WO2013175853A1 - 砥粒、スラリー、研磨液及びこれらの製造方法 - Google Patents
砥粒、スラリー、研磨液及びこれらの製造方法 Download PDFInfo
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- WO2013175853A1 WO2013175853A1 PCT/JP2013/058769 JP2013058769W WO2013175853A1 WO 2013175853 A1 WO2013175853 A1 WO 2013175853A1 JP 2013058769 W JP2013058769 W JP 2013058769W WO 2013175853 A1 WO2013175853 A1 WO 2013175853A1
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- Prior art keywords
- polishing
- abrasive grains
- liquid
- slurry
- producing
- Prior art date
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- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- ACZVSMNFVFBOTM-UHFFFAOYSA-N beta-alanine betaine Chemical compound C[N+](C)(C)CCC([O-])=O ACZVSMNFVFBOTM-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- 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
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
-
- 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
-
- 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
- H01L21/31—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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
Definitions
- the present invention relates to abrasive grains, slurry, polishing liquid and methods for producing them.
- the present invention relates to abrasive grains, slurry and polishing liquid used in the manufacturing process of semiconductor elements, and methods for manufacturing these.
- CMP Chemical Mechanical Polishing
- STI shallow trench isolation
- an insulating material such as silicon oxide formed by a method such as a CVD (chemical vapor deposition) method or a spin coating method is planarized by CMP.
- a silica-based polishing liquid containing silica particles such as colloidal silica and fumed silica is used as abrasive grains.
- the silica-based polishing liquid is produced by growing abrasive grains by a method such as thermal decomposition of silicon tetrachloride and adjusting pH.
- a silica-based polishing liquid has a technical problem that the polishing rate is low.
- STI is used for element isolation in the integrated circuit.
- CMP is used to remove excess portions of insulating material deposited on the substrate.
- a stopper (polishing stop layer) having a low polishing rate is formed under the insulating material.
- the stopper material (constituting material) is made of silicon nitride, polysilicon, or the like, and has a high polishing selectivity ratio of the insulating material to the stopper material (polishing speed ratio: polishing speed of the insulating material / polishing speed of the stopper material). desirable.
- Conventional silica-based polishing liquids have a polishing selectivity ratio of an insulating material to a stopper material as small as about 3 and tend not to have practical characteristics for STI.
- polishing liquids using tetravalent metal element hydroxide particles have been studied (for example, see Patent Document 2 below).
- a method for producing hydroxide particles of a tetravalent metal element has also been studied (for example, see Patent Document 3 below).
- JP-A-10-106994 International Publication No. 02/067309 JP 2006-249129 A JP 2002-241739 A Japanese Patent Application Laid-Open No. 08-022970
- the polishing speed may decrease in exchange for the effect of adding the additive, and both the polishing speed and other polishing characteristics are compatible. There is a problem that is difficult.
- the storage stability of conventional polishing liquids may be low.
- the polishing characteristics change with time and are greatly reduced (the stability of the polishing characteristics is low).
- a typical polishing characteristic is a polishing rate, and there is a problem that the polishing rate decreases with time (the stability of the polishing rate is low).
- abrasive grains may aggregate or precipitate during storage, which may adversely affect polishing characteristics (low dispersion stability).
- the present invention is intended to solve the above-mentioned problems, and it is possible to polish the material to be polished at an excellent polishing rate while maintaining the additive effect of the additive, and to improve the storage stability. It is an object of the present invention to provide an abrasive that provides a possible polishing liquid and a method for producing the same.
- the present invention is capable of polishing a material to be polished at an excellent polishing rate while maintaining the effect of adding an additive, and provides a slurry that provides a polishing liquid capable of improving storage stability, and It aims at providing the manufacturing method.
- the present invention is a polishing liquid capable of polishing a material to be polished at an excellent polishing rate while maintaining the additive effect of an additive, and capable of improving storage stability, and a method for producing the same
- the purpose is to provide.
- the inventor mixed a metal salt solution containing a salt of a tetravalent metal element and an alkali solution to obtain a tetravalent metal element.
- a metal salt solution containing a salt of a tetravalent metal element and an alkali solution to obtain a tetravalent metal element.
- particles containing a hydroxide of a tetravalent metal element by heating the particles after obtaining particles containing the hydroxide of the above, and abrasive grains containing a hydroxide of the tetravalent metal element It has been found that the stability of the slurry and the polishing liquid containing the drastically improved.
- the material to be polished is polished at an excellent polishing rate while maintaining the additive effect.
- storage stability can be improved.
- the storage stability in particular, the dispersion stability and the stability of the polishing rate can be improved.
- the material to be polished when a slurry containing abrasive grains obtained by the production method is used for polishing, the material to be polished can be polished at an excellent polishing rate and stored. Stability can also be improved.
- the storage stability in particular, the dispersion stability and the stability of the polishing rate can be improved.
- the abrasive grains obtained by the production method contain a hydroxide of a tetravalent metal element, thereby suppressing the occurrence of polishing flaws on the surface to be polished. it can.
- abrasive grains In the method for producing abrasive grains according to the present invention, it is preferable to heat particles containing a tetravalent metal element hydroxide at 100 ° C. or lower. In this case, the stability of the abrasive grains can be further improved.
- the inventor can easily obtain abrasive grains capable of polishing a material to be polished at an excellent polishing rate by mixing a metal salt solution and an alkaline solution under the condition that the following parameters are not less than a specific value. I found. That is, in the method for producing abrasive grains according to the present invention, it is preferable to mix the metal salt solution and the alkali solution under the condition that the parameter Z represented by the following formula (1) is 5.00 or more.
- the ⁇ pH is preferably 1.000 or less. In this case, it is possible to obtain abrasive grains capable of polishing the material to be polished at a further excellent polishing rate.
- the circulation number N may be represented by the following formula (2).
- N (u ⁇ S) / Q (2)
- u represents the linear velocity (m / min) of the stirring blade for stirring the mixed solution
- S represents the area (m 2 ) of the stirring blade
- Q represents the amount of the mixed solution. (M 3 ) is shown. ]
- the linear velocity u is preferably 5.00 m / min or more in the following formula (3). In this case, it is possible to obtain abrasive grains capable of polishing the material to be polished at a further excellent polishing rate.
- u 2 ⁇ ⁇ R ⁇ r (3)
- R represents the rotational speed (min ⁇ 1 ) of the stirring blade
- r represents the rotational radius (m) of the stirring blade.
- the rotation speed R is preferably 30 min ⁇ 1 or more. In this case, it is possible to obtain abrasive grains capable of polishing the material to be polished at a further excellent polishing rate.
- the circulation number N is preferably 1.00 min ⁇ 1 or more. In this case, it is possible to obtain abrasive grains capable of polishing the material to be polished at a further excellent polishing rate.
- the substitution number M may be represented by the following formula (4).
- M v / Q (4)
- v denotes the mixing rate of the metal salt solution and alkali solution (m 3 / min)
- Q represents the amount of liquid mixture (m 3).
- the mixing speed v is preferably 5.00 ⁇ 10 ⁇ 3 m 3 / min or less. In this case, it is possible to obtain abrasive grains capable of polishing the material to be polished at a further excellent polishing rate.
- the substitution number M is preferably 1.0 min ⁇ 1 or less. In this case, it is possible to obtain abrasive grains capable of polishing the material to be polished at a further excellent polishing rate.
- the concentration of the tetravalent metal element salt in the metal salt solution is preferably 0.010 mol / L or more (L represents “liter”; the same applies hereinafter). In this case, it is possible to obtain abrasive grains capable of polishing the material to be polished at a further excellent polishing rate.
- the alkali concentration in the alkali solution is preferably 15.0 mol / L or less. In this case, it is possible to obtain abrasive grains capable of polishing the material to be polished at a further excellent polishing rate.
- the pH of the mixed solution of the metal salt solution and the alkali solution is preferably 1.5 to 7.0. In this case, it is possible to obtain abrasive grains capable of polishing the material to be polished at a further excellent polishing rate.
- the tetravalent metal element is preferably tetravalent cerium. In this case, it is possible to obtain abrasive grains capable of polishing the material to be polished at a further excellent polishing rate.
- the method for producing a slurry according to the present invention includes a step of obtaining a slurry by mixing the abrasive obtained by the method for producing an abrasive and water.
- the slurry production method of the present invention when a polishing liquid obtained by adding an additive to the slurry obtained by the production method is used, the slurry can be coated at an excellent polishing rate while maintaining the additive addition effect.
- the polishing material can be polished and storage stability can be improved.
- the slurry production method of the present invention when the slurry obtained by the production method is used for polishing, the material to be polished can be polished at an excellent polishing rate and the storage stability is improved. You can also.
- the method for producing a polishing liquid according to the present invention may comprise a step of obtaining a polishing liquid by mixing the slurry obtained by the method for producing a slurry and an additive, and the method for producing the abrasive grain.
- the aspect provided with the process of mixing the abrasive grain obtained by above, an additive, and water and obtaining polishing liquid may be sufficient.
- the manufacturing method of the polishing liquid according to the present invention when the polishing liquid obtained by the manufacturing method is used, the material to be polished can be polished at an excellent polishing rate while maintaining the additive effect. At the same time, storage stability can be improved.
- the abrasive according to the present invention is obtained by the method for manufacturing an abrasive.
- the slurry according to the present invention is obtained by the slurry production method.
- the polishing liquid according to the present invention is obtained by the manufacturing method of the polishing liquid.
- the material to be polished when a polishing liquid containing the abrasive grains is used, the material to be polished can be polished at an excellent polishing rate while maintaining the additive effect. At the same time, storage stability can be improved. Moreover, according to the abrasive grain and the method for producing the same according to the present invention, when a polishing liquid obtained by adding an additive to the slurry containing the abrasive grain is used, the additive is excellent while maintaining the additive effect. The material to be polished can be polished at the polishing rate, and storage stability can be improved.
- the abrasive grain and the method for producing the same according to the present invention when the slurry containing the abrasive grain is used for polishing, the material to be polished can be polished at an excellent polishing rate and the storage stability can be improved. You can also. Furthermore, according to the abrasive grain and the method for producing the same according to the present invention, the abrasive grain contains a hydroxide of a tetravalent metal element, whereby the generation of polishing scratches on the surface to be polished can be suppressed.
- a material to be polished when a polishing liquid obtained by adding an additive to the slurry is used, a material to be polished can be obtained at an excellent polishing rate while maintaining the additive addition effect. While being able to grind
- the polishing liquid and the method for producing the same when the polishing liquid is used for polishing, the material to be polished can be polished at an excellent polishing rate and the storage stability can be improved.
- the polishing rate is determined based on the polishing rate before storage.
- the rate of change can be reduced (for example, kept within 5.0%).
- abrasive grains, slurry, and polishing liquid to a planarization process of a substrate surface in a semiconductor element manufacturing process.
- application of the abrasive grains, slurry, and polishing liquid to a planarization process of a shallow trench isolation insulating material, a premetal insulating material, an interlayer insulating material, and the like is provided.
- slurry and “polishing liquid” are compositions that come into contact with a material to be polished during polishing, and contain at least water and abrasive grains.
- aqueous dispersion in which the content of abrasive grains is adjusted to a predetermined amount means a liquid containing a predetermined amount of abrasive grains and water.
- the abrasive according to this embodiment contains a hydroxide of a tetravalent metal element.
- a manufacturing method for obtaining such abrasive grains includes a metal salt solution containing a salt of a tetravalent metal element (first solution, for example, a metal salt aqueous solution) and an alkali solution containing a alkali source (base) (second solution).
- first solution for example, a metal salt aqueous solution
- base alkali solution containing a alkali source
- Liquid for example, a solution containing tetravalent metal element hydroxide by reacting a salt of the tetravalent metal element with an alkali source by mixing with an aqueous alkali solution (hereinafter referred to as “hydroxide of tetravalent metal element”).
- means for stirring the mixed solution obtained by mixing the metal salt solution and the alkali solution is not limited, and a bar-like, plate-like or propeller-like stirrer that rotates around the rotation axis or A method of stirring the mixture using a stirring blade; A method of stirring the mixture using a magnetic stirrer that transmits power from the outside of the container with a rotating magnetic field; A pump installed outside the tank The method of stirring a liquid mixture; The method etc. which stir a liquid mixture by pressurizing external air and blowing in a tank vigorously are mentioned.
- a method of heating the hydroxide particles of the tetravalent metal element in the heating step a method of directly heating the mixed solution obtained by mixing the metal salt solution and the alkali solution using a heat source such as a heater; The method of heating a liquid mixture with the vibration emitted from an ultrasonic transmitter is mentioned.
- the present inventor has found that by using abrasive grains obtained through the heating step, the polishing rate can be improved and the storage stability can be improved. Although this reason is not necessarily clear, this inventor thinks as follows.
- the tetravalent metal (M 4+ ), 1 to 3 hydroxide ions (OH ⁇ ), and 1 to 3 anions (X c- ) containing M (OH) a X b (wherein a + b ⁇ c 4) is considered to be produced as part of the abrasive grains.
- the electron-withdrawing anion (X c ⁇ ) acts to improve the reactivity of hydroxide ions, and the amount of M (OH) a X b increases. It is considered that the polishing rate is improved along with this.
- abrasive grains containing a tetravalent metal element hydroxide may contain not only M (OH) a Xb but also M (OH) 4 , MO 2 and the like.
- examples of the anion (X c ⁇ ) include NO 3 ⁇ , SO 4 2 ⁇ and the like.
- the abrasive grains contain M (OH) a Xb after the abrasive grains are thoroughly washed with pure water and then the FT-IR ATR method (Fourier transform Infrared Spectrometer Attenuated Total Reflection method, Fourier transform infrared spectrophotometer This can be confirmed by a method of detecting a peak corresponding to an anion (X c ⁇ ) by a total reflection measurement method. The presence of anions (X c ⁇ ) can also be confirmed by XPS (X-ray Photoelectron Spectroscopy, X-ray photoelectron spectroscopy).
- the hydroxide particles of the tetravalent metal element are granulated and then heated, the anions (X c ⁇ ) that can be desorbed from the particles are desorbed from the particles in advance. It is considered that the storage stability can be improved while maintaining the polishing rate.
- the heating temperature in the heating step is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, and more preferably 38 ° C. from the viewpoint of further improving the storage stability while maintaining an excellent polishing rate by making it easier to obtain a heating effect.
- the above is more preferable, 40 ° C. or higher is particularly preferable, and 50 ° C. or higher is extremely preferable.
- the heating temperature is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and still more preferably 85 ° C. or lower, from the viewpoint of suppressing boiling of water or the like as a solvent and from the viewpoint of suppressing oxidation and aggregation of particles. 80 ° C. or less is particularly preferable.
- the heating time in the heating step is preferably 3 hours or more, more preferably 6 hours or more, still more preferably 9 hours or more, particularly preferably 18 hours or more, and particularly preferably 24 hours or more, from the viewpoint that a sufficient stabilizing effect is easily obtained. Is very preferred.
- the heating time is preferably 720 hours or less, more preferably 480 hours or less, and even more preferably 240 hours or less, from the viewpoints of productivity and suppression of particle aggregation.
- salts of a tetravalent metal element when the metal is represented as M, M (NO 3 ) 4 , M (SO 4 ) 2 , M (NH 4 ) 2 (NO 3 ) 6 , M (NH 4 ) 4 (SO 4 ) 4 etc. are mentioned. These salts can be used alone or in combination of two or more.
- the lower limit of concentration (the metal salt concentration) C a salt of tetravalent metal element in the metal salt solution from the viewpoint of moderating the increase of pH, 0.010 mol / L or more is preferable, based on the total of the metal salt solution, 0.020 mol / L or more is more preferable, and 0.030 mol / L or more is still more preferable.
- the alkali source of the alkali solution is not particularly limited, and examples thereof include organic bases and inorganic bases.
- Organic bases include nitrogen-containing organic bases such as guanidine, triethylamine and chitosan; nitrogen-containing heterocyclic organic bases such as pyridine, piperidine, pyrrolidine and imidazole; ammonium carbonate, ammonium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide And ammonium salts such as tetramethylammonium chloride and tetraethylammonium chloride.
- inorganic bases include inorganic salts of alkali metals such as ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.
- alkali metals such as ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.
- An alkali source can be used individually by 1 type or in combination of 2 or more types.
- the alkali source preferably exhibits weak basicity from the viewpoint of easily suppressing a rapid reaction.
- nitrogen-containing heterocyclic organic bases are preferable, and pyridine, piperidine, pyrrolidine and imidazole are more preferable, pyridine and imidazole are further preferable, and imidazole is particularly preferable.
- the alkali concentration in the alkali solution limit of C b is preferably not more than 15.0 mol / L, 12. 0 mol / L or less is more preferable, 10.0 mol / L or less is more preferable, and 5.0 mol / L or less is particularly preferable.
- alkali concentration C lower limit of b is particularly from the viewpoint of productivity, based on the total of the alkali solution, or 0.001 mol / L is preferred.
- the alkali concentration in the alkali solution is preferably adjusted as appropriate depending on the alkali source selected.
- the upper limit of the alkali concentration is preferably 0.10 mol / L or less on the basis of the entire alkali solution from the viewpoint of gradual increase in pH.
- 0.05 mol / L or less is more preferable, and 0.01 mol / L or less is more preferable.
- the minimum of alkali concentration is not specifically limited, From a viewpoint of productivity, 0.001 mol / L or more is preferable on the basis of the whole alkali liquid.
- the upper limit of the alkali concentration is preferably 1.0 mol / L or less on the basis of the whole alkali solution from the viewpoint of gradual increase in pH. 0.50 mol / L or less is more preferable, and 0.10 mol / L or less is still more preferable.
- the minimum of an alkali concentration is not specifically limited, 0.01 mol / L or more is preferable on the basis of the whole alkaline liquid from a viewpoint of productivity.
- the upper limit of the alkali concentration is preferably 15.0 mol / L or less on the basis of the entire alkali solution, from the viewpoint of gradual increase in pH. 0.0 mol / L or less is more preferable, and 5.0 mol / L or less is still more preferable.
- the minimum of alkali concentration is not specifically limited, From a viewpoint of productivity, 0.1 mol / L or more is preferable on the basis of the whole alkali liquid.
- alkali source examples include 1,8-diazabicyclo [5.4.0] undec-7-ene (pKa: 25) and the like as the alkali source in which the pKa of the conjugate acid of the alkali source is 20 or more.
- Examples of the alkali source in which the pKa of the conjugate acid of the alkali source is 12 or more and less than 20 include potassium hydroxide (pKa: 16), sodium hydroxide (pKa: 13) and the like.
- Examples of the alkali source in which the pKa of the conjugate acid of the alkali source is less than 12 include ammonia (pKa: 9) and imidazole (pKa: 7).
- the pKa value of the conjugate acid of the alkali source used is not particularly limited as long as the alkali concentration is appropriately adjusted, but the pKa of the conjugate acid of the alkali source is preferably less than 20, preferably less than 12. Is more preferably less than 10, and particularly preferably less than 8.
- the pH of the liquid mixture obtained by mixing the metal salt solution and the alkali liquid is preferably 1.5 or more from the viewpoint of the stability of the liquid mixture in the stable state after mixing the metal salt solution and the alkali liquid. .8 or more is more preferable, and 2.0 or more is more preferable. From the viewpoint of the stability of the mixed solution, the pH of the mixed solution is preferably 7.0 or less, more preferably 6.0 or less, and even more preferably 5.5 or less.
- the pH of the mixed solution can be measured with a pH meter (for example, model number PH81 manufactured by Yokogawa Electric Corporation).
- a pH meter for example, model number PH81 manufactured by Yokogawa Electric Corporation.
- two-point calibration was performed using a standard buffer solution (phthalate pH buffer solution: pH 4.01 (25 ° C.), neutral phosphate pH buffer solution: pH 6.86 (25 ° C.)). Thereafter, an electrode is put into the liquid to be measured, and a value after 2 minutes or more has passed and stabilized is adopted.
- the tetravalent metal element hydroxide particles are prepared by mixing a metal salt solution and an alkali solution under the condition that the parameter Z represented by the following formula (1) is 5.00 or more. It is preferably obtained by reacting with a source.
- Z [1 / ( ⁇ pH ⁇ k)] ⁇ (N / M) / 1000 (1)
- ⁇ pH represents the amount of pH change per minute of the mixed solution
- k represents the reaction temperature coefficient
- N represents the circulation number (min ⁇ 1 )
- M represents the number of substitutions. (Min ⁇ 1 ) is indicated. ]
- Abrasive grains obtained by a production method that satisfies the condition of parameter Z are likely to satisfy the following condition (a) and at least one of condition (b) and condition (c).
- the present inventor has found that when the abrasive grains obtained through the heating step satisfy the condition (a), it becomes easy to polish the material to be polished at an excellent polishing rate and to improve the storage stability. It was. Further, when the abrasive grains further satisfy at least one of the condition (b) and the condition (c), the material to be polished can be easily polished at a further excellent polishing rate, and the storage stability can be easily improved. I found it. Further, the present inventor has found that the polishing liquid and the slurry containing the abrasive grains satisfying the above conditions are slightly yellowish visually, and that the polishing speed is improved as the yellowness of the polishing liquid and the slurry becomes darker.
- Element A is set mainly as an index related to reactivity in this synthesis.
- the pH change amount ⁇ pH per unit time (1 minute) of the mixed solution is preferably small, and it is assumed that the reaction proceeds more gently as the ⁇ pH is smaller. From the above, ⁇ pH was set as the denominator in equation (1).
- the reaction temperature coefficient k is expressed by, for example, the following formula (5).
- the inventor tends to increase the stability of the particles by increasing the temperature T of the mixed solution, but the reaction proceeds vigorously when the reaction temperature coefficient k is high, so that the polishing rate and storage stability are reduced. I found out that there is a tendency to become incompatible.
- the reaction temperature coefficient k is preferably small, and the reaction proceeds more gently as the reaction temperature coefficient k is smaller (that is, the temperature T is lower). I guess that. From the above, k is set as the denominator in equation (1).
- k 2 [(T-20) / 10] (5)
- T shows the temperature (degreeC) of a liquid mixture. ]
- element B was set mainly as an index relating to the reactivity in the synthesis and the diffusibility of the solution.
- the circulation number N is an index indicating the degree of diffusion speed when two or more kinds of substances are mixed. As a result of the examination, it is preferable that the circulation number N is large. The larger the circulation number N is, the more uniformly the metal salt solution and the alkali solution are mixed. From the above, the circulation number N was set to numerator in the formula (1).
- the calculation number of the circulation number N is well known to those skilled in the art, although the calculation formula varies depending on the stirring means used. For example, it is described in detail in “Chemical Engineering Handbook (5th edition)” edited by Maruzen Co., Ltd., Chemical Engineering Association, or “Chemical Engineering Explanation and Exercise” edited by Sakai Shoten Chemical Engineering Association. Taking the case where the reaction is performed using a stirring blade as an example, the circulation number N is expressed by, for example, the following formula (2), and the linear velocity u of the stirring blade in the formula (2) and the mixed liquid are stirred. It depends on the area S of the stirring blade and the liquid volume Q of the mixed liquid.
- the linear velocity u is expressed by the following formula (3), for example, and depends on the rotation speed R and the rotation radius r of the stirring blade.
- N (u ⁇ S) / Q (2)
- u represents the linear velocity (m / min) of the stirring blade for stirring the mixed solution
- S represents the area (m 2 ) of the stirring blade
- Q represents the mixing solution.
- the amount of liquid (m 3 ) is shown.
- ⁇ represents the angular velocity (rad / min) of the stirring blade
- R represents the rotational speed (min ⁇ 1 ) of the stirring blade
- r represents the rotational radius (m) of the stirring blade. Show. ]
- N F / Q (2 ') Can be obtained as
- the number M of substitutions is an index representing the rate at which the substance A is replaced by the substance B when another substance B is mixed with the certain substance A. As a result of the examination, it is preferable that the substitution number M is small, and it is assumed that the smaller the substitution number M, the more slowly the reaction proceeds. From the above, the substitution number M was set as the denominator in the equation (1).
- the number of substitutions M is represented by the following formula (4), for example, and depends on the mixing speed v and the liquid volume Q of the liquid mixture.
- M v / Q (4) Wherein (4), v denotes the mixing rate of the metal salt solution and alkali solution (m 3 / min), Q represents the liquid amount of the mixed solution (m 3).
- the lower limit of the parameter Z is preferably 7.50 or more, more preferably 10.00 or more, from the viewpoint of easily obtaining tetravalent metal element hydroxide particles capable of polishing the material to be polished at an excellent polishing rate. 12.50 or more is particularly preferable.
- the upper limit of the parameter Z is preferably 5000.00 or less from the viewpoint of easily obtaining tetravalent metal element hydroxide particles capable of polishing the material to be polished at an excellent polishing rate and excellent productivity.
- the parameter Z can be adjusted to a predetermined value by controlling each parameter of the formula (1).
- each parameter used when adjusting the parameter Z will be described in more detail.
- the amount of change in pH ⁇ pH is the amount of change in pH per unit time (1 minute) from the start of mixing of the metal salt solution and the alkali solution until the pH of the mixture reaches a constant pH and stabilizes. Average value.
- the value of parameter Z can be increased by controlling ⁇ pH. Specifically, the value of the parameter Z tends to increase by keeping ⁇ pH low. Specific means for achieving this include increasing the metal salt concentration in the metal salt solution, decreasing the alkali concentration in the alkali solution, or using a weakly basic alkali source as the alkali source in the alkali solution. And so on.
- the upper limit of ⁇ pH is preferably 1.000 or less, more preferably 0.500 or less, from the viewpoint of further suppressing rapid reaction.
- the lower limit of ⁇ pH is not particularly limited, but is preferably 0.0001 or more per unit time from the viewpoint of productivity.
- reaction temperature T The parameter Z can be increased by controlling the temperature T of the mixed solution in the reaction step (hereinafter, sometimes referred to as “reaction temperature T”). Specifically, the value of the parameter Z tends to increase by decreasing the reaction temperature T, that is, by decreasing the reaction temperature coefficient k.
- the reaction temperature T is, for example, the temperature of the mixed solution that can be read by installing a thermometer in the mixed solution, and is preferably 0 to 100 ° C.
- the reaction temperature T is preferably 100 ° C. or less, more preferably 60 ° C. or less, still more preferably 50 ° C. or less, particularly preferably 40 ° C. or less, particularly preferably 30 ° C. or less, in view of further suppressing rapid reaction. C. or less is very preferable.
- the reaction temperature T is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, still more preferably 10 ° C. or higher, particularly preferably 15 ° C. or higher, and extremely preferably 20 ° C. or higher from the viewpoint of allowing the reaction to proceed easily.
- reaction temperature T for example, a temperature range of reaction temperature T ⁇ 3 ° C.
- the method for adjusting the reaction temperature is not particularly limited.
- a container containing one of a metal salt solution or an alkali solution is placed in a water tank filled with water, and the water temperature of the water tank is adjusted to an external circulation device COOLNICS circulator ( There is a method of mixing a metal salt solution and an alkali solution while adjusting with a product manufactured by Tokyo Rika Kikai Co., Ltd. (EYELA), product name cooling thermopump (CTP101).
- the lower limit of the circulation number N from the further suppression of the deviation of the response in the local, preferably 1.00 min -1 or more, more preferably 10.00Min -1 or more, more preferably 15.00Min -1 or higher, 20. 00 min ⁇ 1 or more is particularly preferable.
- the upper limit of the circulation number N is not particularly limited, from the viewpoint of suppressing the splashing during manufacture, preferably 200.00Min -1 or less, 150.00Min -1 or less is more preferable.
- the linear velocity indicates the flow rate of the fluid per unit time (1 minute) and unit area (m 2 ), and is an index indicating the degree of material diffusion.
- the linear velocity u means the linear velocity of the stirring blade when mixing the metal salt solution and the alkali solution.
- the parameter Z can be increased by controlling the linear velocity u. Specifically, the value of the parameter Z tends to increase by increasing the linear velocity u.
- the lower limit of the linear velocity u represented by the formula (3) is preferably 5.00 m / min or more from the viewpoint of further suppressing the reaction from becoming non-uniform because the substance does not diffuse well and is localized, 10.00 m / min or more is more preferable, 20.00 m / min or more is further more preferable, 50.00 m / min or more is especially preferable, and 70.00 m / min or more is very preferable.
- the upper limit of the linear velocity u is not particularly limited, but is preferably 200.00 m / min or less from the viewpoint of suppressing liquid splash during production.
- the area S of the stirring blade for stirring the mixed liquid means the surface area of one surface of the stirring blade, and when there are a plurality of stirring blades, it means the total area of the stirring blades.
- the parameter Z can be increased by controlling the area S. Specifically, when the area S is increased, the value of the parameter Z tends to increase.
- the area S is adjusted according to the size of the liquid amount Q of the mixed liquid. For example, when the liquid amount Q of the mixed liquid is 0.0010 to 0.0050 m 3 , the area S is preferably 0.0005 to 0.0100 m 2 .
- the liquid volume Q of the mixed liquid is a total liquid volume of the metal salt solution and the alkaline liquid (Q b ).
- the amount of the mixed solution is not particularly limited, but is, for example, 0.0010 to 10.00 m 3 .
- the parameter Z can be increased by controlling the rotational speed R. Specifically, the value of the parameter Z tends to increase by increasing the rotation speed R.
- the lower limit of the rotational speed R from the viewpoint of the mixing efficiency, preferably 30min -1 or more, more preferably 100 min -1 or more, 300 min -1 or more is more preferable.
- the upper limit of the rotation speed R is not particularly limited and needs to be adjusted as appropriate depending on the size and shape of the stirring blade, but is preferably 1000 min ⁇ 1 or less from the viewpoint of suppressing liquid splashing.
- the parameter Z can be increased by controlling the turning radius r. Specifically, the value of the parameter Z tends to increase by increasing the rotation radius r.
- the lower limit of the rotation radius r is preferably 0.001 m or more and more preferably 0.01 m or more from the viewpoint of stirring efficiency.
- the upper limit of the turning radius r is not particularly limited, but is preferably 10 m or less from the viewpoint of ease of handling.
- the average value of the rotation radius is within the above range.
- the parameter Z By controlling the number of substitutions M, the parameter Z can be increased. Specifically, the value of the parameter Z tends to increase by decreasing the number of substitutions M.
- the upper limit of the substitution number M is further from the viewpoint of suppressing the reaction would proceed rapidly, preferably 1.0 min -1 or less, more preferably 0.1 min -1 or less, still is 0.02Min -1 or less Preferably, 0.01 min ⁇ 1 or less is particularly preferable.
- the lower limit of the substitution number M is not particularly limited, but is preferably 1.0 ⁇ 10 ⁇ 5 min ⁇ 1 or more from the viewpoint of productivity.
- the mixing speed v means the supply speed of the liquid A when supplying one liquid A of the metal salt solution or the alkali liquid to the other liquid B.
- the parameter Z can be increased by controlling the mixing speed v. Specifically, the value of the parameter Z tends to increase by decreasing the mixing speed v.
- the upper limit of the mixing speed v is 5.00 ⁇ 10 ⁇ 3 m 3 / min (5 L / min) or less from the viewpoint of further suppressing rapid progress of the reaction and further suppressing local reaction bias.
- 1.00 ⁇ 10 ⁇ 3 m 3 / min (1 L / min) or less is more preferable
- 5.00 ⁇ 10 ⁇ 4 m 3 / min (500 mL / min) or less is more preferable
- 1.00 ⁇ 10 ⁇ 4 m 3 / min (100 mL / min) or less is particularly preferable.
- the lower limit of the mixing speed v is not particularly limited, but is preferably 1.00 ⁇ 10 ⁇ 7 m 3 / min (0.1 mL / min) or more from the viewpoint of productivity.
- the tetravalent metal element hydroxide particles produced as described above may contain impurities, the impurities may be removed.
- the method for removing impurities is not particularly limited, and examples thereof include methods such as centrifugation, filter press, and ultrafiltration. This makes it possible to adjust the absorbance with respect to light having a wavelength of 450 to 600 nm, which will be described later.
- a mixed liquid obtained by mixing a metal salt solution and an alkali liquid contains hydroxide particles of a tetravalent metal element, and the material to be polished may be polished using the mixed liquid.
- the slurry manufacturing method is obtained by mixing the abrasive grain manufacturing process for obtaining abrasive grains by the abrasive grain manufacturing method, the abrasive grains obtained in the abrasive grain manufacturing process, and water.
- the abrasive grains are dispersed in water.
- the method for dispersing the abrasive grains in water is not particularly limited, and examples thereof include a dispersion method by stirring; a dispersion method using a homogenizer, an ultrasonic disperser, a wet ball mill, or the like.
- the method for producing a polishing liquid may include a slurry production step for obtaining a slurry by the slurry production method and a polishing liquid preparation step for obtaining a polishing liquid by mixing the slurry and an additive.
- a slurry production step for obtaining a slurry by the slurry production method
- a polishing liquid preparation step for obtaining a polishing liquid by mixing the slurry and an additive.
- the method for producing a polishing liquid comprises the above-mentioned abrasive grain production step, a polishing liquid preparation step for obtaining a polishing liquid by mixing abrasive grains obtained in the abrasive grain production step, an additive, and water.
- the aspect provided may be sufficient. In this case, you may mix the abrasive grain obtained in the abrasive grain manufacturing process, another kind of abrasive grain, and water.
- the polishing liquid according to this embodiment contains at least abrasive grains, additives, and water.
- abrasive grains for abrasive sands.
- additives for abrasive sands.
- water for sands.
- the abrasive grains are characterized by containing a hydroxide of a tetravalent metal element.
- the “tetravalent metal element hydroxide” is a compound containing a tetravalent metal (M 4+ ) and at least one hydroxide ion (OH ⁇ ).
- the hydroxide of the tetravalent metal element may contain an anion other than the hydroxide ion (for example, nitrate ion NO 3 ⁇ , sulfate ion SO 4 2 ⁇ ).
- a hydroxide of a tetravalent metal element may contain an anion (for example, nitrate ion NO 3 ⁇ , sulfate ion SO 4 2 ⁇ ) bonded to the tetravalent metal element.
- an anion for example, nitrate ion NO 3 ⁇ , sulfate ion SO 4 2 ⁇
- the tetravalent metal element is preferably at least one selected from the group consisting of rare earth elements and zirconium.
- the tetravalent metal element is preferably a rare earth element from the viewpoint of further improving the polishing rate.
- the rare earth element capable of taking tetravalence include lanthanoids such as cerium, praseodymium, and terbium. Among them, cerium (tetravalent cerium) is preferable from the viewpoint of easy availability and excellent polishing rate.
- a rare earth element hydroxide and a zirconium hydroxide may be used in combination, or two or more kinds of rare earth element hydroxides may be selected and used.
- abrasive grains can be used in combination as long as the characteristics of the abrasive grains containing a tetravalent metal element hydroxide are not impaired.
- abrasive grains such as silica, alumina, and zirconia can be used.
- the content of the tetravalent metal element hydroxide in the abrasive grains is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and more preferably 80% by mass or more based on the total mass of the abrasive grains. Is particularly preferable, 90% by mass or more is very preferable, 95% by mass or more is very preferable, 98% by mass or more is more preferable, and 99% by mass or more is still more preferable. It is particularly preferable that the abrasive grains are substantially composed of a hydroxide of a tetravalent metal element (substantially 100% by mass of the abrasive grains are hydroxide particles of a tetravalent metal element).
- the content of tetravalent cerium hydroxide in the abrasive grains is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and more preferably 80% by mass or more based on the total mass of the abrasive grains. Particularly preferable is 90% by mass or more, extremely preferable is 95% by mass or more, still more preferable is 98% by mass or more, and further more preferable is 99% by mass or more.
- the abrasive grains are substantially composed of tetravalent cerium hydroxide in that the chemical activity is high and the polishing rate is further improved (substantially 100% by mass of the abrasive grains are tetravalent cerium hydroxide particles). It is particularly preferred.
- the hydroxide of the tetravalent metal element has a great influence on the polishing characteristics. Therefore, by adjusting the content of the hydroxide of the tetravalent metal element, the chemical interaction between the abrasive grains and the surface to be polished can be improved, and the polishing rate can be further improved. That is, the content of the hydroxide of the tetravalent metal element is preferably 0.01% by mass or more based on the total mass of the polishing liquid in that the function of the hydroxide of the tetravalent metal element can be sufficiently expressed. 0.03 mass% or more is more preferable, and 0.05 mass% or more is still more preferable.
- the content of the hydroxide of the tetravalent metal element makes it easy to avoid agglomeration of the abrasive grains, improves the chemical interaction with the surface to be polished, and makes effective use of the characteristics of the abrasive grains. Is preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 1% by mass or less, and most preferably 0.5% by mass or less. .3% by mass or less is very preferable.
- the lower limit of the content of the abrasive grains is not particularly limited, but is preferably 0.01% by mass or more based on the total mass of the polishing liquid in that a desired polishing rate is easily obtained. 0.03 mass% or more is more preferable, and 0.05 mass% or more is still more preferable.
- the upper limit of the content of the abrasive grains is not particularly limited, but it becomes easy to avoid agglomeration of the abrasive grains, and the abrasive grains can effectively act on the surface to be polished so that polishing can proceed smoothly.
- the total amount of the polishing liquid it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, particularly preferably 1% by mass or less, and extremely preferably 0.5% by mass or less, A content of 0.3% by mass or less is very preferable.
- the polishing rate can be further improved by increasing the specific surface area of the abrasive grains in contact with the surface to be polished.
- the mechanical action is suppressed and polishing scratches can be further reduced.
- the upper limit of the average particle diameter is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less, particularly preferably 80 nm or less, in that a further excellent polishing rate can be obtained and polishing scratches can be further reduced. 60 nm or less is very preferable, and 40 nm or less is very preferable.
- the lower limit of the average particle diameter is preferably 1 nm or more, more preferably 2 nm or more, and still more preferably 3 nm or more in that a further excellent polishing rate can be obtained and polishing scratches can be further reduced.
- the average particle diameter of the abrasive grains can be measured by a photon correlation method, and specifically, for example, it can be measured by Malvern apparatus name: Zetasizer 3000HS, Beckman Coulter apparatus name: N5, or the like.
- the measurement method using N5 is, for example, preparing an aqueous dispersion in which the content of abrasive grains is adjusted to 0.2% by mass, putting about 4 mL of this aqueous dispersion in a 1 cm square cell, A cell is installed inside.
- a value obtained by adjusting the refractive index of the dispersion medium to 1.33 and the viscosity to 0.887 mPa ⁇ s and performing the measurement at 25 ° C. can be adopted as the average particle diameter of the abrasive grains.
- the particles containing M (OH) a X b produced according to the production conditions of a hydroxide of a tetravalent metal element absorb light with a wavelength of 400 nm, the abundance of M (OH) a X b It is considered that the polishing rate improves as the absorbance increases with respect to light having a wavelength of 400 nm.
- the absorption peak at a wavelength of 400 nm of M (OH) a X b (for example, M (OH) 3 X) is much smaller than the absorption peak at a wavelength of 290 nm described later.
- the present inventor examined the magnitude of the absorbance using an aqueous dispersion having an abrasive content of 1.0% by mass, which has a relatively large abrasive content and is easily detected with a large absorbance. It has been found that when an abrasive that gives an absorbance of 1.00 or more with respect to light having a wavelength of 400 nm is used in an aqueous dispersion, there is a tendency to improve the polishing rate and to provide excellent storage stability.
- the light absorbency with respect to the light of wavelength 400nm originates in an abrasive grain as above-mentioned, it replaces with the abrasive grain which gives the light absorbency 1.00 or more with respect to the light of wavelength 400nm, and with respect to the light of wavelength 400nm.
- a polishing liquid containing a substance giving an absorbance of 1.00 or higher for example, a yellow pigment component
- the absorbance with respect to light having a wavelength of 400 nm is preferably 1.50 or more from the viewpoint of easy polishing of the material to be polished at an excellent polishing rate.
- the present inventor has found that the abundance of M (OH) a X b is adjusted using the absorbance with respect to light having a wavelength of 400 nm as an index to achieve both the polishing rate and the storage stability. And this inventor uses the abrasive grain which gives the light absorbency 1.00 or more and less than 1.50 with respect to the light of wavelength 400nm in the aqueous dispersion which adjusted content of the abrasive grain to 1.0 mass%, It has been found that excellent storage stability (for example, stability of polishing rate when stored at 60 ° C.
- the absorbance with respect to light having a wavelength of 400 nm is preferably 1.05 or more, more preferably 1.10 or more, further preferably 1.15 or more, particularly preferably 1.20 or more, and 1.25 or more. Highly preferred.
- the inventor of the present invention has an absorbance of 1.000 with respect to light with a wavelength of 290 nm in an aqueous dispersion in which an abrasive that gives an absorbance of 1.00 or more with respect to light with a wavelength of 400 nm is adjusted to 0.0065 mass%. It has been found that when the above is given, the material to be polished can be polished at a further excellent polishing rate.
- polishing rate improvement effect can be obtained by using abrasive grains that give an absorbance of 1.000 or more with respect to light having a wavelength of 290 nm in an aqueous dispersion in which the content of abrasive grains is adjusted to 0.0065 mass% is not always clear.
- the present inventor thinks as follows. That is, a particle containing M (OH) a X b (for example, M (OH) 3 X) generated according to the production conditions of a tetravalent metal element hydroxide has an absorption peak near the wavelength of 290 nm. For example, particles made of Ce 4+ (OH ⁇ ) 3 NO 3 ⁇ have an absorption peak at a wavelength of 290 nm. Therefore, it is considered that the polishing rate is improved as the abundance of M (OH) a Xb increases and the absorbance to light having a wavelength of 290 nm increases.
- the absorbance with respect to light having a wavelength near 290 nm tends to be detected as it exceeds the measurement limit.
- the present inventors examined the magnitude of absorbance using an aqueous dispersion having an abrasive content of 0.0065% by mass with a relatively small abrasive content and a low absorbance that is easily detected. It has been found that when an abrasive that gives an absorbance of 1.000 or more with respect to light having a wavelength of 290 nm is used in the aqueous dispersion, the effect of improving the polishing rate is excellent.
- the present inventor has found that the higher the absorbance of abrasive grains with respect to light near a wavelength of 290 nm, the higher the absorbance of the abrasive grains is, apart from light near a wavelength of 400 nm, where the light-absorbing material tends to exhibit a yellow color. It has been found that the yellowness of the polishing liquid and the slurry using the abrasive grains is increased, and the polishing rate is improved as the yellowness of the polishing liquid and the slurry is increased.
- the lower limit of the absorbance with respect to light having a wavelength of 290 nm is preferably 1.000 or more, more preferably 1.050 or more, still more preferably 1.100 or more, from the viewpoint of polishing the material to be polished at a further excellent polishing rate. 130 or more is particularly preferable.
- the upper limit of absorbance for light having a wavelength of 290 nm is not particularly limited, but is preferably 10.000 or less, more preferably 5.000 or less, and still more preferably 3.000 or less.
- Tetravalent metal element hydroxides (for example, M (OH) a X b ) tend not to absorb light with a wavelength of 450 nm or more, particularly 450 to 600 nm. Therefore, from the viewpoint of polishing the material to be polished at a further excellent polishing rate by suppressing the adverse effect on polishing due to the inclusion of impurities, the abrasive grains have a content of 0.0065% by mass.
- the aqueous dispersion adjusted to (65 ppm) preferably gives an absorbance of 0.010 or less for light having a wavelength of 450 to 600 nm.
- the absorbance with respect to all light in the wavelength range of 450 to 600 nm does not exceed 0.010 in the aqueous dispersion in which the content of the abrasive grains is adjusted to 0.0065% by mass.
- the upper limit of the absorbance with respect to light having a wavelength of 450 to 600 nm is more preferably 0.005 or less, and further preferably 0.001 or less.
- the lower limit of the absorbance with respect to light having a wavelength of 450 to 600 nm is preferably 0.
- the absorbance in the aqueous dispersion can be measured using, for example, a spectrophotometer (device name: U3310) manufactured by Hitachi, Ltd. Specifically, for example, an aqueous dispersion in which the content of abrasive grains is adjusted to 1.0 mass% or 0.0065 mass% is prepared as a measurement sample. About 4 mL of this measurement sample is put into a 1 cm square cell, and the cell is set in the apparatus. Next, the absorbance is measured in the wavelength range of 200 to 600 nm, and the absorbance is judged from the obtained chart.
- a spectrophotometer device name: U3310
- the absorbance is 1.00 or more when the absorbance for light with a wavelength of 400 nm is measured after being diluted excessively so that the content of the abrasive is less than 1.0% by mass, the content of the abrasive is The absorbance may be screened on the assumption that the absorbance is 1.00 or more even when the content is 1.0 mass%. If the absorbance is 1.000 or more when the absorbance for light having a wavelength of 290 nm is measured after being diluted excessively so that the content of the abrasive is less than 0.0065% by mass, the content of the abrasive is Even when the amount is 0.0065% by mass, the absorbance may be screened on the assumption that the absorbance is 1.000 or more.
- the absorbance is 0.010 or less when the absorbance with respect to light having a wavelength of 450 to 600 nm is measured by diluting so that the abrasive content is more than 0.0065% by mass, Even when the amount is 0.0065% by mass, the absorbance may be screened on the assumption that the absorbance is 0.010 or less.
- the polishing liquid according to this embodiment preferably has high transparency to visible light (transparent or nearly transparent by visual observation).
- the abrasive contained in the polishing liquid according to the present embodiment has a light transmittance of 50% with respect to light having a wavelength of 500 nm in an aqueous dispersion in which the content of the abrasive is adjusted to 1.0 mass%. / Cm or more is preferable.
- the lower limit of the light transmittance is more preferably 60% / cm or more, further preferably 70% / cm or more, particularly preferably 80% / cm or more, extremely preferably 90% / cm or more, 95% / Cm or more is very preferable, 98% / cm or more is even more preferable, and 99% / cm or more is still more preferable.
- the upper limit of the light transmittance is 100% / cm.
- the abrasive grains present in the aqueous dispersion are particles having a large particle diameter (hereinafter referred to as “coarse particles”). It is thought that there are relatively many.
- an additive for example, polyvinyl alcohol (PVA)
- PVA polyvinyl alcohol
- the number of abrasive grains acting on the surface to be polished per unit area (the number of effective abrasive grains) is reduced, and the specific surface area of the abrasive grains in contact with the surface to be polished is reduced. Conceivable.
- the abrasive grains present in the aqueous dispersion are considered to be in a state where there are few “coarse particles”. It is done.
- an additive for example, polyvinyl alcohol
- the number of abrasive grains (number of effective abrasive grains) acting on the surface to be polished per unit area is maintained, and the specific surface area of the abrasive grains in contact with the surface to be polished is maintained. It is considered to be.
- the light transmittance is a transmittance for light having a wavelength of 500 nm.
- the light transmittance is measured with a spectrophotometer. Specifically, for example, it is measured with a spectrophotometer U3310 (device name) manufactured by Hitachi, Ltd.
- an aqueous dispersion in which the content of abrasive grains is adjusted to 1.0% by mass is prepared as a measurement sample. About 4 mL of this measurement sample is put into a 1 cm square cell, and the cell is set in the apparatus to perform measurement.
- the content of the abrasive grains is 50% / cm or more in an aqueous dispersion having a content of greater than 1.0% by mass
- the light transmittance is also obtained when this is diluted to 1.0% by mass. Is apparently 50% / cm or more. Therefore, the light transmittance can be screened by a simple method by using an aqueous dispersion having an abrasive content greater than 1.0% by mass.
- the absorbance and light transmittance that the abrasive grains give in the aqueous dispersion are preferably excellent in stability.
- the absorbance with respect to light with a wavelength of 400 nm is preferably 1.00 or more, and the absorbance with respect to light with a wavelength of 290 nm is 1.000 or more.
- the absorbance with respect to light with a wavelength of 450 to 600 nm is preferably 0.010 or less, and the light transmittance with respect to light with a wavelength of 500 nm is preferably 50% / cm or more. Further preferred ranges of these absorbance and light transmittance are the same as those described above for the abrasive grains.
- the absorbance and light transmittance that the abrasive grains contained in the polishing liquid give in the aqueous dispersion are obtained by removing the solid components other than the abrasive grains and the liquid components other than water, and then the aqueous dispersion having a predetermined abrasive grain content. It can be prepared and measured using the aqueous dispersion.
- the solid component or the liquid component may be removed by centrifugation using a centrifugal machine that can apply a gravitational acceleration of several thousand G or less, Centrifugal methods such as ultracentrifugation using a centrifuge; chromatography methods such as distribution chromatography, adsorption chromatography, gel permeation chromatography, ion exchange chromatography; natural filtration, vacuum filtration, pressure filtration, ultrafiltration Filtration methods such as distillation; distillation methods such as vacuum distillation and atmospheric distillation can be used, and these may be combined as appropriate.
- Centrifugal methods such as ultracentrifugation using a centrifuge
- chromatography methods such as distribution chromatography, adsorption chromatography, gel permeation chromatography, ion exchange chromatography
- natural filtration, vacuum filtration, pressure filtration, ultrafiltration Filtration methods such as distillation
- distillation methods such as vacuum distillation and atmospheric distillation can be used, and these may be combined as appropriate.
- a chromatography method, a filtration method and the like can be mentioned, and among them, gel permeation chromatography and ultrafiltration are preferable.
- the abrasive grains contained in the polishing liquid can pass through the filter by setting appropriate conditions.
- examples thereof include a chromatography method, a filtration method, and a distillation method, and gel permeation chromatography, ultrafiltration, and vacuum distillation are preferable.
- abrasive grains When other types of abrasive grains are included, examples thereof include filtration methods and centrifugal separation methods. In the case of filtration, in the filtrate, in the liquid phase in the case of centrifugation, abrasive grains containing a hydroxide of a tetravalent metal element. Is included more.
- the abrasive grain components can be fractionated and / or other components can be fractionated under the following conditions.
- Sample solution 100 ⁇ L of polishing liquid Detector: UV-VIS detector manufactured by Hitachi, Ltd., trade name “L-4200”, wavelength: 400 nm Integrator: Hitachi, Ltd. GPC integrator, product name “D-2500” Pump: Hitachi, Ltd., trade name “L-7100” Column: Hitachi Chemical Co., Ltd. water-based HPLC packed column, trade name “GL-W550S” Eluent: Deionized water Measurement temperature: 23 ° C Flow rate: 1 mL / min (pressure is about 40-50 kg / cm 2 ) Measurement time: 60 minutes
- a deaeration device it is preferable to deaerate the eluent using a deaeration device before performing chromatography.
- the deaerator cannot be used, it is preferable to deaerate the eluent in advance with ultrasonic waves or the like.
- the abrasive components contained in the polishing liquid it may not be possible to separate the abrasive components even under the above conditions.In that case, by optimizing the sample solution amount, column type, eluent type, measurement temperature, flow rate, etc. Can be separated. Further, by adjusting the pH of the polishing liquid, there is a possibility that the distillation time of the components contained in the polishing liquid can be adjusted and separated from the abrasive grains. When there are insoluble components in the polishing liquid, it is preferable to remove the insoluble components by filtration, centrifugation, or the like, if necessary.
- the polishing liquid according to this embodiment can obtain a particularly excellent polishing rate with respect to an insulating material (for example, silicon oxide), and thus is particularly suitable for use in polishing a substrate having an insulating material.
- an insulating material for example, silicon oxide
- the polishing rate and the polishing characteristics other than the polishing rate can be made highly compatible by appropriately selecting the additive.
- the additive examples include a dispersant that increases the dispersibility of abrasive grains, a polishing rate improver that improves the polishing rate, a flattening agent (a flattening agent that reduces irregularities on the polished surface after polishing, and a substrate after polishing.
- a dispersant that increases the dispersibility of abrasive grains
- a polishing rate improver that improves the polishing rate
- a flattening agent a flattening agent that reduces irregularities on the polished surface after polishing
- Known additives such as a global planarizing agent for improving global planarity) and a selective ratio improver for improving the polishing selectivity of an insulating material with respect to a stopper material such as silicon nitride or polysilicon can be used without particular limitation. .
- Examples of the dispersant include vinyl alcohol polymer and derivatives thereof, betaine, lauryl betaine, lauryl dimethylamine oxide and the like.
- Examples of the polishing rate improver include ⁇ -alanine betaine and stearyl betaine.
- Examples of the flattening agent that reduces the unevenness of the surface to be polished include ammonium lauryl sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, and the like.
- Examples of the global flattening agent include polyvinyl pyrrolidone and polyacrolein.
- Examples of the selectivity improver include polyethyleneimine, polyallylamine, and chitosan. These can be used alone or in combination of two or more.
- the polishing liquid according to this embodiment preferably contains at least one selected from the group consisting of vinyl alcohol polymers and derivatives thereof as an additive.
- the additive coats the surface of the abrasive grains, the adhesion of the abrasive grains to the surface to be polished is suppressed, so that the dispersibility of the abrasive grains is improved and the stability of the abrasive grains is further improved. be able to.
- the cleanability of the surface to be polished can be improved.
- vinyl alcohol which is a monomer of polyvinyl alcohol, tends not to exist as a stable compound by itself.
- polyvinyl alcohol is generally obtained by polymerizing a vinyl carboxylate monomer such as a vinyl acetate monomer to obtain vinyl polycarboxylate and then saponifying (hydrolyzing) it. Therefore, for example, a vinyl alcohol polymer obtained using a vinyl acetate monomer as a raw material has —OCOCH 3 and hydrolyzed —OH as functional groups in the molecule, and becomes —OH. Ratio is defined as the degree of saponification. That is, a vinyl alcohol polymer whose saponification degree is not 100% has a structure substantially like a copolymer of vinyl acetate and vinyl alcohol.
- the vinyl alcohol polymer is a portion derived from a vinyl carboxylate monomer by copolymerizing a vinyl carboxylate monomer such as vinyl acetate monomer and other vinyl group-containing monomers (for example, ethylene, propylene, styrene, vinyl chloride). All or a part of the saponified product may be saponified.
- a vinyl carboxylate monomer such as vinyl acetate monomer and other vinyl group-containing monomers (for example, ethylene, propylene, styrene, vinyl chloride). All or a part of the saponified product may be saponified.
- these are generically defined as “vinyl alcohol polymer”, and “vinyl alcohol polymer” is ideally a polymer having the following structural formula. (Where n represents a positive integer)
- “Derivatives” of vinyl alcohol polymers include derivatives of vinyl alcohol homopolymers (ie, polymers having a saponification degree of 100%), and vinyl alcohol monomers and other vinyl group-containing monomers (eg, ethylene, propylene, styrene, Vinyl chloride) as a copolymer derivative.
- Examples of the vinyl alcohol polymer derivatives include those obtained by substituting some of the hydroxyl groups of the polymer with amino groups, carboxyl groups, ester groups, and the like, and those obtained by modifying some of the hydroxyl groups of the polymer.
- Examples of such derivatives include reactive polyvinyl alcohol (for example, GOHSEIMER (registered trademark) Z manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and cationized polyvinyl alcohol (for example, GOHSEIMER manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
- the vinyl alcohol polymer and its derivative function as an abrasive dispersing agent, and have the effect of further improving the stability of the polishing liquid.
- the hydroxyl group of the vinyl alcohol polymer and its derivatives interacts with abrasive grains containing tetravalent metal element hydroxides, thereby suppressing the aggregation of abrasive grains and suppressing changes in the grain size of the abrasive grains in the polishing liquid.
- the stability can be further improved.
- Vinyl alcohol polymer and its derivatives are used in combination with abrasive grains containing tetravalent metal element hydroxide, and polishing selection of insulating material (eg silicon oxide) against stopper material (eg silicon nitride, polysilicon)
- insulating material eg silicon oxide
- stopper material eg silicon nitride, polysilicon
- the ratio polishing rate of insulating material / polishing rate of stopper material
- the vinyl alcohol polymer and derivatives thereof can improve the flatness of the polished surface after polishing, and can also prevent adhesion of abrasive grains to the polished surface (improvement of cleaning properties).
- the saponification degree of the vinyl alcohol polymer and its derivatives is preferably 95 mol% or less in that the polishing selectivity of the insulating material to the stopper material can be further increased.
- the upper limit of the degree of saponification is more preferably 90 mol% or less, still more preferably 88 mol% or less, particularly preferably 85 mol% or less, extremely preferably 83 mol% or less, and very preferably 80 mol% or less.
- the lower limit of the saponification degree is not particularly limited, but is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol% or more from the viewpoint of excellent solubility in water.
- the saponification degree of a vinyl alcohol polymer and its derivative can be measured based on JIS K 6726 (polyvinyl alcohol test method).
- the upper limit of the average degree of polymerization (weight average molecular weight) of the vinyl alcohol polymer and derivatives thereof is not particularly limited, but is preferably 3000 or less, more preferably 2000 or less, from the viewpoint of further suppressing a decrease in the polishing rate of the material to be polished. 1000 or less is more preferable.
- the lower limit of the average polymerization degree is preferably 50 or more, more preferably 100 or more, and further preferably 150 or more.
- the average degree of polymerization of the vinyl alcohol polymer and its derivatives can be measured according to JIS K 6726 (polyvinyl alcohol test method).
- the vinyl alcohol polymer and its derivatives for the purpose of adjusting the polishing selectivity of the insulating material relative to the stopper material and the flatness of the substrate after polishing, a plurality of polymers having different saponification degrees or average polymerization degrees are used. You may use it in combination.
- the saponification degree of at least one vinyl alcohol polymer and its derivative is preferably 95 mol% or less, and from the viewpoint of further improving the polishing selectivity, the average calculated from the respective saponification degree and blending ratio More preferably, the saponification degree is 95 mol% or less.
- the preferable range of the degree of saponification is the same as that described above.
- the content of the additive is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.08% by mass based on the total mass of the polishing liquid from the viewpoint of more effectively obtaining the effect of the additive. % Or more is more preferable, and 0.1% by mass or more is particularly preferable.
- the content of the additive is preferably 10% by mass or less, more preferably 5.0% by mass or less, and more preferably 3.0% by mass based on the total mass of the polishing liquid from the viewpoint of further suppressing the decrease in the polishing rate of the material to be polished. The following is more preferable, and 1.0% by mass or less is particularly preferable.
- water Although there is no restriction
- the water content is not particularly limited, and may be the remainder of the polishing liquid excluding the content of other components.
- the method for dispersing the abrasive grains in water is not particularly limited, and specific examples include a dispersion method by stirring; a dispersion method by a homogenizer, an ultrasonic disperser, a wet ball mill, or the like.
- the pH of the polishing liquid (25 ° C.) is preferably 2.0 to 9.0 from the viewpoint that a further excellent polishing rate can be obtained. This is presumably because the surface potential of the abrasive grains becomes good with respect to the surface potential of the surface to be polished, and the abrasive grains easily act on the surface to be polished.
- the lower limit of the pH is preferably 2.0 or more, more preferably 3.0 or more, and even more preferably 4.0 or more, in that the pH of the polishing liquid is stabilized and problems such as aggregation of abrasive grains are less likely to occur. .
- the upper limit of the pH is preferably 9.0 or less, more preferably 8.0 or less, and even more preferably 7.5 or less in that the dispersibility of the abrasive grains is excellent and a further excellent polishing rate is obtained.
- the pH of the polishing liquid can be measured by the same method as the pH of the mixed liquid.
- a conventionally known pH adjusting agent can be used without particular limitation.
- the pH adjuster include inorganic acids such as phosphoric acid, sulfuric acid, and nitric acid; formic acid, acetic acid, propionic acid, maleic acid, phthalic acid, citric acid, succinic acid, malonic acid, glutaric acid, and adipic acid.
- Organic acids such as carboxylic acids such as fumaric acid, lactic acid and benzoic acid; amines such as ethylenediamine, toluidine, piperazine, histidine, aniline, 2-aminopyridine, 3-aminopyridine, picolinic acid, morpholine, piperidine and hydroxylamine
- nitrogen-containing heterocyclic compounds such as pyridine, imidazole, triazole, pyrazole, benzimidazole, and benzotriazole.
- the pH adjuster may be contained in a slurry (including a slurry precursor, a slurry storage solution, and the like), an additive solution, and the like described later.
- the pH stabilizer refers to an additive for adjusting to a predetermined pH, and a buffer component is preferable.
- the buffer component is preferably a compound having a pKa within ⁇ 1.5 with respect to a predetermined pH, and more preferably a compound having a pKa within ⁇ 1.0.
- Examples of such compounds include amino acids such as glycine, arginine, lysine, asparagine, aspartic acid, and glutamic acid; a mixture of the carboxylic acid and the base; a salt of the carboxylic acid, and the like.
- the slurry according to this embodiment may be used as it is for polishing, or may be used as a slurry in a so-called two-component type polishing liquid in which the constituents of the polishing liquid are divided into a slurry and an additive liquid.
- the polishing liquid and the slurry differ in the presence or absence of an additive, and the polishing liquid can be obtained by adding the additive to the slurry.
- the slurry according to this embodiment contains at least abrasive grains similar to the polishing liquid according to this embodiment, and water.
- the abrasive grains are characterized by containing a hydroxide of a tetravalent metal element, and the preferred range and measuring method of the average secondary particle diameter of the abrasive grains are used in the polishing liquid according to this embodiment. It is the same as the abrasive grain to be used.
- the hydroxide of the tetravalent metal element has a great influence on the polishing characteristics. Therefore, by adjusting the content of the hydroxide of the tetravalent metal element, the chemical interaction between the abrasive grains and the surface to be polished can be improved, and the polishing rate can be further improved. That is, the content of the hydroxide of the tetravalent metal element is preferably 0.01% by mass or more based on the total mass of the slurry in that the function of the hydroxide of the tetravalent metal element can be sufficiently expressed. 0.03 mass% or more is more preferable, and 0.05 mass% or more is still more preferable.
- the content of the tetravalent metal element hydroxide makes it easy to avoid agglomeration of the abrasive grains, improves the chemical interaction with the surface to be polished, and improves the characteristics of the abrasive grains (for example, improving the polishing rate). 8 mass% or less, more preferably 5 mass% or less, still more preferably 3 mass% or less, particularly preferably 1 mass% or less, and 0.7 mass% based on the total mass of the slurry. % Or less is very preferable, and 0.5% by mass or less is very preferable.
- the lower limit of the content of abrasive grains is preferably 0.01% by mass or more, and 0.03% by mass or more based on the total mass of the slurry, in that a desired polishing rate is easily obtained. More preferably, 0.05 mass% or more is still more preferable.
- the upper limit of the content of the abrasive grains is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the slurry, in that it is easy to avoid agglomeration of the abrasive grains. Less than 1% by mass is more preferable, 1% by mass or less is particularly preferable, 0.7% by mass or less is very preferable, and 0.5% by mass or less is very preferable.
- the pH (25 ° C.) of the slurry according to the present embodiment is such that the surface potential of the abrasive grains with respect to the surface potential of the surface to be polished becomes good, and the abrasive grains easily act on the surface to be polished.
- the lower limit of the pH is preferably 2.0 or more, more preferably 2.2 or more, and even more preferably 2.5 or more, in that the pH of the slurry is stabilized and problems such as agglomeration of abrasive grains are less likely to occur.
- the upper limit of the pH is preferably 9.0 or less, more preferably 8.0 or less, still more preferably 7.0 or less, and 6.5 in that the abrasive dispersibility is excellent and a further excellent polishing rate is obtained.
- the following is particularly preferable, and 6.0 or less is very preferable.
- the pH of the slurry can be measured by the same method as the pH of the mixed solution.
- the constituents of the polishing liquid are the slurry and the additive liquid so that the slurry (first liquid) and the additive liquid (second liquid) are mixed to become the polishing liquid. It is stored separately.
- the slurry the slurry according to this embodiment can be used.
- the additive solution a solution in which the additive is dissolved in water (a solution containing the additive and water) can be used.
- the polishing liquid set is used as a polishing liquid by mixing the slurry and the additive liquid during polishing.
- the constituents of the polishing liquid in at least two liquids, problems such as agglomeration of abrasive grains and changes in polishing characteristics, which are a concern when stored for a long time after mixing the additives, Can be avoided, and the polishing liquid can be further improved in storage stability.
- the constituent components may be divided into three or more liquids.
- the same additive as described in the polishing solution can be used.
- the content of the additive in the additive liquid is 0.01 mass on the basis of the total mass of the additive liquid from the viewpoint of suppressing an excessive decrease in the polishing rate when the additive liquid and the slurry are mixed to prepare a polishing liquid. % Or more is preferable, and 0.02 mass% or more is more preferable.
- the content of the additive in the additive solution is 20% by mass or less based on the total mass of the additive solution from the viewpoint of suppressing an excessive decrease in the polishing rate when the additive solution and the slurry are mixed to prepare a polishing solution. Is preferred.
- the water in the additive solution is not particularly limited, but deionized water, ultrapure water or the like is preferable.
- the water content is not particularly limited, and may be the remainder excluding the content of other components.
- the substrate polishing method using the polishing liquid, slurry or polishing liquid set, and the substrate obtained thereby will be described.
- the polishing method according to this embodiment is a polishing method using a one-liquid type polishing liquid when the polishing liquid or slurry is used, and a two-liquid type polishing liquid or three liquids or more when using the polishing liquid set. This is a polishing method using this type of polishing liquid. According to these polishing methods, the material to be polished can be polished at an excellent polishing rate. Further, according to these polishing methods, it is possible to suppress the generation of polishing flaws and to obtain a substrate having excellent flatness.
- the substrate according to the present embodiment is polished by the polishing method.
- a substrate having a material to be polished on its surface is polished.
- the material to be polished may be polished using a stopper formed under the material to be polished.
- the substrate polishing method according to the present embodiment includes, for example, at least a preparation process, a substrate arrangement process, and a polishing process.
- a substrate having a material to be polished on the surface is prepared.
- the substrate placement step the substrate is placed so that the material to be polished is placed facing the polishing pad.
- the polishing step at least a part of the material to be polished is removed using a polishing liquid, a slurry, or a polishing liquid set.
- the shape of the material to be polished which is an object to be polished, is not particularly limited, but is, for example, a film shape (film to be polished).
- Examples of materials to be polished include inorganic insulating materials such as silicon oxide; organic insulating materials such as organosilicate glass and wholly aromatic ring-based low-k materials; and stopper materials such as silicon nitride and polysilicon. Materials and organic insulating materials are preferable, and inorganic insulating materials are more preferable.
- the silicon oxide film can be obtained by a low pressure CVD method, a plasma CVD method, or the like.
- the silicon oxide film may be doped with an element such as phosphorus or boron. It is preferable that the surface of the material to be polished (surface to be polished) has irregularities. In the substrate polishing method according to this embodiment, the uneven surface of the material to be polished is preferentially polished, and a substrate with a flattened surface can be obtained.
- the polishing step at least a part of the material to be polished is polished by supplying the polishing liquid or slurry between the material to be polished on the substrate and the polishing pad on the polishing surface plate.
- a polishing liquid or slurry is supplied between the polishing pad and the material to be polished, and the base and the polishing surface plate are moved relatively to each other. A part is polished.
- the polishing liquid and the slurry may be directly supplied onto the polishing pad as a composition having a desired water content.
- the polishing liquid and slurry according to the present embodiment are used by diluting the liquid component by, for example, twice or more (mass basis) with a liquid medium such as water from the viewpoint of suppressing costs related to storage, transportation, storage, and the like. It can be stored as a stock solution for polishing liquid or a stock solution for slurry.
- a liquid medium such as water from the viewpoint of suppressing costs related to storage, transportation, storage, and the like. It can be stored as a stock solution for polishing liquid or a stock solution for slurry.
- Each of the storage liquids may be diluted with a liquid medium immediately before polishing, or may be diluted on the polishing pad by supplying the storage liquid and the liquid medium onto the polishing pad.
- the lower limit of the dilution ratio (mass basis) of the stock solution is preferably 2 times or more, more preferably 3 times or more, and more preferably 5 times or more because the higher the magnification, the higher the cost-saving effect on storage, transportation, storage, etc. Further preferred is 10 times or more.
- the upper limit of the dilution rate is not particularly limited, but the higher the magnification, the greater the amount of components contained in the stock solution (the higher the concentration), and the lower the stability during storage. Preferably, 200 times or less is more preferable, 100 times or less is more preferable, and 50 times or less is particularly preferable. The same applies to the polishing liquid in which the constituent components are divided into three or more liquids.
- the content of abrasive grains is not particularly limited, but is preferably 20% by mass or less, and preferably 15% by mass or less, based on the total mass of the storage liquid, in that it is easy to avoid agglomeration of abrasive grains. More preferably, 10% by mass or less is further preferable, and 5% by mass or less is particularly preferable.
- the content of the abrasive grains is preferably 0.02% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the storage liquid, from the viewpoint of suppressing costs related to storage, transportation, storage, and the like. More preferably, it is more preferably at least 1% by mass.
- the substrate polishing method according to the present embodiment may have a polishing liquid preparation step of obtaining a polishing liquid by mixing the slurry and the additive liquid before the polishing step.
- the material to be polished is polished using the polishing liquid obtained in the polishing liquid preparation process.
- the slurry and the additive liquid may be fed through separate pipes, and these pipes may be joined just before the supply pipe outlet to obtain a polishing liquid.
- the polishing liquid may be directly supplied onto the polishing pad as a polishing liquid having a desired water content, or may be diluted on the polishing pad after being supplied onto the polishing pad as a storage liquid having a low water content.
- the slurry and the additive liquid are supplied between the polishing pad and the material to be polished, respectively, and the slurry and the additive liquid are mixed, and the slurry is added by the polishing liquid obtained. At least a part of the polishing material may be polished.
- the slurry and the additive liquid can be supplied onto the polishing pad by separate liquid feeding systems.
- the slurry and / or additive liquid may be directly supplied onto the polishing pad as a liquid having a desired water content, or may be diluted on the polishing pad after being supplied onto the polishing pad as a storage liquid having a low water content. .
- a polishing apparatus used in the polishing method according to the present embodiment for example, a holder for holding a substrate having a material to be polished, a motor whose rotation speed can be changed, and the like can be attached and a polishing pad can be attached.
- polishing pad For example, a general nonwoven fabric, a polyurethane foam, and a porous fluororesin can be used. It is preferable that the polishing pad is grooved so as to collect a polishing liquid or the like.
- the polishing conditions are not particularly limited, but from the viewpoint of suppressing the substrate from popping out, the rotation speed of the polishing platen is preferably a low rotation of 200 min ⁇ 1 (rpm) or less.
- the pressure (working load) applied to the substrate is preferably 100 kPa or less from the viewpoint of further suppressing the occurrence of polishing scratches.
- the substrate after polishing is preferably washed thoroughly under running water, and then water droplets adhering to the substrate are removed by a spin dryer or the like and then dried.
- a [L] water was put in a container, and an aqueous solution of cerium ammonium nitrate having a concentration of 50% by mass (general formula Ce (NH 4 ) 2 (NO 3 ) 6 , formula weight 548.2 g / mol, manufactured by Nippon Chemical Industry Co., Ltd., Product name 50% CAN solution) was added and mixed with B [L]. Thereafter, the liquid temperature was adjusted to C [° C.] to obtain an aqueous metal salt solution.
- the metal salt concentration of the metal salt aqueous solution is as shown in Table 1.
- the container containing the metal salt aqueous solution was placed in a water tank filled with water.
- the water temperature of the water tank was adjusted to a temperature C [° C.] with an external circulation device COOLNICS circulator (manufactured by Tokyo Rika Kikai Co., Ltd. (EYELA), product name cooling thermopump CTP101).
- COOLNICS circulator manufactured by Tokyo Rika Kikai Co., Ltd. (EYELA), product name cooling thermopump CTP101.
- the pH of the slurry precursor 1 is as shown in Table 1 as “end pH”, and the pH change ⁇ pH per unit time is as shown in Table 1.
- ⁇ pH the average value of the amount of change in pH per minute from the start of mixing the aqueous metal salt solution to the alkaline solution until the pH of the mixed solution reaches the “end pH” was adopted.
- the parameter Z is also as shown in Table 1.
- the slurry precursor 1 was centrifuged at 3000 G, and solid-liquid separation was performed by decantation to remove the liquid. An appropriate amount of water was added to the obtained filtrate and the mixture was stirred well, and then solid-liquid separation was further performed three times by centrifugation and decantation.
- the abrasive grains contained in the slurry precursor 2 contain at least a part of particles having nitrate ions bonded to the cerium element.
- the abrasive grains contained cerium hydroxide since at least a part of the particles having hydroxide ions bonded to the cerium element was contained, it was confirmed that the abrasive grains contained cerium hydroxide. From these results, it was confirmed that the hydroxide of cerium contains hydroxide ions bonded to the cerium element.
- a measurement sample (aqueous dispersion).
- About 4 mL of the measurement sample was placed in a 1 cm square cell, and the cell was placed in a spectrophotometer (device name: U3310) manufactured by Hitachi, Ltd.
- Absorbance was measured in the wavelength range of 200 to 600 nm, and the absorbance with respect to light with a wavelength of 400 nm and the light transmittance with respect to light with a wavelength of 500 nm were measured. The results are shown in Table 2.
- the measurement sample similar to the measurement sample used for the measurement of absorbance and light transmittance in Examples 1 to 5 was held at 60 ° C. for 72 hours, and then the absorbance and light transmittance were measured in the same manner.
- Absorbance for light with a wavelength of 400 nm is 1.00 or more and less than 1.50
- absorbance for light with a wavelength of 290 nm is 1.000 or more
- absorbance for light with a wavelength of 450 to 600 nm is 0.010 or less
- the light transmittance for the light was 50% / cm or more.
- An additive liquid 1 containing 5% by mass of polyvinyl alcohol and X% by mass of imidazole was prepared as an additive.
- 150 g of water was added to 100 g of additive liquid 1 to obtain additive liquid 2.
- Slurry 1 abrasive grain content: 0.2 mass%, polyvinyl alcohol content: 1.0 mass% was obtained by mixing Slurry 1 and additive liquid 2 at 1: 1 (mass ratio).
- the X mass% was determined so that the pH of the polishing liquid was 6.0.
- the saponification degree of polyvinyl alcohol in the polyvinyl alcohol aqueous solution was 80 mol%, and the average polymerization degree was 300.
- the slurry 2 (slurry obtained from the slurry storage solution stored at 60 ° C./72 hours) and the additive solution 2 were mixed to obtain a polishing solution 2.
- the change in film thickness before and after polishing was measured using an optical interference type film thickness measuring device to determine the polishing rate. Further, the ratio of the difference between the polishing rate of the polishing solution 1 and the polishing rate of the polishing solution 2 with respect to the polishing rate of the polishing solution 1 (difference in polishing rate / polishing rate of the polishing solution 1 ⁇ 100) was calculated as the rate of change in polishing rate. .
- the results are shown in Table 3.
- the polishing liquids of the examples are transparent in appearance even after storage at 60 ° C./72 hours, and the rate of change in the polishing rate is small.
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Abstract
Description
Z=[1/(ΔpH×k)]×(N/M)/1000 ・・・(1)
[式(1)中、ΔpHは、金属塩溶液及びアルカリ液の混合液の1分間当たりのpH変化量を示し、kは、反応温度係数を示し、Nは、循環数(min-1)を示し、Mは、置換数(min-1)を示す。]
N=(u×S)/Q ・・・(2)
[式(2)中、uは、混合液を撹拌する撹拌羽根の線速度(m/min)を示し、Sは、撹拌羽根の面積(m2)を示し、Qは、混合液の液量(m3)を示す。]
u=2π×R×r ・・・(3)
[式(3)中、Rは、撹拌羽根の回転数(min-1)を示し、rは、撹拌羽根の回転半径(m)を示す。]
M=v/Q ・・・(4)
[式(4)中、vは、金属塩溶液及びアルカリ液の混合速度(m3/min)を示し、Qは、混合液の液量(m3)を示す。]
本実施形態に係る砥粒は、4価金属元素の水酸化物を含む。このような砥粒を得るための製造方法は、4価金属元素の塩を含む金属塩溶液(第一の液。例えば金属塩水溶液)と、アルカリ源(塩基)を含むアルカリ液(第二の液。例えばアルカリ水溶液)とを混合して4価金属元素の塩とアルカリ源とを反応させることにより、4価金属元素の水酸化物を含む粒子(以下、「4価金属元素の水酸化物粒子」という)を得る反応工程と、反応工程において得られた4価金属元素の水酸化物粒子を加熱して、4価金属元素の水酸化物を含む砥粒を得る加熱工程と、を備える。当該製造方法により、粒子径が極めて細かい粒子を得ることができ、研磨傷の低減効果に優れた砥粒を得ることができる。
Z=[1/(ΔpH×k)]×(N/M)/1000 ・・・(1)
[式(1)中、ΔpHは、混合液の1分間当たりのpH変化量を示し、kは、反応温度係数を示し、Nは、循環数(min-1)を示し、Mは、置換数(min-1)を示す。]
条件(a):砥粒の含有量を1.0質量%に調整した水分散液において波長400nmの光に対して吸光度1.00以上を与える。
条件(b):砥粒の含有量を1.0質量%に調整した水分散液において波長500nmの光に対して光透過率50%/cm以上を与える。
条件(c):砥粒の含有量を0.0065質量%(65ppm)に調整した水分散液において波長290nmの光に対して吸光度1.000以上を与える。なお、「ppm」は、質量ppm、すなわち「parts per million mass」を意味するものとする。
本発明者は、検討の結果、4価金属元素の水酸化物粒子の製造に際して、4価金属元素の塩とアルカリ源との反応を穏やかに且つ均一に進行させることで、優れた研磨速度で被研磨材料を研磨可能であり且つ保管安定性が高い4価金属元素の水酸化物粒子が得られやすくなることを見出した。このような知見に基づき、本発明者は、式(1)のパラメータZを制御することにより、優れた研磨速度で被研磨材料を研磨可能であり且つ保管安定性が高い4価金属元素の水酸化物粒子を製造しやすくなることを見出した。具体的には、式(1)の各パラメータをパラメータZが大きくなるように調整することで前記4価金属元素の水酸化物粒子を製造しやすくなる。
要素A:[1/(ΔpH×k)]
要素B:(N/M)
k=2[(T-20)/10] ・・・(5)
[式(5)中、Tは、混合液の温度(℃)を示す。]
N=(u×S)/Q ・・・(2)
[式(2)中、uは、前記混合液を撹拌する撹拌羽根の線速度(m/min)を示し、Sは、撹拌羽根の面積(m2)を示し、Qは、前記混合液の液量(m3)を示す。]
u=ω×r=2π×R×r ・・・(3)
[式(3)中、ωは、撹拌羽根の角速度(rad/min)を示し、Rは、撹拌羽根の回転数(min-1)を示し、rは、撹拌羽根の回転半径(m)を示す。]
N=F/Q ・・・(2′)
として求めることができる。
M=v/Q ・・・(4)
[式(4)中、vは、金属塩溶液及びアルカリ液の混合速度(m3/min)を示し、Qは、前記混合液の液量(m3)を示す。
pH変化量ΔpHとは、金属塩溶液とアルカリ液との混合開始時から、混合液のpHが一定のpHに達して安定するまでの間における単位時間(1分間)当たりのpHの変化量の平均値である。ΔpHを制御することにより、パラメータZの値を高めることができる。具体的には、ΔpHを低く抑えることにより、パラメータZの値は高くなる傾向がある。これを達成するための具体的手段としては、金属塩溶液における金属塩濃度を高くすること、アルカリ液におけるアルカリ濃度を低くすること、又は、アルカリ液におけるアルカリ源として弱塩基性のアルカリ源を使用すること等が挙げられる。
反応工程における混合液の温度T(以下、場合により「反応温度T」という。)を制御することにより、パラメータZを高めることができる。具体的には、反応温度Tを低くする、すなわち反応温度係数kを低くすることにより、パラメータZの値が高くなる傾向がある。
循環数Nの下限は、局所における反応の偏りを更に抑制する観点から、1.00min-1以上が好ましく、10.00min-1以上がより好ましく、15.00min-1以上が更に好ましく、20.00min-1以上が特に好ましい。循環数Nの上限は、特に制限されないが、製造中の液はねを抑制する観点から、200.00min-1以下が好ましく、150.00min-1以下がより好ましい。
線速度とは、単位時間(1分間)及び単位面積(m2)当たりの流体の流量を示すものであり、物質の拡散度合いを示す指標である。本実施形態において線速度uは、金属塩溶液及びアルカリ液の混合時における撹拌羽根の線速度を意味する。線速度uを制御することによりパラメータZを高めることができる。具体的には、線速度uを高めることにより、パラメータZの値が高くなる傾向がある。
混合液を撹拌する撹拌羽根の面積Sとは、撹拌羽根の一方面の表面積を意味しており、撹拌羽根が複数存在する場合には、各撹拌羽根の面積の合計を意味する。面積Sを制御することによりパラメータZを高めることができる。具体的には、面積Sを大きくすることにより、パラメータZの値が高くなる傾向がある。
混合液の液量Qは、金属塩溶液の液量及びアルカリ液の液量(Qb)の総液量である。例えば、原料として50質量%の金属塩溶液を用いる場合は、50質量%の金属塩溶液の液量(Qa)と、それを希釈する水の液量(Qw)と、アルカリ液の液量(Qb)との総液量となる。混合液の液量は、特に制限されないが、例えば0.0010~10.00m3である。式(2)において循環数Nに含まれる液量Qと、式(4)において置換数Mに含まれる液量Qとは互いに相殺されることとなり、パラメータZは、液量Qの値に大きく依存しない傾向がある。
回転数Rを制御することによりパラメータZを高めることができる。具体的には、回転数Rを大きくすることにより、パラメータZの値が高くなる傾向がある。
回転半径rを制御することによりパラメータZを高めることができる。具体的には、回転半径rを大きくすることにより、パラメータZの値が高くなる傾向がある。
置換数Mを制御することにより、パラメータZを高めることができる。具体的には、置換数Mを小さくすることにより、パラメータZの値が高くなる傾向がある。
混合速度vとは、金属塩溶液又はアルカリ液の一方の液Aを他方の液Bに供給する際における液Aの供給速度を意味する。混合速度vを制御することにより、パラメータZを高めることができる。具体的には、混合速度vを遅くすることにより、パラメータZの値が高くなる傾向がある。
本実施形態に係るスラリーの製造方法は、前記砥粒の製造方法により砥粒を得る砥粒製造工程と、当該砥粒製造工程において得られた砥粒と、水とを混合してスラリーを得るスラリー製造工程と、を備える。スラリー製造工程では、前記砥粒を水に分散させる。前記砥粒を水に分散させる方法としては、特に制限はないが、撹拌による分散方法;ホモジナイザー、超音波分散機又は湿式ボールミル等による分散方法などが挙げられる。なお、砥粒製造工程において得られた砥粒と、他の種類の砥粒と、水とを混合してスラリーを得てもよい。
研磨液の製造方法は、前記スラリーの製造方法によりスラリーを得るスラリー製造工程と、当該スラリーと添加剤とを混合して研磨液を得る研磨液調製工程と、を備える態様であってもよい。この場合、砥粒を含むスラリーと、添加剤を含む添加液とに分けた、いわゆる二液タイプの研磨液として各液を準備し、スラリーと添加液とを混合して研磨液を得てもよい。また、研磨液の製造方法は、前記砥粒製造工程と、当該砥粒製造工程において得られた砥粒と、添加剤と、水とを混合して研磨液を得る研磨液調製工程と、を備える態様であってもよい。この場合、砥粒製造工程において得られた砥粒と、他の種類の砥粒と、水とを混合してもよい。
本実施形態に係る研磨液は、砥粒と添加剤と水とを少なくとも含有する。以下、各構成成分について説明する。
砥粒は、4価金属元素の水酸化物を含むことを特徴とする。「4価金属元素の水酸化物」は、4価の金属(M4+)と、少なくとも一つの水酸化物イオン(OH-)とを含む化合物である。4価金属元素の水酸化物は、水酸化物イオン以外の陰イオン(例えば硝酸イオンNO3 -、硫酸イオンSO4 2-)を含んでいてもよい。例えば、4価金属元素の水酸化物は、4価金属元素に結合した陰イオン(例えば硝酸イオンNO3 -、硫酸イオンSO4 2-)を含んでいてもよい。
前記加熱工程を経て得られる砥粒が、該砥粒の含有量を1.0質量%に調整した水分散液において波長400nmの光に対する吸光度1.00以上を与える場合に、研磨速度を向上させやすくなると共に、保管安定性を向上させやすくなる。この理由は必ずしも明らかではないが、本発明者は次のように考えている。すなわち、4価金属元素の水酸化物の製造条件等に応じて生成するM(OH)aXbを含む粒子は、波長400nmの光を吸光するため、M(OH)aXbの存在量が増加して波長400nmの光に対する吸光度が高くなるに伴い、研磨速度が向上するものと考えられる。
本実施形態に係る研磨液は、可視光に対する透明度が高い(目視で透明又は透明に近い)ことが好ましい。具体的には、本実施形態に係る研磨液に含まれる砥粒は、該砥粒の含有量を1.0質量%に調整した水分散液において波長500nmの光に対して光透過率50%/cm以上を与えるものであることが好ましい。これにより、添加剤の添加に起因する研磨速度の低下を更に抑制することができるため、研磨速度を維持しつつ他の特性を得ることが容易になる。この観点で、前記光透過率の下限は、60%/cm以上がより好ましく、70%/cm以上が更に好ましく、80%/cm以上が特に好ましく、90%/cm以上が極めて好ましく、95%/cm以上が非常に好ましく、98%/cm以上がより一層好ましく、99%/cm以上が更に好ましい。光透過率の上限は100%/cmである。
検出器:株式会社日立製作所製UV-VISディテクター、商品名「L-4200」、波長:400nm
インテグレータ:株式会社日立製作所製GPCインテグレータ、商品名「D-2500」
ポンプ:株式会社日立製作所製、商品名「L-7100」
カラム:日立化成株式会社製水系HPLC用充填カラム、商品名「GL-W550S」
溶離液:脱イオン水
測定温度:23℃
流速:1mL/分(圧力は40~50kg/cm2程度)
測定時間:60分
本実施形態に係る研磨液は、絶縁材料(例えば酸化ケイ素)に対して特に優れた研磨速度を得ることができるため、絶縁材料を有する基体を研磨する用途に特に適している。本実施形態に係る研磨液によれば、添加剤を適宜選択することにより、研磨速度と、研磨速度以外の研磨特性とを高度に両立させることができる。
本実施形態に係る研磨液における水は、特に制限はないが、脱イオン水、超純水等が好ましい。水の含有量は、他の構成成分の含有量を除いた研磨液の残部でよく、特に限定されない。
研磨液のpH(25℃)は、更に優れた研磨速度が得られる点で、2.0~9.0が好ましい。これは、被研磨面の表面電位に対する砥粒の表面電位が良好となり、砥粒が被研磨面に対して作用しやすくなるためと考えられる。研磨液のpHが安定して、砥粒の凝集等の問題が生じにくくなる点で、pHの下限は、2.0以上が好ましく、3.0以上がより好ましく、4.0以上が更に好ましい。砥粒の分散性に優れ、更に優れた研磨速度が得られる点で、pHの上限は、9.0以下が好ましく、8.0以下がより好ましく、7.5以下が更に好ましい。研磨液のpHは、前記混合液のpHと同様の方法で測定することができる。
本実施形態に係るスラリーは、該スラリーをそのまま研磨に用いてもよく、研磨液の構成成分をスラリーと添加液とに分けた、いわゆる二液タイプの研磨液におけるスラリーとして用いてもよい。本実施形態において、研磨液とスラリーとは添加剤の有無の点で異なり、スラリーに添加剤を添加することで研磨液が得られる。
本実施形態に係る研磨液セットでは、スラリー(第一の液)と添加液(第二の液)とを混合して研磨液となるように、該研磨液の構成成分がスラリーと添加液とに分けて保存される。スラリーとしては、本実施形態に係るスラリーを用いることができる。添加液としては、添加剤を水に溶解させた液(添加剤と水とを含む液)を用いることができる。研磨液セットは、研磨時にスラリーと添加液とを混合することにより研磨液として使用される。このように、研磨液の構成成分を少なくとも二つの液に分けて保存することで、添加剤を混合した後に長時間保存される場合に懸念される砥粒の凝集、研磨特性の変化等の問題を回避することが可能であり、保存安定性に更に優れる研磨液とすることができる。なお、本実施形態に係る研磨液セットでは、三液以上に構成成分を分けてもよい。
前記研磨液、スラリー又は研磨液セットを用いた基体の研磨方法、及び、これにより得られる基体について説明する。本実施形態に係る研磨方法は、前記研磨液又はスラリーを用いる場合、一液タイプの研磨液を用いた研磨方法であり、前記研磨液セットを用いる場合、二液タイプの研磨液又は三液以上のタイプの研磨液を用いた研磨方法である。これらの研磨方法によれば、優れた研磨速度で被研磨材料を研磨することができる。また、これらの研磨方法によれば、研磨傷の発生を抑制することができると共に、平坦性に優れた基体を得ることもできる。本実施形態に係る基体は、前記研磨方法により研磨されたものである。
(4価金属元素の水酸化物粒子を含む砥粒の作製)
下記の手順に従って、4価金属元素の水酸化物粒子を含む砥粒を作製した。なお、下記説明中の符号A~Jで示される値は、表1にそれぞれ示される値である。
スラリー前駆体2を適量採取し、真空乾燥して砥粒を単離した。純水で充分に洗浄して得られた試料について、FT-IR ATR法による測定を行ったところ、水酸化物イオンに基づくピークの他に、硝酸イオン(NO3 -)に基づくピークが観測された。また、同試料について、窒素に対するXPS(N-XPS)測定を行ったところ、NH4 +に基づくピークは観測されず、硝酸イオンに基づくピークが観測された。これらの結果より、スラリー前駆体2に含まれる砥粒は、セリウム元素に結合した硝酸イオンを有する粒子を少なくとも一部含有することが確認された。また、セリウム元素に結合した水酸化物イオンを有する粒子を少なくとも一部含有することから、砥粒がセリウムの水酸化物を含有することが確認された。これらの結果より、セリウムの水酸化物が、セリウム元素に結合した水酸化物イオンを含むことが確認された。
スラリー前駆体2を適量採取し、砥粒含有量が0.0065質量%(65ppm)となるように水で希釈して測定サンプル(水分散液)を得た。測定サンプルを1cm角のセルに約4mL入れ、株式会社日立製作所製の分光光度計(装置名:U3310)内にセルを設置した。波長200~600nmの範囲で吸光度測定を行い、波長290nmの光に対する吸光度と、波長450~600nmの光に対する吸光度とを測定した。結果を表2に示す。
スラリー前駆体2を適量採取し、砥粒含有量が0.2質量%となるように水で希釈して測定サンプル(水分散液)を得た。測定サンプルを1cm角のセルに約4mL入れ、ベックマンコールター社製の装置名:N5内にセルを設置した。分散媒の屈折率を1.33、粘度を0.887mPa・sに調整して、25℃において測定を行い、表示された平均粒子径値を平均二次粒子径とした。結果を表2に示す。
スラリー前駆体2に水を加え、砥粒含有量を1.0質量%に調整してスラリー用貯蔵液1を得た。また、スラリー用貯蔵液1とは別に、スラリー用貯蔵液1を60℃/72時間保管してスラリー用貯蔵液2を作製した。スラリー用貯蔵液1、2の外観の観察結果を表3に示す。
スラリー用貯蔵液1及びスラリー用貯蔵液2のpH(25℃)を横河電機株式会社製の型番PH81を用いて測定した。結果を表3に示す。
スラリー用貯蔵液1及び2各100gに純水を150g添加して、砥粒含有量0.4質量%のスラリー1及び2を得た。
添加剤として5質量%のポリビニルアルコールと、X質量%のイミダゾールとを含む添加液1を準備した。100gの添加液1に水を150g加えて添加液2を得た。スラリー1と添加液2とを1:1(質量比)で混合することにより研磨液1(砥粒含有量:0.2質量%、ポリビニルアルコール含有量:1.0質量%)を得た。ここで、前記X質量%は、研磨液のpHが6.0となるように決定した。なお、ポリビニルアルコール水溶液中のポリビニルアルコールのケン化度は80mol%であり、平均重合度は300であった。
研磨装置における基体取り付け用の吸着パッドを貼り付けたホルダーに、絶縁膜として酸化ケイ素膜が形成されたφ200mmシリコンウエハをセットした。多孔質ウレタン樹脂製パッドを貼り付けた定盤上に、絶縁膜がパッドに対向するようにホルダーを載せた。前記で得られた研磨液を、供給量200mL/minでパッド上に供給しながら、研磨荷重20kPaで基体をパッドに押し当てた。このとき定盤を78min-1、ホルダーを98min-1で1分間回転させ研磨を行った。研磨後のウエハを純水でよく洗浄し乾燥させた。研磨液1、2のそれぞれについて、光干渉式膜厚測定装置を用いて研磨前後の膜厚変化を測定して研磨速度を求めた。また、研磨液1の研磨速度に対する研磨液1の研磨速度と研磨液2の研磨速度との差の割合(研磨速度の差/研磨液1の研磨速度×100)を研磨速度変化率として算出した。結果を表3に示す。
Claims (23)
- 4価金属元素の塩を含む金属塩溶液と、アルカリ液とを混合して、前記4価金属元素の水酸化物を含む粒子を得る工程と、
前記4価金属元素の水酸化物を含む粒子を加熱する工程と、を備える、砥粒の製造方法。 - 前記4価金属元素の水酸化物を含む粒子を30℃以上で加熱する、請求項1に記載の砥粒の製造方法。
- 前記4価金属元素の水酸化物を含む粒子を40℃以上で加熱する、請求項1又は2に記載の砥粒の製造方法。
- 前記4価金属元素の水酸化物を含む粒子を100℃以下で加熱する、請求項1~3のいずれか一項に記載の砥粒の製造方法。
- 下記式(1)で示されるパラメータZが5.00以上である条件で前記金属塩溶液と前記アルカリ液とを混合する、請求項1~4のいずれか一項に記載の砥粒の製造方法。
Z=[1/(ΔpH×k)]×(N/M)/1000 ・・・(1)
[式(1)中、ΔpHは、前記金属塩溶液及び前記アルカリ液の混合液の1分間当たりのpH変化量を示し、kは、反応温度係数を示し、Nは、循環数(min-1)を示し、Mは、置換数(min-1)を示す。] - 前記ΔpHが1.000以下である、請求項5に記載の砥粒の製造方法。
- 前記循環数Nが、下記式(2)で示されるものである、請求項5又は6に記載の砥粒の製造方法。
N=(u×S)/Q ・・・(2)
[式(2)中、uは、前記混合液を撹拌する撹拌羽根の線速度(m/min)を示し、Sは、前記撹拌羽根の面積(m2)を示し、Qは、前記混合液の液量(m3)を示す。] - 前記線速度uが下記式(3)において5.00m/min以上である、請求項7に記載の砥粒の製造方法。
u=2π×R×r ・・・(3)
[式(3)中、Rは、前記撹拌羽根の回転数(min-1)を示し、rは、前記撹拌羽根の回転半径(m)を示す。] - 前記回転数Rが30min-1以上である、請求項8に記載の砥粒の製造方法。
- 前記循環数Nが1.00min-1以上である、請求項5~9のいずれか一項に記載の砥粒の製造方法。
- 前記置換数Mが、下記式(4)で示されるものである、請求項5~10のいずれか一項に記載の砥粒の製造方法。
M=v/Q ・・・(4)
[式(4)中、vは、前記金属塩溶液及び前記アルカリ液の混合速度(m3/min)を示し、Qは、前記混合液の液量(m3)を示す。] - 前記混合速度vが5.00×10-3m3/min以下である、請求項11に記載の砥粒の製造方法。
- 前記置換数Mが1.0min-1以下である、請求項5~12のいずれか一項に記載の砥粒の製造方法。
- 前記金属塩溶液における前記4価金属元素の塩の濃度が0.010mol/L以上である、請求項1~13のいずれか一項に記載の砥粒の製造方法。
- 前記アルカリ液におけるアルカリ濃度が15.0mol/L以下である、請求項1~14のいずれか一項に記載の砥粒の製造方法。
- 前記金属塩溶液及び前記アルカリ液の混合液のpHが1.5~7.0である、請求項1~15のいずれか一項に記載の砥粒の製造方法。
- 前記4価金属元素が4価セリウムである、請求項1~16のいずれか一項に記載の砥粒の製造方法。
- 請求項1~17のいずれか一項に記載の砥粒の製造方法により得られた砥粒と、水とを混合してスラリーを得る工程を備える、スラリーの製造方法。
- 請求項18に記載のスラリーの製造方法により得られたスラリーと、添加剤とを混合して研磨液を得る工程を備える、研磨液の製造方法。
- 請求項1~17のいずれか一項に記載の砥粒の製造方法により得られた砥粒と、添加剤と、水とを混合して研磨液を得る工程を備える、研磨液の製造方法。
- 請求項1~17のいずれか一項に記載の砥粒の製造方法により得られた、砥粒。
- 請求項18に記載のスラリーの製造方法により得られた、スラリー。
- 請求項19又は20に記載の研磨液の製造方法により得られた、研磨液。
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