Classifications

• • 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
• • 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
• • 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

Definitions

• the present invention relates to a CMP polishing slurry and a method of polishing a substrate that are favorably used in a step of smoothening the surface of a substrate in production of semiconductor devices, in particular in steps of smoothening an inter layer dielectric film and a BPSG (silicon dioxide film doped with boron and phosphorus) film and forming a shallow trench isolation film, and others.
• BPSG silicon dioxide film doped with boron and phosphorus
• CMP chemical mechanical polishing
• inorganic insulation film layers such as a silicon oxide insulation film are formed by methods such as plasma CVD and low-pressure CVD.
• Polishing slurries of fumed silica are commonly studied as a conventional chemical mechanical abrasive in state of slurry for use in smoothening the inorganic insulation film layer.
• the fumed silica polishing slurries are produced by grain growth, for example, by oxidative thermolysis of tetrachlorosilane and subsequent pH adjustment.
• a fumed silica polishing slurry still has a problem that the polishing speed is lower.
• a shallow trench isolation method has been used for isolation of elements in an integrated circuit in devices in the generation of a design rule of 0.25 ⁇ m or later.
• CMP is used for removal of excessive silicon oxide films formed on a substrate, and a stopper film smaller in polishing speed is formed under the silicon oxide film for termination of polishing.
• silicon nitride is used for the stopper film, and the difference in polishing speed between the silicon oxide film and the stopper film is preferably greater.
• colloidal silica-based polishing slurries have a smaller polishing speed ratio between the silicon oxide film and the stopper film at approximately 3, and thus, do not have properties practically usable for shallow trench isolation.
• cerium oxide polishing slurries have been used as abrasives for use on the surface of glasses such as of photomask and lens.
• Cerium oxide particles are softer than silica or alumina particles, less likely to cause scratching on the polishing surface, and thus, useful for finishing mirror-surface polishing.
• the particles also have an advantage that the polishing speed therewith is faster than that of silica polishing slurries.
• CMP polishing slurries for semiconductor processing containing a high-purity cerium oxide polishing powder have been used. (See Japanese Patent Application Laid-Open No. 10-106994.
• a water-soluble polymer having a hydrophilic carboxyl or carboxyl salt group is known to be added as an additive to the cerium oxide CMP polishing slurry for control of the polishing speed of a cerium oxide CMP polishing slurry and improvement of global smoothness (see, for example, Japanese Patent No. 3,278,532).
• Examples of monomers for the additive include an acrylic acid, an itaconic acid, a maleic acid, and the salts, and the most polymerizable acrylic acid is seemingly most preferable.
• cerium oxide CMP polishing slurries containing an additive of water-soluble polymer as the monomer could not reduce the difference in residual film thickness due to the pattern density difference of the film to be polished sufficiently.
• methacrylic acid polymers There are fewer studies on methacrylic acid polymers, because a methacrylic acid is more hydrophobic and only soluble in water at a concentration of 18% at room temperature and hardly gives a high-molecular weight polymer by polymerization. Accordingly, it is not regarded as a monomer suitable for the polymer for use as the additive.
• the present invention provides a CMP polishing slurry and a polishing method that, after polishing, give a polished film having a smaller difference in residual film thickness due to a pattern density difference.
• the present invention relates to the following inventions (1) to (13).
• a CMP polishing slurry containing (A) cerium oxide particles, (B) a dispersant, (C) water, and (D) at least one of a polymer of at least one of a methacrylic acid and the salt thereof, and a polymer of at least one of a methacrylic acid and the salt thereof and a monomer having an unsaturated double bond.
• a CMP polishing slurry containing (A) cerium oxide particles, (C) water, and (D) at least one of a polymer of at least one of a methacrylic acid and the salt thereof, and a polymer of at least one of a methacrylic acid and the salt thereof and a monomer having an unsaturated double bond.
• a CMP polishing slurry containing (A) cerium oxide particles, (C) water, (D) at least one of a polymer of at least one of a methacrylic acid and the salt thereof, and a polymer of at least one of a methacrylic acid and the salt thereof and a monomer having an unsaturated double bond, and (E) at least one of a polymer of at least one of an acrylic acid and the salts thereof, and a polymer of at least one of an acrylic acid and the salt thereof and a monomer having an unsaturated double bond.
• a polymerization initiator for use in preparation of the polymer is a compound soluble completely at 25° C. when it is added at a ratio of 0.5 part in 99.5 mass parts of water or a compound soluble at 25° C. when it is added at a ratio of 0.5 mass part in 99.5 mass parts of water and at least one of an organic acid and an inorganic acid is added thereto in an amount of 2 moles with respect to 1 mole of the polymerization initiator.
• a polymerization initiator for use in preparation of the polymer is a compound soluble completely at 25° C. when it is added at a ratio of 3.0 parts in 97.0 mass parts of water or a compound soluble at 25° C. when it is added at a ratio of 3.0 mass parts in 97.0 mass parts of water and at least one of an organic acid and an inorganic acid is added thereto in an amount of 2 moles with respect to 1 mole of the polymerization initiator.
• a method of polishing a substrate characterized by pressing a substrate having a formed film to be polished onto a polishing cloth of a polishing table, and polishing the film to be polished by moving the substrate and the polishing table relatively to each other while supplying the CMP polishing slurry according to any one of (1) to (12) into the space between the film to be polished and the polishing cloth.
• the CMP polishing slurry and the polishing method according to the present invention give a film to be polished smaller in the difference in residual film thickness due to a pattern density difference.
• a CMP polishing slurry according to the present invention is produced, for example, by preparing a cerium oxide slurry containing cerium oxide particles, a dispersant and water, and a supplementary solution containing an additive and water, followed by mixing these liquids.
• the cerium oxide particles (A) according to the present invention are prepared, for example, by oxidizing a cerium compound such as a carbonate salt, a nitrate salt, a sulfate salt or oxalate salt.
• a cerium oxide polishing slurry for use in polishing a silicon oxide film formed, for example, by a TEOS-CVD method allows high-speed polishing, but leaves more polishing scratches on the polished film, when the crystallite diameter of the particle becomes greater and the crystal distortion becomes smaller, i.e., when the crystallinity thereof is higher.
• the method of producing the cerium oxide particles for use in the present invention is not particularly limited, the crystallite diameter of the cerium oxide is preferably 1 nm or more and 400 nm or less.
• the content of alkali metals and halogens in the cerium oxide particle is preferably kept, for example, to 10 ppm or less by mass.
• the cerium oxide particles can be prepared, for example, by calcining or by oxidation with hydrogen peroxide or the like.
• the calcining temperature is preferably in the range of 350° C. to 900° C.
• the cerium oxide particles prepared by the method are preferably pulverized mechanically, if aggregated.
• the pulverization method is preferably a dry pulverization method, for example, by using a jet mill, or a wet pulverization method, for example, by using a planetary bead mill.
• the jet mill is described, for example, in Kagaku Kogaku Ronbunshu (Chemical Engineering Paper Collection), Vol. 6, No. 5 (1980) pp. S27 to 532.
• cerium oxide particles can be dispersed in water which is a primary dispersion medium, by dispersing the mixture in a homogenizer, an ultrasonic dispersing machine, a wet ball mill, or the like as well as a common stirrer.
• cerium oxide dispersion is prepared, for example, by a sedimentation classification method of leaving a cerium oxide dispersion for a long period to allow sedimentation of larger particles and withdrawing a supernatant liquid by a pump.
• the cerium oxide particles in the dispersion medium may be pulverized further in a high-pressure homogenizer that pulverizes particles by collision under high pressure.
• the average particle diameter of the cerium oxide particles in the CMP polishing slurry thus prepared is preferably 1 to 400 nm, more preferably 1 to 300 nm, and still more preferably 1 to 200 nm.
• An average cerium oxide particle diameter of less than 1 nm may lead to decrease in polishing speed, while an average cerium oxide particle diameter of more than 400 nm may lead to more frequent scratching on the polished film.
• the average particle diameter of cerium oxide particles is a D50 value (median diameter of volumetric distribution, cumulative median value), as determined in a laser-diffraction particle size distribution analyzer.
• the concentration of the cerium oxide particles is preferably in the range of 0.1 mass part or more and 5 mass parts or less, more preferably in the range of 0.2 mass part or more and 2 mass parts or less, and still more preferably in the range of 0.5 mass part or more and 1.5 mass parts or less, with respect to 100 mass parts of the CMP polishing slurry.
• a concentration of less than 0.1 mass part leads to deterioration in polishing speed, while a concentration of more than 5 mass parts leads to easier aggregation of cerium oxide particles.
• the CMP polishing slurry according to the present invention preferably contains a dispersant (B).
• a dispersant examples include water-soluble anionic dispersants, water-soluble nonionic dispersants, water-soluble cationic dispersants, and water-soluble amphoteric dispersants; polycarboxylic acid-based polymer dispersants described below are preferable; and polymer dispersants containing, as a copolymer component, an ammonium acrylate salt as its structural unit are more preferable.
• polymer dispersants containing, as a copolymer component, an ammonium acrylate salt as its structural unit include ammonium polyacrylate, copolymers of acrylic amide and ammonium acrylate, and the like.
• a mixture of two or more dispersants for example a mixture of at least one polymer dispersant containing, as a copolymer component, an ammonium acrylate salt as its structural unit and at least one other dispersant, for example, selected from water-soluble anionic, nonionic, cationic and amphoteric dispersants, may be used.
• the total content of alkali metals such as sodium and potassium ions, and halogen and sulfur atoms in the dispersant is preferably kept, for example, to 10 ppm or less by mass with respect to the CMP polishing slurry.
• water-soluble anionic dispersants examples include triethanolamine laurylsulfate, ammonium laurylsulfate, triethanolamine polyoxyethylene alkylether sulfates, and polycarboxylic acid-based polymer dispersants.
• polycarboxylic acid-based polymer dispersants examples include polymers from a carboxylic acid monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, or itaconic acid; copolymers from a carboxylic acid monomer having an unsaturated double bond and another monomer having an unsaturated double bond; and the ammonium or amine salts thereof.
• water-soluble nonionic dispersants examples include polyoxyethylene laurylether, polyoxyethylene cetylether, polyoxyethylene stearylether, polyoxyethylene oleylether, polyoxyethylene higher alcohol ethers, polyoxyethylene octylphenylether, polyoxyethylene nonylphenylether, polyoxyalkylene alkylether, polyoxyethylene derivatives, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethyltetraoleate ethylene sorbitol, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, 2-hydroxyethyl methacrylate, and alkyl
• water-soluble cationic dispersants examples include polyvinylpyrrolidone, coconut amine acetate, and stearylamine acetate.
• water-soluble amphoteric dispersants examples include laurylbetaine, stearylbetaine, lauryldimethylamine oxide, and 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.
• the dispersants (B) are used alone or in combination of two or more.
• the dispersant is effective in dispersing the cerium oxide particles stably in a dispersion medium (C) such as water.
• the amount of the dispersant added is preferably 0.01 mass part or more and 10 mass parts or less, more preferably 0.05 mass part or more and 8 mass parts or less, and particularly preferably 0.1 mass part or more and 5 mass parts or less, with respect to 100 mass parts of the cerium oxide particles, from the viewpoints of improvement of dispersion and for prevention of sedimentation of the particles in the polishing slurry and polishing scratch.
• An addition amount of less than 0.01 mass part leads to insufficient dispersion of the particles and thus generation of more polishing scratches on the polished film, while an addition amount of more than 10 mass parts leads to aggregation and sedimentation of the particles and generation of more polishing scratches on the polished film.
• the weight-average molecular weight of the dispersant is preferably 100 to 50,000, more preferably 1,000 to 10,000, from the viewpoints of polishing speed and storage stability.
• a weight-average molecular weight of less than 100 leads to insufficient polishing speed, while that of more than 50,000 leads to increase in viscosity and deterioration in the storage stability of the polishing slurry.
• the weight-average molecular weight is a value as polyethylene glycol, as determined with a HPLC pump (Model No. L-7100, manufactured by Hitachi, Ltd.) equipped with a differential refractometer (Model No. L-3300, manufactured by Hitachi, Ltd.) and a GPC column (Model No.
• Gelpack GL-W550 manufactured by Hitachi Chemical Co., Ltd.
• the CMP polishing slurry according to the present invention contains a polymer of at least one of a methacrylic acid and the salt thereof and/or a polymer of at least one of a methacrylic acid and the salt thereof and a monomer having an unsaturated double bond (D). Presence of the polymer (D) improves smoothening characteristics. It also reduces the polishing speed of the stopper film (silicon nitride film) more effectively than that of the film to be polished mainly (silicon oxide film), making process management of polishing easier.
• the content of the methacrylic acid and the salt thereof for the polymer (D) is preferably 10 to 100 mol %, more preferably 30 to 100 mol %, still more preferably 50 to 100 mol %, particularly preferably 60 to 100 mol %, very preferably 70 to 100 mol %, extremely preferably 80 to 100 mol %, and most preferably 90 to 100 mol %, with respect to the total amount of the monomer components, from the viewpoint of global smoothening characteristics.
• a content of the methacrylic acid and the salt thereof at less than 10 mol % leads to increase of the difference in residual film thickness of the polished film due to the pattern density difference.
• An ammonium, potassium, alkylamine or other salt of a methacrylic acid may be used alone or in combination with a methacrylic acid as the monomer for the polymer (D).
• the polymer (D) may be a polymer containing at least one of a methacrylic acid and the salt thereof as part of the monomers, a polymer containing only at least one of a methacrylic acid and the salt as the monomer, or a combination of these polymers.
• the polymer may also function as a dispersant occasionally.
• Examples of the monomers having an unsaturated double bond include carboxylic acids such as acrylic acid, crotonic acid, vinylacetic acid, tiglic acid, 2-trifluoromethylacrylic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, mesaconic acid, and gluconic acid; and sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid.
• carboxylic acids such as acrylic acid, crotonic acid, vinylacetic acid, tiglic acid, 2-trifluoromethylacrylic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, mesaconic acid, and gluconic acid
• sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid.
• a salt thereof such as ammonium, potassium, or alkylamine salt may be used.
• the monomers having an unsaturated double bond for use include radical polymerizable monomers such as C 1 - to C 18 -acrylic esters, C 1 - to C 18 -methacrylic esters, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-iso-propylacrylamide, acryloylmorpholine, vinylalcohol, acrylonitrile, vinylpyrrolidone, and vinylpyridine.
• radical polymerizable monomers such as C 1 - to C 18 -acrylic esters, C 1 - to C 18 -methacrylic esters, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-iso-propylacrylamide, acryloylmorpholine, vinylalcohol, acrylonitrile, vinylpyrrolidone, and vinylpyridine.
• These monomers may be used alone or in combination of two or more.
• the polymer (D) may be used in combination with (E) a polymer of at least one of an acrylic acid and the salt thereof and/or a polymer of at least one of an acrylic acid and the salt thereof and a monomer having an unsaturated double bond.
• the polymer (E) is favorable as it controls the solubility in water.
• a polymerization initiator polymerizing these monomers and giving a polymer is preferably, for example, a water-soluble compound.
• the initiator preferably have a solubility to the degree that the initiator is completely soluble when it is added in an amount of 0.5 mass part in 99.5 mass parts of water and stirred in water at 25° C., or that the initiator is soluble completely when it is added in an amount of 0.5 mass part in 99.5 mass parts of water and an organic acid and/or an inorganic acid are added thereto in an amount of 2 moles with respect to 1 mole of the polymerization initiator.
• the complete solubilization can be determined, for example, by placing and sealing 0.15 g of a polymerization initiator and 29.85 g of purified water in a capped polypropylene centrifugal tube having a capacity of 50 ml at 25° C., rotating the tube in a test tube mixer at 2,500 rpm for 3 minutes, and examining the presence of an insoluble matter by visual observation.
• the polymerization initiator more preferably has a solubility to the degree that the initiator is completely soluble when it is added in an amount of 3.0 mass parts in 97.0 mass parts of water or when it is added in an amount of 3.0 mass parts in 97.0 mass parts of water and an organic acid and/or an inorganic acid are added thereto in an amount of 2 moles with respect to 1 mole of the polymerization initiator.
• the complete solubilization can be determined, for example, by placing and sealing 0.9 g of a polymerization initiator and 29.1 g of purified water in a capped polypropylene centrifugal tube having a capacity of 50 ml at 25° C., rotating the tube in a test tube mixer at 2,500 rpm for 3 minutes, and examining the presence of an insoluble matter by visual observation.
• polymerization initiators include the followings: peroxides such as ammonium persulfate, potassium persulfate, and sodium persulfate; redox initiators in combination of a sulfite salt such as aluminum sulfite, ammonium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, sodium sulfite or sodium hydrogen sulfite, and oxygen, air, peroxide, or the like; amphoteric azo compounds such as 2,2′-azobis[N-(2-carboxyethyl)-2-methyl propionamide]; and cationic azo compounds such as 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2′-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide ⁇ , 2,2′-azobis ⁇ 2-methyl-N-[2-(1-hydroxybutyl)]-propionamide ⁇ , 2,2′-azobis
• a salt of an organic acid such as acetic acid, oxalic acid, malonic acid, succinic acid, malic acid, tartaric acid, or citric acid; or a salt of an inorganic acid such as phosphoric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, nitric acid, or sulfuric acid may be added, for improvement of the water solubility of the polymerization initiator described above.
• the organic acid and/or the inorganic acid are preferably added in an amount of 2 moles with respect to 1 mole of the polymerization initiator.
• 2,2′-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide ⁇ , 2,2′-azobis[2-methyl-N-(1-hydroxyethyl)]-propionamide and 2,2′-azobis[2-(2-imidazolin-2-yl)propane] are preferably used, as it is mixed with the organic acid and/or the inorganic acid above.
• An anionic azo compound such as 4,4′-azobis(4-cyanovaleric acid) may be used, for example, as a polymerization initiator other than the water-soluble compounds above.
• a solvent for use during polymerization is not particularly limited, but favorable examples thereof include water, and C 1 to C 4 alcohols such as methanol, isopropanol, propanol and butanol. These solvents are used alone or in combination of two or more.
• the weight-average molecular weight of the polymer thus obtained is preferably 200 to 100,000, more preferably 300 to 70,000, and particularly preferably 500 to 50,000 (as polyethylene glycol).
• a polymer having a weight-average molecular weight of less than 200 may lead to insufficient global smoothening characteristics, while a polymer having a molecular weight of more than 100,000 may lead to insufficient polishing speed.
• the weight-average molecular weight is a value as polyethylene glycol, as determined with a HPLC pump (Model No. L-7100, manufactured by Hitachi, Ltd.) equipped with a differential refractometer (Model No. L-3300, manufactured by Hitachi, Ltd.) and a GPC column (Model No.
• Gelpack GL-W550 manufactured by Hitachi Chemical Co., Ltd.
• a mercapto compound-based molecular-weight-regulating agent such as mercaptoethanol may be used for control of the weight-average molecular weight during polymerization.
• the amount of the polymer used in the present invention is preferably 0.01 to 5 mass parts, more preferably 0.05 to 3 mass parts, and particularly preferably 0.10 to 1 mass part with respect to 100 mass parts of the CMP polishing slurry.
• An addition amount of less than 0.01 mass part may prohibit high global smoothening characteristics, while an addition amount of more than 5 mass parts may lead to aggregation of the cerium oxide particles.
• convex regions thereon should be polished selectively.
• a protection film made of the polymer is formed on the surface of the cerium oxide particles and the film to be polished.
• the film to be polished in concave regions having a smaller effective polishing load is protected by the protection film, but the protection film on the film to be polished on the convex regions having a greater effective polishing load is selectively eliminated by polishing.
• water-soluble polymers commonly used as an additive such as a polyacrylic acid are higher in water solubility and seemingly form a thick protection film coarsely spotted on the film to be polished.
• the polymer (D) seems to form a thin dense adsorption layer on the film to be polished, because it contains a methacrylic acid, which is more hydrophobic than an acrylic acid, i.e., a monomer traditionally used for the polyacrylic acid, as its monomer. As a result, it forms a strong protection film on the surface of the film to be polished, allowing global smoothening with little pattern density dependency.
• the polymer according to the present invention seems to function also as a dispersant.
• the supplementary solution used in the present invention may contain another water-soluble polymer with the polymer described above.
• the another water-soluble polymer is not particularly limited, and examples thereof include polysaccharides such as alginic acid, pectin acid, carboxymethylcellulose, agar, curdlan and pullulan; polycarboxylic acids and the salts such as polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polyamic acid, ammonium polyamate salt, sodium polyamate salt and polyglyoxylic acid, and the salts thereof; and vinyl polymers such as polyvinylalcohol, polyvinylpyrrolidone, and polyacrolein.
• the CMP polishing slurry according to the present invention may be stored as a two-liquid CMP polishing slurry, for example, consisting of a cerium oxide slurry and a supplementary solution, or as a single-liquid CMP polishing slurry which is a mixture of a cerium oxide slurry and a supplementary solution.
• the polishing slurry is stored as the two-liquid polishing slurry consisting of a cerium oxide slurry and a supplementary solution, it is possible to adjust the global smoothening efficiency and the polishing speed easily by changing the blending ratio of these two liquids.
• the supplementary solution and the cerium oxide slurry are fed to a polishing table as they are supplied separately from different pipes and mixed immediately before an supply pipe outlet where these pipes are connected, or the supplementary solution is mixed with the cerium oxide slurry immediately before polishing. It is also possible to adjust the polishing characteristics by adding deionized water as needed to the cerium oxide slurry and the additive immediately before mixing or during mixing in piping as described above.
• the CMP polishing slurry according to the present invention is preferably used for polishing, after it is adjusted to a desirable pH.
• a pH adjuster for use is not particularly limited, but ammonia water or an acid component is used more favorably than an alkali metal when the polishing slurry is used for semiconductor polishing.
• the ammonium salt prepared by partial neutralization of the polymer or water-soluble polymer described above with ammonia may be used as the pH adjuster.
• the pH of the CMP polishing slurry is preferably 4.5 to 6.0, more preferably 4.8 to 5.6. A pH of less than 4.5 leads to deterioration in polishing speed, while a pH of more than 6.0 leads to deterioration in smoothness of the polished film.
• the pH of the CMP polishing slurry according to the present invention can be determined by using a pH meter (for example, Model PH81, manufactured by Yokogawa Electric Corporation), and after two-point calibration with a standard buffer solution (a phthalate pH buffer solution, pH: 4.21 (25° C.) and a neutral phosphate pH buffer solution, pH 6.86 (25° C.)), an electrode is immersed in the CMP polishing slurry, and the pH stabilized after 2 minutes or longer is determined.
• a pH meter for example, Model PH81, manufactured by Yokogawa Electric Corporation
• a standard buffer solution a phthalate pH buffer solution, pH: 4.21 (25° C.) and a neutral phosphate pH buffer solution, pH 6.86 (25° C.
• the CMP polishing slurry according to the present invention is resistant to the increase of the difference in residual film thickness of the polished film due to the pattern density difference, when it contains a strong acid ion additionally.
• the strong acid is an acid having a pKa of the first dissociable acidic group (pK a1 ) at 3.2 or less.
• the value above in parenthesis is the pKa value described in the literature: “Chemical Handbook (Basic)” Revised Ed., 4th, (Chemical Society of Japan Ed., Sep. 30, 2003, Maruzen Co., Ltd.) pp. II-317 to 322.
• the strong acid is more effective when the pKa of its first dissociable acidic group is lower, and thus, the pKa of the first dissociable acidic group is preferably 2.0 or less, more preferably 1.5 or less. A pKa of the first dissociable acidic group at more than 3.2 may result in insufficient effect.
• the method of adding a strong acid for use in the present invention is not particularly limited, and the strong acid may be added, for example, separately from the polymer and the water-soluble polymer, or may be contained previously in the polymerization initiator. Alternatively, the strong acid may be added to the polishing slurry in the form of a salt.
• the strong acid ion added seems to prevent dissociation of the carboxyl groups in the polymer and other water-soluble polymers by preferential dissociation thereof over the polymer and other water-soluble polymers, and the polymer and the other water-soluble polymers prohibited from dissociation are adsorbed on the surface of the film to be polished, easily forming a protection film. As a result, it is possible to reduce the difference in residual film thickness of the film to be polished on a wafer having a pattern density difference further.
• the content of the strong acid ion in the CMP polishing slurry is preferably 50 to 10,000 ppm, more preferably 100 to 1,000 ppm, and particularly preferably 200 to 600 ppm by mass.
• a content of less than 50 ppm leads to deterioration in reduction of the pattern density dependency, while a content of more than 10,000 ppm leads to deterioration in the dispersion stability of cerium oxide particles.
• Water (C) is the main dispersion medium and is not particularly limited, but deionized water is preferable.
• the polishing method according to the present invention is characterized by pressing a substrate having a film to be polished onto a polishing cloth of a polishing table, and polishing the film to be polished by moving the substrate and the polishing table relatively to each other while the CMP polishing slurry according to the present invention is supplied to the space between the film to be polished and the polishing cloth.
• the substrates include substrates for semiconductor device production, for example, substrates having an inorganic insulation layer formed on a semiconductor substrate such as a semiconductor substrate having a circuit device and a wiring pattern formed thereon and a semiconductor substrate having a circuit device formed thereon.
• the films to be polished include the inorganic insulation layers described above including a silicon oxide film layer, a silicon nitride layer and the like. Surface irregularity is eliminated by polishing the silicon oxide or nitride film layer formed on the substrate with the CMP polishing slurry above, and the semiconductor substrate is smoothened over the entire surface.
• the polishing method according to the present invention can also be used for shallow trench isolation.
• the ratio of the silicon-oxide-film polishing speed to the silicon-nitride-film polishing speed i.e., (silicon-oxide-film polishing speed)/(silicon nitride film polishing speed)
• a ratio of 10 or more leads to greater drop of polishing speed after exposure of the silicon nitride film and thus, to easier termination of polishing.
• a ratio of less than 10 leads to difficulty in termination polishing at a predetermined position.
• the substrate is preferably protected from scratching during polishing.
• polishing method taking a semiconductor substrate carrying an inorganic insulation layer such as a silicon oxide film formed thereon as an example.
• a common polishing machine having: a polishing table with a removable polishing cloth (pad) connected, for example, to a rotational frequency-variable motor; and a holder capable of holding a substrate carrying a film to be polished such as a semiconductor substrate may be used as the polishing machine.
• the polishing machines include a polishing machine, Model No. EPO-111 manufactured by Ebara Corporation, and the like.
• the polishing cloth is not particularly limited, and examples thereof include general nonwoven fabrics, foamed polyurethane, porous fluoroplastics, and the like.
• the polishing cloth preferably has trenches for holding the CMP polishing slurry processed thereon.
• the polishing condition is not particularly limited, but the rotational velocity of the polishing table is preferably lower at 200 rpm or lower for prevention of separation of the semiconductor substrate, and the pressure applied onto the semiconductor substrate (processing load) is preferably 100 kPa or less for prevention of scratching after polishing. It is preferable to supply the CMP polishing slurry continuously, for example, by a pump to the polishing cloth during polishing.
• the feed rate is not particularly limited, but the surface of the polishing cloth is preferably, always covered with the CMP polishing slurry.
• the semiconductor substrate after polishing is preferably washed thoroughly with running water and dried, as the water droplets on the semiconductor substrate are removed, for example, by a spin dryer. It is thus possible to eliminate surface irregularity and form a smooth surface over the entire area of the semiconductor substrate by polishing the inorganic insulation film, which is the film to be polished, with the polishing slurry. After the surface-smoothened shallow trenches are formed, aluminum wiring is formed on the inorganic insulation film layer; and then, an inorganic insulation film is formed between and on the wirings by a method described below and polished similarly with the CMP polishing slurry above, to give a smoothened surface. It is possible to produce a semiconductor substrate having a desired number of layers by repeating the steps above several times.
• the inorganic insulation film such as a silicon oxide film, to which the CMP polishing slurry according to the present invention is used, is produced, for example, by low-pressure CVD, plasma CVD, or the like.
• the silicon oxide film is obtained in the SiH 4 —O 2 oxidation reaction at a temperature of 400° C. or lower.
• the silicon oxide film is heat-treated as needed after CVD at a temperature of 1,000° C. or lower.
• phosphorus P is doped for surface smoothening by high temperature reflow
• use of a SiH 4 —O 2 —PH 3 reaction gas is preferable.
• the plasma CVD method has an advantage that the chemical reaction, which demands high temperature under normal thermal equilibrium, can be carried out at low temperature.
• the plasma generation methods include two methods: a capacitively coupled method and an inductively coupled method.
• reaction gases examples include a SiH 4 —N 2 O gas containing SiH 4 as the Si source and N 2 O as the oxygen source; and a TEOS-O gas (TEOS-plasma CVD method) containing tetraethoxysilane (TEOS) as the Si source.
• the substrate temperature is preferably 250° C. to 400° C., and the reaction pressure is preferably in the range of 67 to 400 Pa.
• the silicon oxide film for used in the present invention may be doped with an element such as phosphorus or boron.
• the silicon nitride film is formed by use of dichlorosilane (SiH 2 Cl 2 ) as the Si source and ammonia (NH 3 ) as the nitrogen source.
• the silicon oxide film is obtained at a high temperature of 900° C. in the SiH 2 Cl 2 —NH 3 oxidation reaction.
• the reaction gas used in forming a silicon nitride film by the plasma CVD method is a SiH 4 —NH 3 gas containing SiH 4 as the Si source and NH 3 as the nitrogen source.
• the support temperature is preferably 300° C. to 400° C.
• the CMP polishing slurry and the polishing method according to the present invention can be applied not only to the silicon oxide film formed on a semiconductor substrate but also can be used in the production processes for various semiconductor devices.
• it can be used in polishing: silicon oxide films formed on a wiring board having a particular wiring; inorganic insulation films such as of glass or silicon nitride; films mainly containing polysilicon, Al, Cu, Ti, TiN, W, Ta, TaN, or the like; optical glasses such as photomask, lens, and prism; inorganic conductive films such as of ITO film; optical integrated circuit, photoswitching element, and optical waveguides such as of glass or a crystalline material; end face of optical fiber; optical single crystals such as scintillator; solid state laser single crystals; blue laser LED sapphire substrates; semiconductor single crystals such as of Sic, GaP, and GaAs; glass plates for magnetic disk; magnetism heads, and the like.
• the content of the nonvolatile matter therein was found to be 25 mass %.
• the slurry was diluted to a suitable concentration for measurement of the average particle diameter of the particles in the cerium oxide slurry, and the average particle diameter D50, as determined by using a laser-diffraction particle size distribution analyzer Master Sizer Microplus (trade name, manufactured by Malvern) at a refractive index of 1.93 and an absorption of 0, was 170 nm.
• An International SEMATECH wafer (864 wafer ( ⁇ 200 mm, SiN film thickness: 150 nm, SiO 2 film thickness in convex region: 610 nm, in concave region: 610 nm, trench depth: 320 nm, manufactured by International SEMATECH) was used as a test wafer for evaluation of shallow-trench-device-isolation insulation film CMP.
• the test wafer was placed on a holder carrying an adsorption pad for fixing the substrate of the polishing machine (trade name: EPO-111, manufactured by Ebara Corporation), while a porous urethane resin polishing pad (perforated groove, Model No. IC-1000, prepared by Rodel) was connected to a 4600 mm polishing table.
• the holder was placed on the pad with the wafer's insulation film face downward, and the processing load and the backside pressure were respectively set to 30 and 15 kPa.
• the CMP polishing slurry prepared above was applied on the polishing table dropwise at a speed of 200 mL/minute, and the polishing table and the wafer were rotated respectively at frequencies of 50 and 50 rpm, to polish the test sample for evaluation of STI insulation film CMP.
• the polishing end point was determined by monitoring the torque current of the polishing table.
• the wafer after polishing was washed thoroughly with purified water and then dried.
• a convex pattern density 10% means a pattern in which a convex region and a concave region are aligned alternately in the ratio in width of 10 and 90
• a convex pattern density 70% means a pattern in which a convex region and a concave region are aligned alternately in the ratio in width of 70 and 30.
• a test wafer for evaluation of shallow-trench-device-isolation insulation film CMP was polished in the same manner as in Example 1 except that the polishing slurry thus obtained was used, to give the results shown in Table 1.
• the content of the nonvolatile matter therein was found to be 25 mass %.
• a test wafer for evaluation of shallow-trench-device-isolation insulation film CMP was polished in the same manner as in Example 1 except that the polishing slurry thus obtained was used, to give the results shown in Table 1.
• a polyacrylic acid-50 mol % methacrylic acid copolymer solution The content of the nonvolatile matter therein was found to be 25 mass %.
• a test wafer for evaluation of shallow-trench-device-isolation insulation film CMP was polished in the same manner as in Example 1 except that the polishing slurry thus obtained was used, to give the results shown in Table 1.
• a polyacrylic acid-30 mol % methacrylic acid copolymer solution The content of the nonvolatile matter therein was found to be 25 mass %.
• a test wafer for evaluation of shallow-trench-device-isolation insulation film CMP was polished in the same manner as in Example 1 except that the polishing slurry thus obtained was used, to give the results shown in Table 1.
• a polyacrylic acid-10 mol % methacrylic acid copolymer solution The content of the nonvolatile matter therein was found to be 25 mass %.
• a test wafer for evaluation of shallow-trench-device-isolation insulation film CMP was polished in the same manner as in Example 1 except that the polishing slurry thus obtained was used, to give the results shown in Table 1.
• a wafer for evaluation was polished with each of the CMP polishing slurries prepared in Examples 1 to 6, and the convex SiO 2 film in the high-density area (convex region: 70%) was removed and the SiN film was exposed in 185 to 260 seconds, as shown in Table 1.
• the convex-region residual SiN film thickness in the low-density area (convex region: 10%) was 118 to 140 nm, while the concave-region SiO 2 film thickness was 340 to 390 nm.
• the convex-region residual SiN film thickness in the low-density area (convex region: 10%) was 127 to 140 nm, and the concave-region residual SiO 2 film thickness was 354 to 390 nm; and the difference in convex-region residual SiN film thickness between in the high-density area (convex region: 70%) and in the low-density area (convex region: 10%) was 10 to 23 nm, and the difference in concave-region residual SiO 2 film thickness was 96 to 136 nm, indicating that uniform polishing with less influence by the difference in pattern density was performed.
• a test wafer for evaluation of shallow-trench-device-isolation insulation film CMP was polished in the same manner as in Example 1 except that the polishing slurry thus obtained was used, to give the results shown in Table 2.
• a test wafer for evaluation of shallow-trench-device-isolation insulation film CMP was polished in the same manner as in Example 1 except that the polishing slurry thus obtained was used, to give the results shown in Table 2.
• a test wafer for evaluation of shallow-trench-device-isolation insulation film CMP was polished in the same manner as in Example 1 except that the polishing slurry thus obtained was used, to give the results shown in Table 2.
• the convex-region SiN residual film thickness in the low-density area was 82 to 91 nm, while the concave-region SiO 2 residual film thickness was 305 to 342 nm; and the difference in convex-region residual SiN film thickness between in the high-density area (convex region: 70%) and in the low-density area (convex region: 10%) was 57 to 64 nm, while the difference in concave-region residual SiO 2 film thickness between them was 165 to 186 nm, indicating that influence by the difference in pattern density occurred and irregular polishing was performed.
• the present invention provides a polishing slurry for use in CMP methods of smoothening the surface of an inter layer dielectric film, a BPSG film, a shallow-trench-isolation insulation film, and the like, that is resistant to the fluctuation in film thickness due to difference in pattern density, allows polishing of a silicon oxide film and others in high-speed processing and easier process management, and a polishing method by using the polishing slurry.

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