Classifications

• • 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
• • 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
  • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
  • H01L21/3105—After-treatment
  • H01L21/31051—Planarisation of the insulating layers
  • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
  • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
• • 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
• • 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
  • C09G1/04—Aqueous dispersions
• • 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
  • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
  • C09K3/1463—Aqueous liquid suspensions
• • 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
• • 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
  • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
  • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
• • 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
  • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
  • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
  • H01L21/321—After treatment
  • H01L21/32115—Planarisation
  • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
• • 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

Definitions

• the high-K metal gate module was introduced for modern logic devices (45 nm technology node and beyond) for performance improvement.
• the replacement metal gate (gate-last) approach has become the mainstream technology for the high-k metal gate module in advanced device manufacturing, especially for 20 nm and beyond.
• CMP processes including selective oxide/nitride polishing, poly open polishing (POP) and self aligned contact (SAC), must be optimized to meet the stringent planarity and defect requirements. While there exist multiple processes for fabricating the devices, frequently silicon nitride is used as a capping layer and as an etch stop layer.
• RMG replacement metal gate
• nitride to oxide selectivity is needed for POP polishing to meet the stringent requirements in the RMG process.
• the challenge in SAC similarly requires a higher selectivity of nitride to oxide which provides excellent planarization efficiency and topography.
• the invention provides a chemical-mechanical polishing composition
• a chemical-mechanical polishing composition comprising (a) colloidal silica particles that are surface modified with metal ions selected from Mg, Ca, Al, B, Be, and combinations thereof, and wherein the colloidal silica particles have a surface hydroxyl group density of from about 1.5 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 of a surface area of the particles, (b) an anionic surfactant, (c) a buffering agent, and (d) water, wherein the polishing composition has a pH of about 2 to about 7, and wherein the polishing composition is free or substantially free of an oxidizing agent that oxidizes a metal.
• the invention also provides a method of chemically mechanically polishing a substrate comprising (i) contacting a substrate with a polishing pad and a chemical- mechanical polishing composition comprising (a) colloidal silica particles that are surface modified with metal ions selected from Mg, Ca, Al, B, Be, and combinations thereof, and wherein the colloidal silica particles have a surface hydroxyl group density of from about 1.5 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 of a surface area of the particles, (b) an anionic surfactant, (c) a buffering agent, and (d) water, wherein the polishing composition has a pH of about 2 to about 7, and wherein the polishing composition is free or substantially free of an oxidizing agent that oxidizes a metal, (ii) moving the polishing pad and the chemical mechanical polishing composition relative to the substrate, and (iii) abrading at least a portion of the substrate to polish the substrate.
• a chemical- mechanical polishing composition comprising
• the invention provides a chemical-mechanical polishing composition
• a chemical-mechanical polishing composition comprising, consisting essentially of, or consisting of (a) colloidal silica particles that are surface modified with metal ions selected from Mg, Ca, Al, B, Be, and combinations thereof, and wherein the colloidal silica particles have a surface hydroxyl group density of from about 1.5 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 of a surface area of the particles, (b) an anionic surfactant, (c) a buffering agent, and (d) water, wherein the polishing composition has a pH of about 2 to about 7, and wherein the polishing composition is free or substantially free of an oxidizing agent that oxidizes a metal.
• the polishing composition comprises an abrasive consisting of colloidal silica particles that are surface-modified with metal ions selected from Mg, Ca, Al, B, Be, and combinations thereof.
• the metal ions are aluminum ions (i.e., Al(III)).
• the colloidal silica particles can be any suitable colloidal silica particles and are typically "wet-process" colloidal silica particles.
• "wet-process" silica refers to a silica prepared by a precipitation, condensation-polymerization, or similar process (as opposed to, for example, fumed or pyrogenic silica).
• the colloidal silica particles are prepared in the absence of a metal ion, such that the colloidal silica particles, prior to surface modification with metal ions selected from Mg, Ca, Al, B, and/or Be, are free or substantially free of metal ions.
• the colloidal silica particles are prepared by
• the precursor Si(OH) 4 can be obtained, for example, by hydrolysis of high purity alkoxysilanes such as tetraethylorthosilicate (TEOS).
• TEOS tetraethylorthosilicate
• colloidal silica can be obtained as various commercially available products, such as the Fuso PL-1, PL-1H, PL-1SL, PL-2, PL-2L, PL-3, PL-3H, PL-3L, PL-5, PL-6L, PL-7, PL-7H, PL-10H, PL-SH3 and PL-20 products, and the Nalco 1050, 2327, and 2329 products, as well as other similar products available from DuPont, Bayer, Applied Research, Nissan Chemical, and Clariant.
• the colloidal silica particles can have a surface hydroxyl group density of about 1.5 hydroxyls per nm 2 of the surface area of the particles or more, for example, about 1.6 hydroxyls per nm 2 or more, about 1.7 hydroxyls per nm 2 or more, about 1.8 hydroxyls per nm 2 or more, about 1.9 hydroxyls per nm 2 or more, about 2.0 hydroxyls per nm 2 or more, about 2.2 hydroxyls per nm 2 or more, about 2.4 hydroxyls per nm 2 or more, about 2.6 hydroxyls per nm 2 or more, about 2.8 hydroxyls per nm 2 or more, about 3 hydroxyls per nm 2 or more, about 4 hydroxyls per nm 2 or more, or about 5 hydroxyls per nm 2 or more.
• the colloidal silica particles can have a surface hydroxyl group density of about 8 hydroxyls per nm 2 of the surface area of the particles or less, for example, about 7.5 hydroxyls per nm 2 or less, about 7 hydroxyls per nm 2 or less, about 6.5 hydroxyls per nm 2 or less, about 6 hydroxyls per nm 2 or less, about 5.5 hydroxyls per nm 2 or less, or about 5 hydroxyls per nm 2 or less.
• the colloidal silica particles can have a surface hydroxyl group density bounded by any two of the aforementioned endpoints.
• the colloidal silica particles can have a surface hydroxyl group density of from about 1.5 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 of the surface area of the particles, about 1.6 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 , about 1.7 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 , about 1.8 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 , about 1.9 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 , about 2.0 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 , about 2.2 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 , about 2.4 hydroxyls per nm 2 to about 8 hydroxyls per nm 2 , about 2.6 hydroxyls per nm 2 to about 8 hydroxyls per , about
• the surface hydroxyl group density colloidal silica particles can be determined using any suitable method.
• an aqueous dispersion of the colloidal silica particles can be adjusted to have a pH of 4.0 to prepare a titration sample.
• the titration sample can be titrated with an aqueous sodium hydroxide solution having a known concentration to a pH of 9.0 to determine the number of hydroxyl groups present in the titration sample.
• the surface area of the colloidal silica particles can be determined using any suitable method, for example, by the BET method. The number of hydroxyl groups per nm 2 can thus be determined.
• the colloidal silica particles can be surface-modified using any suitable method.
• the colloidal silica particles are dispersed in a carrier such as water and are then surface-treated with a suitable source of metal ions.
• the source of metal ions is a water-soluble metallic salt.
• an aqueous dispersion of colloidal silica particles can be treated with an aqueous solution of a metal salt such that the surface of the colloidal silica particles becomes associated with the metal ions.
• the association of the metal ions with the surface of the colloidal silica particles is thought to involve bonding with silanol groups found on the surface of the colloidal silica particles.
• the metal ions are associated with the surface of the colloidal silica particle, and are not within the interior of the particles.
• the colloidal silica particles comprise about 0.1 or more, for example, about 0.11 or more, about 0.12 or more, about 0.13 or more, about 0.14 or more, or about 0.15 or more metal ions per nm 2 of the surface area of the particles.
• the colloidal silica particles comprise about 0.2 or less, for example, about 0.19 or less, about 0.18 or less, about 0.17 or less, or about 0.16 or less) of metal ions per nm 2 of the surface area of the particles.
• the colloidal silica particles can comprise an amount of metal ions per nm 2 of the surface area of the particles bounded by any two of the aforementioned endpoints.
• the colloidal silica particles can comprise about 0.1 to about 0.2, about 0.1 to about 0.19, about 0.1 to about 0.18, about 0.1 to about 0.17, about 0.1 to about 0.16, about 0.11 to about 0.2, about 0.12 to about 0.2, about 0.13 to about 0.2, about 0.14 to about 0.2, or about 0.15 to about 0.2 of metal ions per nm 2 of the surface area of the particles.
• the number of metal ions per nm 2 of the surface area of the particles can be determined using any suitable method.
• the surface area can be determined, for example, using a BET method.
• a dispersion of colloidal silica particles can be treated with an aqueous solution having a known concentration of metal ions. After a suitable treatment period, the concentration of metal ions remaining in solution can be determined. The difference in starting metal ion concentration and the concentration after treatment represents the amount of metal ions associated with the surface of the colloidal silica particles, thereby allowing calculation of the number of metal ions per nm 2 of the surface area of the particles.
• the colloidal silica particles can have any suitable average particle size.
• the colloidal silica particles can have an average particle size of about 20 nm or more, about 25 nm or more, about 30 nm or more, about 35 nm or more, about 40 nm or more, about 45 nm or more, or about 50 nm or more.
• the colloidal silica particles can have an average particle size of about 100 nm or less, for example, about 90 nm or less, about 80 nm or less, about 70 nm or less, or about 60 nm or less.
• the colloidal silica particles can have an average particle size bounded by any two of the aforementioned endpoints.
• the colloidal silica particles can have an average particle size of about 20 nm to about 100 nm, about 20 nm to about 90 nm, about 20 nm to about 80 nm, about 20 nm to about 70 nm, about 20 nm to about 60 nm, about 30 nm to about 100 nm, about 30 nm to about 90 nm, about 30 nm to about 80 nm, about 30 nm to about 70 nm, or about 30 nm to about 60 nm.
• the colloidal silica can have any suitable morphology.
• the colloidal silica can have a spherical morphology, an oval morphology, or a nonspherical "cocoon" morphology.
• the size of the particle is the diameter of the smallest sphere that encompasses the particle.
• the particle size of the colloidal silica particles can be measured using any suitable technique, for example, using laser diffraction techniques. Suitable particle size measurement instruments are available from e.g., Malvem Instruments (Malvern, UK).
• the colloidal silica particles preferably are colloidally stable in the inventive polishing composition.
• the term colloid refers to the suspension of particles in the liquid carrier (e.g., water).
• Colloidal stability refers to the maintenance of that suspension through time.
• an abrasive is considered colloidally stable if, when the abrasive is placed into a 100 mL graduated cylinder and allowed to stand unagitated for a time of 2 hours, the difference between the concentration of particles in the bottom 50 mL of the graduated cylinder ([B] in terms of g/mL) and the concentration of particles in the top 50 mL of the graduated cylinder ([T] in terms of g/mL) divided by the initial concentration of particles in the abrasive composition ([C] in terms of g/mL) is less than or equal to 0.5 (i.e., ⁇ [B] - [T] ⁇ /[C] ⁇ 0.5). More preferably, the value of [B]-[T
• the polishing composition can comprise any suitable amount of colloidal silica particles.
• the polishing composition can comprise about 5 wt.% or less, for example, about 4 wt.% or less, about 3 wt.% or less, about 2 wt.% or less, about 1 wt. % or less, about 0.9 wt.% or less, about 0.8 wt.% or less, about 0.7 wt.% or less, about 0.6 wt.% or less, or about 0.5 wt.% or less of colloidal silica particles.
• the polishing composition can comprise about 0.1 wt.% or more, for example, about 0.2 wt.% or more, about 0.3 wt.% or more, about 0.4 wt.% or more, about 0.5 wt.% or more, or about 1 wt.% or more of colloidal silica particles.
• the polishing composition can comprise colloidal silica particles in an amount bounded by any two of the aforementioned endpoints.
• the polishing composition can comprise about 0.1 wt.% to about 5 wt.% of colloidal silica particles, about 0.1 wt.% to about 4 wt.%, about 0.1 wt.% to about 3 wt.%, about 0.1 wt.% to about 2 wt.%, about 0.1 wt.% to about 1 wt.%, about 0.2 wt.% to about 2 wt.%, or about 0.2 wt.% to about 1 wt.% of colloidal silica particles.
• the polishing composition comprises an anionic surfactant.
• the anionic surfactant can be a polymer or copolymer of monomers comprising functional groups selected from carboxylic acids, sulfonic acids, phosphoric acids, and combinations thereof.
• the anionic surfactant is a polymer or copolymer comprising acrylic acid monomers.
• the anionic surfactant is a poly(acrylic)
• the polishing composition comprises any suitable amount of anionic surfactant.
• the polishing composition can comprise about 1 ppm or more, for example, 5 ppm or more, about 10 ppm or more, about 25 ppm or more, or about 50 ppm or more of the anionic surfactant.
• the polishing composition can comprise about 1000 ppm or less, for example, about 900 ppm or less, about 800 ppm or less, about 700 ppm or less, about 600 ppm or less, about 500 ppm or less, about 400 ppm or less, about 300 ppm or less, or about 200 ppm or less, of the anionic surfactant.
• the polishing composition can comprise the anionic surfactant in an amount bounded by any two of the aforementioned endpoints.
• the polishing composition can comprise about 1 ppm to about 1000 ppm, about 5 ppm to about 500 ppm, about 5 ppm to about 400 ppm, about 5 ppm to about 300, about 5 ppm to about 200 ppm, or about 10 ppm to about 200 ppm of the anionic surfactant, and the like.
• the anionic surfactant when the anionic surfactant is a polymer or copolymer, the anionic surfactant can have any suitable molecular weight. Typically, the anionic surfactant can have a molecular weight of about 100,000 Daltons or less, e.g., about 90,000 Daltons or less, about 80,000 Daltons or less, about 70,000 Daltons or less, about 60,000 Daltons or less, or about 50,000 Daltons or less.
• the anionic surfactant can be a polymer or copolymer comprising sulfonic acid groups.
• Non-limiting examples of polymers or copolymers comprising sulfonic acid groups include polystyrenesulfonic acid and WE001.
• the anionic surfactant can be a monomeric surfactant comprising sulfonic acid groups.
• the surfactant can be an alkyldiphenyloxide sulfonate surfactant having the structure:
• R is a C1-C30, preferably C6-C30, more preferably C6-C22, linear or branched, saturated or unsaturated alkyl group, wherein the alkyl group optionally contains one or more heteroatoms selected from the group consisting of O and N, and wherein X + is H or a cation, e.g., an alkali metal cation or alkaline earth cation (e.g., sodium, potassium, lithium, calcium, magnesium, and the like).
• a cation e.g., an alkali metal cation or alkaline earth cation (e.g., sodium, potassium, lithium, calcium, magnesium, and the like).
• alkyldiphenyloxide sulfonate surfactants examples include surfactants commercially available from the Dow Chemical Company (Midland, MI) under the trade names DowfaxTM 2A1, DowfaxTM 3B2, DowfaxTM 8390, DowfaxTM C6L, DowfaxTM CIOL, and DowfaxTM 30599.
• the anionic surfactant can be a linear or branched alkylbenzenesulfonate, such as dodecylbenzene sulfonate.
• the anionic surfactant can be in the form of a free acid, a salt thereof (e.g., a sodium, potassium, or ammonium salt) or, when the anionic surfactant possesses more than one acidic group, in the form of a partial salt thereof.
• a salt thereof e.g., a sodium, potassium, or ammonium salt
• the polishing composition can further comprise a nonionic surfactant.
• the nonionic surfactant can be any suitable nonionic surfactant.
• Non-limiting examples of suitable nonionic surfactants include BRIJTM and polyethylene oxide surfactants, PLURONICTM L-64, polyvinylmethylether, polyethylene glycol, polyoxyethylene 23 lauryl ether, polypropanoic acid, polyacrylic acid, and polyether glycol to(ether).
• the chemical-mechanical polishing composition can comprise one or more buffering agents (i.e., compounds capable of adjusting the pH of the polishing composition.
• the pH of the polishing composition can be adjusted using any suitable buffering agent capable of adjusting the pH of the polishing composition.
• the buffering agent can be any suitable buffering agent and can be an organic buffering agent or an inorganic buffering agent.
• the buffering agent can be an organic carboxylic acid, for example, acetic acid.
• the buffering agent desirably is water-soluble and compatible with the other components of the polishing composition.
• the chemical-mechanical polishing composition has a pH of about 2 to about 7 at the point-of-use.
• the buffering agent i.e., compounds capable of adjusting the pH of the polishing composition.
• the pH of the polishing composition can be adjusted using any suitable buffering agent capable of adjusting the pH of the polishing composition.
• the buffering agent can be any suitable buffering agent and can be an organic buffering agent or an inorganic buffering agent
• chemical-mechanical polishing composition has a pH of about 3 to about 4 at the point-of- use.
• the buffering agent is capable of buffering an acidic pH of the polishing composition. Accordingly, it is desirable that the pH of the polishing composition is less than 7.0, e.g., 6.5 +/- 0.5, 6.0 +/- 0.5, 5.5 +/- 0.5, 5.0 +/- 0.5, 4.5 +/- 0.5, 4.0 +/- 0.5, 3.5 +/- 0.5, 3.0 +/- 0.5, 2.5 +/- 0.5, or 2.0 +/- 0.5.
• the buffering agent typically has at least one ionizable group having a pKa of about 3 to about 7 when measured at 25° C.
• the polishing composition is free or substantially free of an oxidizing agent that oxidizes a metal.
• the phrase "free of oxidizing agent" means that the polishing composition includes no more than trace contaminant amounts of oxidizing materials, which amounts are insufficient to affect any metal removal rate obtainable with the composition during CMP.
• the polishing composition is free or substantially free of hydrogen peroxide, ferric nitrate, potassium iodate, peracetic acid, and potassium permanganate.
• the chemical-mechanical polishing composition optionally further comprises one or more additives.
• additives include conditioners, complexing agents, chelating agents, biocides, scale inhibitors, dispersants, etc.
• a biocide when present, can be any suitable biocide and can be present in the polishing composition in any suitable amount.
• a suitable biocide is an isothiazolinone biocide.
• the amount of biocide used in the polishing composition typically is about 1 to about 50 ppm, preferably about 10 to about 20 ppm.
• any of the components of the polishing composition that are acids, bases, or salts (e.g., anionic surfactant, buffering agent, etc.), when dissolved in the water of the polishing composition, can exist in dissociated form as cations and anions.
• the amounts of such compounds present in the polishing composition as recited herein will be understood to refer to the weight of the undissociated compound used in the preparation of the polishing composition.
• the polishing composition can be produced by any suitable technique, many of which are known to those skilled in the art.
• the polishing composition can be prepared in a batch or continuous process. Generally, the polishing composition is prepared by combining the components of the polishing composition.
• component includes individual ingredients (e.g., colloidal silica particles that are surface-modified with metal ions, anionic surfactant, buffering agent, and/or any optional additive) as well as any combination of ingredients (e.g., colloidal silica particles that are surface-modified with metal ions, anionic surfactant, buffering agent, etc.).
• the polishing composition can be prepared by (i) providing all or a portion of the liquid carrier, (ii) dispersing the colloidal silica particles that are
• any optional additive using any suitable means for preparing such a dispersion, (iii) adjusting the pH of the dispersion as appropriate, and (iv) optionally adding suitable amounts of any other optional components and/or additives to the mixture.
• the polishing composition can be prepared by (i) providing one or more components (e.g., liquid carrier, anionic surfactant, buffering agent, and/or any optional additive) in a slurry of colloidal silica particles that are surface-modified with metal ions, (ii) providing one or more components in an additive solution (e.g., liquid carrier, anionic surfactant, buffering agent, and/or any optional additive), (iii) combining the slurry of colloidal silica particles that are surface-modified with metal ions and the additive solution to form a mixture, (iv) optionally adding suitable amounts of any other optional additives to the mixture, and (v) adjusting the pH of the mixture as appropriate.
• one or more components e.g., liquid carrier, anionic surfactant, buffering agent, and/or any optional additive
• an additive solution e.g., liquid carrier, anionic surfactant, buffering agent, and/or any optional additive
• the polishing composition can be supplied as a one-package system comprising colloidal silica particles that are surface-modified with metal ions, anionic surfactant, buffering agent, and/or any optional additive, and water.
• the polishing composition of the invention is supplied as a two-package system comprising a slurry of colloidal silica particles that are surface-modified with metal ions and an additive solution, wherein the slurry of colloidal silica particles that are surface-modified with metal ions consists essentially of, or consists of, colloidal silica particles that are surface-modified with metal ion and water, and wherein the additive solution consists essentially of, or consists of, anionic surfactant, buffering agent, and/or any optional additive.
• the slurry of colloidal silica particles that are surface-modified with metal ions and additive solution can be delivered to the polishing table by different pipes that are joined and connected at the outlet of supply piping.
• the slurry of colloidal silica particles that are surface-modified with metal ions and additive solution can be mixed shortly or immediately before polishing, or can be supplied simultaneously on the polishing table.
• deionized water can be added, as desired, to adjust the polishing composition and resulting substrate polishing characteristics.
• each of multiple containers contains different components of the inventive chemical-mechanical polishing composition, one or more optional components, and/or one or more of the same components in different concentrations.
• the storage devices typically are provided with one or more flow lines leading from each storage device to the point-of-use of the polishing composition (e.g., the platen, the polishing pad, or the substrate surface).
• the term "point-of-use” refers to the point at which the polishing composition is applied to the substrate surface (e.g., the polishing pad or the substrate surface itself).
• flow line is meant a path of flow from an individual storage container to the point- of-use of the component stored therein.
• the flow lines can each lead directly to the point-of- use, or two or more of the flow lines can be combined at any point into a single flow line that leads to the point-of-use. Furthermore, any of the flow lines (e.g., the individual flow lines or a combined flow line) can first lead to one or more other devices (e.g., pumping device, measuring device, mixing device, etc.) prior to reaching the point-of-use of the component(s).
• devices e.g., pumping device, measuring device, mixing device, etc.
• the components of the polishing composition can be delivered to the point-of-use independently (e.g., the components are delivered to the substrate surface whereupon the components are mixed during the polishing process), or one or more of the components can be combined before delivery to the point-of-use, e.g., shortly or immediately before delivery to the point-of-use.
• Components are combined "immediately before delivery to the point-of- use” if the components are combined about 5 minutes or less prior to being added in mixed form onto the platen, for example, about 4 minutes or less, about 3 minutes or less, about 2 minutes or less, about 1 minute or less, about 45 s or less, about 30 s or less, about 10 s or less prior to being added in mixed form onto the platen, or simultaneously to the delivery of the components at the point-of-use (e.g., the components are combined at a dispenser).
• Components also are combined "immediately before delivery to the point-of-use" if the components are combined within 5 m of the point-of-use, such as within 1 m of the point-of- use or even within 10 cm of the point-of-use (e.g., within 1 cm of the point-of-use).
• the components can be combined in the flow line and delivered to the point-of-use without the use of a mixing device.
• one or more of the flow lines can lead into a mixing device to facilitate the combination of two or more of the components.
• Any suitable mixing device can be used.
• the mixing device can be a nozzle or jet (e.g., a high pressure nozzle or jet) through which two or more of the components flow.
• the mixing device can be a container-type mixing device comprising one or more inlets by which two or more components of the polishing slurry are introduced to the mixer, and at least one outlet through which the mixed components exit the mixer to be delivered to the point-of-use, either directly or via other elements of the apparatus (e.g., via one or more flow lines).
• the mixing device can comprise more than one chamber, each chamber having at least one inlet and at least one outlet, wherein two or more components are combined in each chamber.
• the mixing device preferably comprises a mixing mechanism to further facilitate the combination of the components. Mixing mechanisms are generally known in the art and include stirrers, blenders, agitators, paddled baffles, gas sparger systems, vibrators, etc.
• the polishing composition also can be provided as a concentrate which is intended to be diluted with an appropriate amount of water prior to use.
• the polishing composition concentrate comprises the components of the polishing composition in amounts such that, upon dilution of the concentrate with an appropriate amount of water, each component of the polishing composition will be present in the polishing composition in an amount within the appropriate range recited above for each component.
• the colloidal silica particles that are surface-modified with metal ions, anionic surfactant, buffering agent, and/or any optional additive can each be present in the concentrate in an amount that is about 2 times (e.g., about 3 times, about 4 times, or about 5 times) greater than the concentration recited above for each component so that, when the concentrate is diluted with an equal volume of water (e.g., 2 equal volumes water, 3 equal volumes of water, or 4 equal volumes of water, respectively), each component will be present in the polishing composition in an amount within the ranges set forth above for each component.
• an equal volume of water e.g., 2 equal volumes water, 3 equal volumes of water, or 4 equal volumes of water, respectively
• the concentrate can contain an appropriate fraction of the water present in the final polishing composition in order to ensure that the colloidal silica particles that are surface-modified with metal ions, anionic surfactant, buffering agent, and/or any optional additive are at least partially or fully dissolved in the concentrate.
• the invention also provides a method of chemically-mechanically polishing a substrate comprising (i) contacting a substrate with a polishing pad and the chemical- mechanical polishing composition as described herein, (ii) moving the polishing pad relative to the substrate with the chemical-mechanical polishing composition therebetween, and (iii) abrading at least a portion of the substrate to polish the substrate.
• the chemical-mechanical polishing composition can be used to polish any suitable substrate and is especially useful for polishing substrates comprising at least one layer (typically a surface layer) comprised of silicon nitride.
• Suitable substrates include wafers used in the semiconductor industry.
• the wafers typically comprise or consist of, for example, a metal, metal oxide, metal nitride, metal composite, metal alloy, a low dielectric material, or combinations thereof.
• the method of the invention is particularly useful for polishing substrates comprising silicon nitride, silicon oxide, and/or polysilicon, e.g., any one, two, or especially all three of the aforementioned materials.
• the substrate comprises polysilicon in combination with silicon nitride and/or silicon oxide.
• the polysilicon can be any suitable polysilicon, many of which are known in the art.
• the polysilicon can have any suitable phase, and can be amorphous, crystalline, or a combination thereof.
• the silicon oxide similarly can be any suitable silicon oxide, many of which are known in the art. Suitable types of silicon oxide include but are not limited to borophosphosilicate glass (BPSG), PETEOS, thermal oxide, undoped silicate glass, and HDP oxide. Other suitable metal oxides include
• PSD partially-stabilized zirconia
• the chemical-mechanical polishing composition of the invention desirably exhibits a high removal rate when polishing a substrate comprising silicon nitride according to a method of the invention.
• the polishing composition desirably exhibits a silicon nitride removal rate of about 100 A/min or higher, 150 A/min or higher, about 200 A/min or higher, about 250 A/min or higher, about 300 A/min or higher, about 350 A/min or higher, about 400 A/min or higher, about 450 A/min or higher, or about 500 A/min or higher.
• the chemical-mechanical polishing composition of the invention desirably exhibits a low removal rate when polishing a substrate comprising silicon oxide according to a method of the invention.
• the polishing composition desirably exhibits a removal rate of the silicon oxide of about 50 A/min or lower, about 45 A/min or lower, about 40 A/min or lower, about 35 A/min or lower, about 30 A/min or lower, about 25 A/min or lower, about 20 A/min or lower, about 15 A/min or lower, about 10 A/min or lower, or even about 5 A/min or lower.
• the chemical-mechanical polishing composition of the invention desirably exhibits a low removal rate when polishing a substrate comprising polysilicon according to a method of the invention.
• the polishing composition desirably exhibits a removal rate of polysilicon of about 50 A/min or lower, about 45 A/min or lower, about 40 A/min or lower, about 35 A/min or lower, about 30 A/min or lower, about 25 A/min or lower, about 20 A/min or lower, about 15 A/min or lower, about 10 A/min or lower, or even about 5 A/min or lower.
• the chemical-mechanical polishing composition of the invention can be tailored to provide effective polishing at the desired polishing ranges selective to specific thin layer materials, while at the same time minimizing surface imperfections, defects, corrosion, erosion, and the removal of stop layers.
• the selectivity can be controlled, to some extent, by altering the relative concentrations of the components of the polishing composition.
• the chemical-mechanical polishing composition of the invention can be used to polish a substrate with a silicon nitride to silicon oxide polishing selectivity of about 5 : 1 or higher (e.g., about 10: 1 or higher, about 15: 1 or higher, about 20: 1 or higher, or about 25 : 1 or even higher).
• the chemical-mechanical polishing composition of the invention can be used to polish a substrate with a silicon nitride to polysilicon polishing selectivity of about 2: 1 or higher (e.g., about 4: 1 or higher, about 6: 1 or higher, or about 8: 1 or higher).
• the chemical-mechanical polishing composition and method of the invention are particularly suited for use in conjunction with a chemical-mechanical polishing apparatus.
• the apparatus comprises a platen, which, when in use, is in motion and has a velocity that results from orbital, linear, or circular motion, a polishing pad in contact with the platen and moving with the platen when in motion, and a carrier that holds a substrate to be polished by contacting and moving the substrate relative to the surface of the polishing pad.
• the polishing of the substrate takes place by the substrate being placed in contact with the polishing pad and the polishing composition of the invention, and then the polishing pad moving relative to the substrate, so as to abrade at least a portion of the substrate to polish the substrate.
• a substrate can be polished with the chemical-mechanical polishing composition using any suitable polishing pad (e.g., polishing surface).
• suitable polishing pads include, for example, woven and non-woven polishing pads.
• suitable polishing pads can comprise any suitable polymer of varying density, hardness, thickness, compressibility, ability to rebound upon compression, and compression modulus.
• Suitable polymers include, for example, polyvinylchloride, polyvinylfluoride, nylon, fluorocarbon, polycarbonate, polyester, polyacrylate, polyether, polyethylene, polyamide, polyurethane, polystyrene, polypropylene, coformed products thereof, and mixtures thereof.
• Soft polyurethane polishing pads are particularly useful in conjunction with the inventive polishing method.
• Typical pads include but are not limited to SURFINTM 000, SURFINTM SSW1, SPM3100 Eminess Technologies), POLITEXTM (Dow Chemical Company), and POLYP ASTM 27 (Fujibo).
• a particularly preferred polishing pad is the EPICTM D100 pad commercially available from Cabot Microelectronics.
• the chemical-mechanical polishing apparatus further comprises an in situ polishing endpoint detection system, many of which are known in the art.
• Techniques for inspecting and monitoring the polishing process by analyzing light or other radiation reflected from a surface of the substrate being polished are known in the art. Such methods are described, for example, in U.S. Patent 5,196,353, U.S. Patent 5,433,651, U.S. Patent 5,609,511, U.S. Patent 5,643,046, U.S. Patent 5,658,183, U.S. Patent 5,730,642, U.S. Patent 5,838,447, U.S. Patent 5,872,633, U.S. Patent 5,893,796, U.S. Patent 5,949,927, and U.S.
• Patent 5,964,643 Desirably, the inspection or monitoring of the progress of the polishing process with respect to a substrate being polished enables the determination of the polishing end-point, i.e., the determination of when to terminate the polishing process with respect to a particular substrate.
• This example demonstrates the effect of surface modification of colloidal silica particles with aluminum on silicon nitride and silicon oxide removal rate.
• polishing Compositions 1A-1C Separate substrates comprising blanket layers of silicon nitride and silicon oxide were polished with three different polishing compositions, Polishing Compositions 1A-1C. All of the polishing compositions comprised 1 wt.% of colloidal silica particles having an average particle size of about 80 nm in water at a pH of 3.5. Polishing Composition 1 A (control) comprised untreated colloidal silica particles. Polishing Compositions IB and IC (invention) comprised colloidal silica particles particles having an average particle size of about 80 nm that were surface-treated with a solution of aluminum nitrate in water at a concentration of 400 ppm and 800 ppm of aluminum, respectively. Following polishing, the removal rates for silicon nitride and silicon oxide were determined. The results, and the silicon nitride/silicon oxide selectivities, are set forth in Table 1.
• Polishing Compositions IB and IC which contained colloidal silica particles that were surface-treated with aluminum ions, exhibited silicon nitride removal rates that were approximately 1.76 and 1.79 times, respectively, greater than the silicon nitride removal rate exhibited by the control polishing composition.
• Polishing Compositions IB and IC which contained colloidal silica particles treated with aluminum ions, exhibited silicon oxide removal rates that were approximately 0.10 and 0.03 times, respectively, the silicon oxide removal rate exhibited by control Polishing Composition 1A.
• This example compares silicon nitride removal rates and silicon oxide removal rates observed with a polishing composition comprising colloidal silica particles that were surface-treated with aluminum ions with silicon nitride removal rates and silicon oxide removal rates observed with a polishing composition comprising colloidal silica particles having a uniform distribution of aluminum ions throughout the particles.
• Polishing Composition 2A (comparative) comprised 1 wt.% of colloidal silica particles having an average particle size of about 45 nm and having a uniform distribution of aluminum ions throughout the particles.
• Polishing Composition 2B (invention) comprised 1 wt.% of colloidal silica particles that were surface-treated with aluminum ions and having an average particle size of about 50 nm. Following polishing, the removal rates for silicon nitride and silicon oxide were determined. The results, and the silicon nitride/silicon oxide selectivities, are set forth in Table 2.
• Polishing Composition 2B which contained colloidal silica particles that were surface-treated with aluminum ions, exhibited a silicon nitride removal rate that was approximately 1.3 times the silicon nitride removal rate exhibited by Polishing Composition 2A, which contained colloidal silica particles having a uniform distribution of aluminum ions throughout the particles.
• Polishing Composition 2B exhibited a SiN/SiO selectivity that was approximately 1.22 times greater than the SiN/SiO selectivity exhibited by Polishing Composition 2A.
• This example demonstrates the effect on active oxide loss in the polishing of patterned substrates comprising a layer of silicon nitride over a patterned silicon oxide substrate observed with a polishing composition comprising colloidal silica particles that were surface-treated with aluminum ions.
• Patterned substrates comprising a layer of silicon nitride over a patterned silicon oxide substrate were polished with two different polishing compositions, Polishing
• Polishing Composition 3 A (comparative) comprised 1 wt.% of colloidal silica particles having an average particle size of about 45 nm and having a uniform distribution of aluminum ions throughout the particles. Polishing Composition 3B
• the substrates comprised the following patterns: (a) 100 ⁇ feature width and 50% pattern density, (b) 200 ⁇ feature width and 50% pattern density, (c) 400 ⁇ feature width and 50% partem density, (d) 900 ⁇ feature width and 50% partem density, (e) 1800 ⁇ feature width and 50% pattern density, (f) 2 ⁇ feature width and 50% pattern density, (g) 20 ⁇ feature width and 50% pattern density, (h) 50 ⁇ feature width and 50% partem density, (i) 50 ⁇ feature width and 90% pattern density, (j) 50 ⁇ feature width and 10% partem density, and (k) 0.36 ⁇ feature width and 38% pattern density. All of the substrates were polished to endpoint and then 10 s of overpolishing.
• Polishing Composition 3B exhibited no greater than an approximately 2.6% reduction in remaining active oxide.
• Polishing Composition 3A exhibited significantly greater reduction in remaining active oxide except at 2 ⁇ feature width at 50% pattern density and at 0.36 ⁇ feature width at 38% pattern density.
• This example demonstrates the effect on silicon nitride and silicon oxide removal rates observed with a polishing composition comprising an anionic surfactant and colloidal silica particles that were surface-treated with aluminum ions.
• Polishing Compositions 4AA-4BB Separate substrates comprising blanket layers of silicon nitride and silicon oxide were polished with 28 different polishing compositions, Polishing Compositions 4AA-4BB.
• Each of the Polishing Compositions contained colloidal silica particles that were surface-treated with aluminum ions in amounts and that have particle sizes as set forth in Table 4.
• Polishing Compositions 4AB-4AD, 4AF-4AJ, 4AL-4AP, 4AQ-4AV, and 4AX-4BB further contained a poly(acrylic acid-co-maleic acid) copolymer in amounts as set forth in Table 4.
• the removal rates for silicon nitride and silicon oxide were determined. The results, and the silicon nitride/silicon oxide selectivities, are set forth in Table 4.
• the silicon nitride removal rate decreased with increased concentrations of the poly(acrylic acid-co-maleic acid) copolymer.
• the silicon oxide removal rate was not particularly affected by increased concentrations of the poly(acrylic acid-co-maleic acid) copolymer.
• polishing Compositions 5A-5I Separate substrates comprising blanket layers of silicon nitride and silicon oxide were polished with 9 different polishing compositions, Polishing Compositions 5A-5I. Each of the polishing compositions contained 1 wt.% of colloidal silica particles having an average particle size of about 25 nm that were surface-treated with aluminum ions. Polishing Composition 5A (control) did not contain an anionic surfactant. Polishing Composition 5B further contained 10 ppm of a poly (aery lie acid-co-maleic acid) copolymer. Polishing Composition 5C further contained 25 ppm of the DOWFAXTM CIOL alkyldiphenyloxide sulfonate surfactant. Polishing Composition 5D further contained 25 ppm of the
• polishing Composition 5E further contained 25 ppm of a polystyrenesulfonate surfactant.
• Polishing Composition 5F further contained 25 ppm of dodecylbenzenesulfonate.
• Polishing Compositions 5G-5I further contained 100 ppm, 150 ppm, and 200 ppm, respectively, of WE001, which is an anionic surfactant containing both carboxylic and sulfonic acid groups. Following polishing, the removal rates for silicon nitride and silicon oxide were determined. The results, and the silicon nitride/silicon oxide selectivities, are set forth in Table 5.
• polishing Composition 5B which contained a poly(acrylic acid-co-maleic acid), exhibited the same SiN/SiO selectivity but an approximately 14% reduction in the SiN removal rate as compared with control Polishing Composition 5A.
• Polishing Composition 5D which contained DOWFAXTM C6L alkyldiphenyloxide sulfonate surfactant, exhibited a slight increase in SiN/SiO selectivity but an approximately 29% reduction in the SiN removal rate as compared with control Polishing Composition 5 A.
• Polishing Composition 5C which contained DOWFAXTM CIOL alkyldiphenyloxide sulfonate surfactant, exhibited a lower SiN/SiO selectivity and an approximately 40% reduction in the SiN removal rate as compared with control Polishing Composition 5A.
• Polishing Compositions 5F-5H which contained dodecylbenzenesulfonate, 100 ppm of WE001, and 150 ppm of WE001, respectively, exhibited improved SiN/SiO selectivities as compared with control Polishing Composition 5A.
• Polishing Composition 51 which contained 200 ppm of WE001, exhibited an approximately 38% increased SiN/SiO selectivity but an approximately 19% reduction in the SiN removal rate as compared with control Polishing Composition 5A.
• This example demonstrates the effect on silicon nitride, silicon oxide, and polysilicon removal rates observed with a polishing composition comprising an anionic surfactant and colloidal silica particles that were surface-treated with aluminum ions.
• polishing Compositions 6A-6D Separate substrates comprising blanket layers of silicon nitride, silicon oxide, and polysilicon were polished with 4 different polishing compositions, Polishing Compositions 6A-6D.
• Each of the polishing compositions contained 1 wt.% of colloidal silica particles having an average particle size of about 25 nm that were surface-treated with aluminum ions.
• Polishing Composition 5A did not an anionic surfactant.
• Polishing Composition 5B (invention) further contained 10 ppm of a poly (aery lie acid-co-maleic acid) copolymer.
• Polishing Composition 5C (comparative) further contained 100 ppm of propyl gallate Polishing Composition 5D (invention) further contained 100 ppm of WE001. Following polishing, the removal rates for silicon nitride, silicon oxide, and polysilicon were determined. The results, and the silicon nitride/polysilicon selectivities, are set forth in Table 6.
• Polishing Compositions 5B and 5D which contained anionic surfactants, exhibited silicon nitride to polysilicon selectivities of 3 and 8, respectively, while control Polishing Composition 5A exhibited a silicon nitride to polysilicon selectivity of 1.
• Polishing Compositions 5B and 5D exhibited silicon nitride removal rates that were approximately 86% and 95% of the silicon nitride removal rate exhibited by the control polishing composition, and exhibited polysilicon removal rates that were approximately 31% and 11% of the polysilicon removal rate exhibited by the control polishing composition, respectively.
• This example shows the reduction of silicon nitride thickness as a function of time achievable with the inventive polishing composition when used to polish pattemed substrates as compared with an industry standard polishing composition.
• Pattemed substrates comprising a layer of silicon nitride over a patterned silicon oxide substrate were polished with two different polishing compositions, Polishing
• Polishing Composition 7A (comparative) comprised about 22 wt.% of fumed silica in water at a pH of about 10.
• Polishing Composition 7B (invention) comprised 1.% colloidal silica particles that were surface-treated with aluminum ions and 50 ppm of a poly(acrylic acid-co-maleic acid) copolymer at a pH of 3.5.
• the substrates comprised the following patterns: (a) 50% pattern density and 20 ⁇ feature width, (b) 50% pattern density and 2 ⁇ feature width, (c) 90% pattern density and 50 ⁇ feature width, and (d) 10% pattern density and 50 ⁇ feature width.
• the silicon nitride thickness was measured after 30, 60, and 90 s of polishing, and the results are set forth in Tables 7-10.
• Polishing Composition 7A Polishing Composition 7B (comparative) (invention)
• inventive Polishing Composition 7B exhibited a significantly faster time for removal rate of the silicon nitride layer than did the comparative Polishing Composition 7A.
• This example provides a method for determining the surface hydroxyl group (silanol group) density for colloidal silica particles.
• [0075] 15 g of silica particles is weighed and placed in a container (X [g]) of which a mass has been measured and then dispersed into an appropriate amount (100 ml or less) of water.
• a container X [g]
• the silica particles are in the form of a dispersion liquid in which the silica particles are dispersed into a medium such as water, the dispersion liquid is weighed and poured into the container so that an amount of the silica particles is 15 g.
• [0078] [4] 30 g of sodium chloride is added to the liquid, and ultrapure water is added until a total amount reaches to 150 g. A 0.1 mol/L sodium hydroxide solution is added to adjust a pH to 4.0 to prepare a titration sample.
• a silanol group density of the silica particles is calculated by the following expression (1):
• NA [number/mol] represents an Avogadro number
• S BET [m 2 /g] represents a BET specific surface area of silica particles

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