrate including a silicon substrate and a polishing stopper film disposed on one main surface side of the silicon substrate for example, a substrate having a polishing stopper film formed on a silicon dioxide layer of a silicon substrate is subjected to a photolithographic technique. is used to form trenches.
• a silicon oxide (SiO 2 ) film which is a film to be polished for embedding trenches, is formed by, for example, a CVD method using silane gas and oxygen gas, and the polishing stopper film is covered with the film to be polished (silicon oxide film).
• a substrate to be polished is obtained.
• the silicon oxide film By forming the silicon oxide film, the trench is filled with the silicon oxide of the silicon oxide film, and the surface of the polishing stopper film opposite to the silicon substrate side is covered with the silicon oxide film.
• the surface of the silicon oxide film thus formed opposite to the surface facing the silicon substrate has steps formed corresponding to the unevenness of the lower layer.
• the silicon oxide film is polished by a CMP method until at least the surface of the polishing stopper film opposite to the silicon substrate side is exposed, and more preferably, the surface of the silicon oxide film and the surface of the polishing stopper film are flush with each other. Polish the silicon oxide film until it becomes
• the polishing liquid composition of the present disclosure can be used in this step of polishing by the CMP method.
• the width of the protrusion formed corresponding to the unevenness of the lower layer of the silicon oxide film is, for example, 0.5 ⁇ m or more and 5000 ⁇ m or less, and the width of the recess is, for example, 0.5 ⁇ m or more and 5000 ⁇ m or less.
• the substrate to be polished and the polishing pad are relatively moved while supplying the polishing liquid composition of the present disclosure to the contact area.
• the polishing stopper film for example, silicon oxide film
• Another insulating film may be formed between the polishing stopper film (for example, silicon nitride film, polysilicon film).
• the rotational speed of the polishing pad is, for example, 30 to 200 rpm/min
• the rotational speed of the substrate to be polished is, for example, 30 to 200 rpm/min.
• the polishing load set in the polishing apparatus can be set to, for example, 20 to 500 gf/cm 2
• the supply rate of the polishing liquid composition can be set to, for example, 10 to 500 mL/min or less.
• conventionally known materials can be used for the material of the polishing pad used.
• the material of the polishing pad include organic polymer foams such as rigid polyurethane foams and non-foamed bodies. Among these, rigid polyurethane foams are preferred.
• polishing composition (Examples 1 to 8, Comparative Examples 1 to 7)
• cerium oxide particles (component A), the anionic polymer (component B or non-component B) shown in Table 1, the unsaturated cyclic compound (component C) shown in Table 2, and water were mixed, and the 8 and Comparative Examples 1 to 7 were obtained.
• the content (% by mass) of each component in the polishing composition is as shown in Table 3, and the content of water is the remainder after component A and component B or non-component B and component C are removed. . pH adjustments were performed using ammonia or nitric acid.
• Cerium oxide particles (component A) Ground ceria [average primary particle size: 49.5 nm, BET specific surface area: 16.8 m 2 /g, surface potential: -50 mV]
• Water-soluble anionic polymer component B or non-component B
• the formaldehyde (co)condensate is obtained by adding formalin at 85 to 105° C. so that the amount of formaldehyde is 0.93 to 0.99 mol per 1 mol of the total amount of monomers. , was added dropwise over 3 to 6 hours, and after the dropwise addition, the condensation reaction was carried out at 95 to 105° C. over 4 to 9 hours.
• the ratio of the constituent monomers in the copolymer was adjusted by the blending amount (molar ratio) of the monomers.
• Unsaturated cyclic compound (component C) (Component C1) HOPO [2-hydroxypyridine N-oxide, manufactured by Tokyo Chemical Industry Co., Ltd.] (Component C3) Ethyl maltol [manufactured by Tokyo Chemical Industry Co., Ltd.]
• pH of polishing composition The pH value of the polishing composition at 25° C. is a value measured using a pH meter (“HW-41K” manufactured by Toa DKK Co., Ltd.). It is the number after minutes.
• the average primary particle size (nm) of the cerium oxide particles (component A) is the specific surface area S (m 2 /g), the true density of the cerium oxide particles was calculated as 7.2 g/cm 3 .
• BET Specific Surface Area of Cerium Oxide Particles (Component A) The specific surface area was obtained by drying a cerium oxide particle dispersion liquid with hot air at 120° C. for 3 hours and finely pulverizing it with an agate mortar. After drying for 15 minutes in an atmosphere of 120 ° C. immediately before the measurement, it was measured by the nitrogen adsorption method (BET method) using a specific surface area measuring device (Micromeritic automatic specific surface area measuring device "Flowsorb III 2305", manufactured by Shimadzu Corporation). .
• polystyrene sodium conversion (monodisperse sodium polystyrene sulfonate: molecular weight, 206, 1,800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000)
• Detector Tosoh Corporation UV-8020
• Test piece A silicon oxide film test piece (blanket substrate) was obtained by forming a silicon oxide film (blanket film) having a thickness of 2000 nm on one side of a silicon wafer by the TEOS-plasma CVD method.
• Pattern substrate A commercially available wafer for CMP characteristics evaluation (“P-TEOS MIT864 PT wafer” manufactured by Advantec, diameter 300 mm) was used as a pattern substrate for evaluation.
• a silicon nitride film with a thickness of 150 nm as a first layer and a silicon oxide film with a thickness of 450 nm as a second layer are arranged as convex portions, and concave portions are also silicon oxide films with a thickness of 450 nm. are arranged, and a linear concave-convex pattern is formed by etching such that the difference in level between the convex portion and the concave portion is 350 nm.
• the silicon oxide film was made of P-TEOS, and the line width of each of the projections and recesses was 100 ⁇ m.
• polishing Rate of Silicon Oxide Film on Protrusions Using each polishing liquid composition, the test piece was polished under the following polishing conditions. After polishing, the sample was washed with ultrapure water and dried, and the test piece was used as an object to be measured by an optical interference type film thickness measuring device described later.
• Amount of dishing during overpolishing 20 of the time (planarization time) required for the silicon oxide film on the projections to be flattened after the silicon oxide film on the projections was flattened and the silicon nitride film was exposed. % of time, and the film thickness of the silicon oxide film in the recesses before and after the overpolishing was measured using ASET F5x (manufactured by KLA-Tencor). The amount of dishing during overpolishing was calculated by the following formula. Polishing amount (nm) of the recess after the nitride film is exposed height of protrusions when nitride film is exposed (nm) - height of recesses after polishing (nm) Table 3 shows the above results.
• the polishing composition of the present disclosure is useful in a method for manufacturing a semiconductor substrate for high density or high integration.

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