US20040209554A1 - Polishing material and method of polishing therewith - Google Patents
Polishing material and method of polishing therewith Download PDFInfo
- Publication number
- US20040209554A1 US20040209554A1 US10/485,297 US48529704A US2004209554A1 US 20040209554 A1 US20040209554 A1 US 20040209554A1 US 48529704 A US48529704 A US 48529704A US 2004209554 A1 US2004209554 A1 US 2004209554A1
- Authority
- US
- United States
- Prior art keywords
- component
- abrasive
- polishing
- polishing pad
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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- 239000000463 material Substances 0.000 title claims abstract description 10
- 238000007517 polishing process Methods 0.000 title claims description 7
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000001268 conjugating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- GJTLFTOKXITQBN-UHFFFAOYSA-N ethanol hydrazine Chemical compound NN.CCO GJTLFTOKXITQBN-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate 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
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- ODZZIKZQNODXFS-UHFFFAOYSA-N n,n'-dimethyl-n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCN(C)CCNC ODZZIKZQNODXFS-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- NADBWXCIVAJJQS-UHFFFAOYSA-N naphthalene-1,3,6-triamine Chemical compound NC1=CC(N)=CC2=CC(N)=CC=C21 NADBWXCIVAJJQS-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
- B24B37/245—Pads with fixed abrasives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/26—Lapping pads for working plane surfaces characterised by the shape of the lapping pad surface, e.g. grooved
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
- B24D3/28—Resins or natural or synthetic macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
- C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Definitions
- the present invention relates to an abrasive and to a polishing method using the same. More specifically, it relates to an abrasive obtained by curing raw materials containing at least (1) an organic polyisocyanate and at least one member selected from an organic polyol and an organic polyamine as matrix resin raw materials and (2) a particle having a hydroxyl group or colloidal silica and the like as an abrasive particle, by a polymerization reaction and to a polishing method using the same.
- CMP Chemical Mechanical Polishing
- JP 5-8178A discloses a semiconductor wafer polishing cloth which is obtained by impregnating a composite substrate prepared by impregnating a felt-like fibrous sheet with a linear thermoplastic polyurethane resin and solidifying it, with a resin harder than the thermoplastic polyurethane resin and heating and drying the resin.
- the polishing ability of this polishing cloth is not reduced by loading in a short period of time but its service life is about 60 hours at best.
- JP 8-216034A discloses an abrasive which comprises 60 to 90 wt % of a soft polyurethane resin matrix having a hardness of 50 to 85 and 10 to 40 wt % of at least one type of abrasive grains selected from the group consisting of silica, alumina and silicon carbide and dispersed in the above matrix and which has an expansion ratio of 1.5 to 5.0.
- this abrasive provides excellent surface smoothness to a semiconductor wafer after polishing and can suppress a surface sagging phenomenon, it has a problem that long-term continuous polishing is not possible to conduct therewith.
- JP 11-204467A discloses a semiconductor manufacturing apparatus which comprises a polishing pad for carrying out the mechanical polishing of the surface of a semiconductor substrate having a difference in level on the surface and a device for supplying a solution for carrying out the chemical polishing of the surface of the semiconductor substrate, wherein particles having hardness higher than the semiconductor substrate are contained.
- This publication discloses that the polishing pad is molded from a mixture of urethane and a silica particle as a raw material.
- Use of the above apparatus has characteristic features that the speed of polishing an insulating film formed on the substrate and the amount of polishing can be made uniform on the entire surface of the substrate and the supply of an excessive amount of a polishing slurry becomes unnecessary.
- the continuous polishing can not be done still for a long time, and dressing must be carried out regularly.
- the polished workpiece must have highly accurate surface smoothness, the polishing speed must be high, and a surface sagging phenomenon (which is a phenomenon of the peripheral portion of the polished surface becoming thinner than the central portion) must not occur, in addition to long-term continuous polishing.
- the matrix resin of the abrasive must have high elasticity so that it can fit to the uneven surface of the workpiece to be polished.
- the inventors of the present invention have conducted studies to solve the above problems and have found that an abrasive which enables long-term continuous polishing, gives high polishing speed and provides the polished workpiece with highly accurate surface smoothness and does not cause a surface sagging phenomenon can be obtained by using a particle having a hydroxyl group or colloidal silica or the like as an abrasive particle in an abrasive obtained by curing raw materials containing at least (1) an organic polyisocyanate and at least one member selected from an organic polyol and an organic polyamine as matrix resin raw materials and (2) an abrasive particle, by a polymerization reaction.
- the present invention has been accomplished based on this finding.
- an abrasive which is obtained by curing raw materials containing at least (1) an organic polyisocyanate (component A) and at least one member selected from an organic polyol (component B) and an organic polyamine (component C) as raw materials of a matrix resin and (2) an abrasive particle (component E), by a polymerization reaction, wherein the particle (component E) is (a) a particle (component E 1 ) having a hydroxyl group in an amount of 0.001 mmol/g or more (measured by neutralization titration, this shall apply hereinafter) and/or (b) at least one member (component E 2 ) selected from fumed silica, colloidal silica, fumed alumina, colloidal alumina, boehmite and bayerite.
- the particle (component E) is (a) a particle (component E 1 ) having a hydroxyl group in an amount of 0.001 mmol/g or more (measured by neutralization
- the matrix resin (resin F) should be a resin having at least an urethane bond
- the matrix resin raw materials should contain an organic polyisocyanate (component A), at least one member selected from an organic polyol (component B) and an organic polyamine (component C), and a foaming agent (component D),
- the matrix resin raw materials should be an organic polyisocyanate (component A), at least one member selected from an organic polyol (component B) and an organic polyamine (component C), and an organic polycarboxylic acid (component J),
- the matrix resin (resin F) should be a resin having at least one of urethane bond, urea bond and amide bond,
- the expansion ratio should be 1.1 to 5
- the particle (component E) should be colloidal silica
- the amount of the hydroxyl group in the particle (component E 1 ) should be 0.01 to 6 mmol/g
- the particle (component E 1 ) should be at least one member selected from diamond, cubic boron nitride, zirconia, ceria, manganese oxide, titanium oxide, calcium carbonate, barium carbonate, magnesium oxide, alumina-silica and silicon carbide all of which are provided with a hydroxyl group,
- the matrix resin (resin F) should be contained in the abrasive in an amount of 60 to 95 wt %,
- the abrasive should be a foamed material obtained by curing raw materials including an organic polyisocyanate compound (component A), at least one member selected from an organic polyol (component B) and an organic polyamine (component C), a foaming agent (component D), a catalyst and a particle (component E), by a polymerization reaction,
- the abrasive should be a foamed material obtained by adding an organic polyisocyanate compound (component A) to a mixture of at least one member selected from an organic polyol (component B) and an organic polyamine (component C), a foaming agent (component D), a catalyst and a particle (component E), mixing them together under stirring, and curing and molding the mixture by a polymerization reaction, and
- the abrasive should be a foamed material obtained by adding a mixture of at least one member selected from an organic polyol (component B) and organic polyamine (component C) and a particle (component E) to a mixture of an organic polyisocyanate compound (component A), a foaming agent (component D) and a catalyst, mixing them together stirring, and curing and molding the mixture by a polymerization reaction.
- a fixed abrasive grain polishing pad which is a fixed abrasive grain polishing pad (polishing pad G) that is composed of an abrasive comprising a matrix resin (resin F) having an urethane bond and obtained by the polymerization reaction of raw materials containing at least an organic polyisocyanate (component A), at least one member selected from an organic polyol (component B) and an organic polyamine (component C) as raw materials of a matrix resin and the above particle (component E) and that is mounted on a polishing table, which is used for polishing a workpiece to be polished by the relative movements of the workpiece and the fixed abrasive grain polishing pad (polishing pad G) while pressing the workpiece between the fixed abrasive grain polishing pad (polishing pad G) and a workpiece holding portion and supplying an abrasive liquid (abrasive liquid H) between the fixed abras
- the fixed abrasive grain polishing pad (polishing pad G) should have grooves extending radially from the center point toward the circumferential direction, and
- the fixed abrasive grain polishing pad (polishing pad G) should have lattice-like grooves.
- a method of polishing a workpiece comprising mounting the above fixed abrasive grain polishing pad (polishing pad G) composed of the above abrasive on a polishing table, pressing the workpiece between the fixed abrasive grain polishing pad (polishing pad G) and a workpiece holding portion, and polishing the workpiece by the relative movements of the fixed abrasive grain polishing pad (polishing pad G) and the workpiece while supplying an abrasive liquid (abrasive liquid H) between the fixed abrasive grain polishing pad (polishing pad) and the workpiece.
- the abrasive liquid should be an alkaline aqueous solution
- the above alkaline aqueous solution should have a pH of 10 or higher.
- the polishing function of the abrasive rarely lowers.
- the particles (component (E)) blended as the abrasive particles are dispersed in the matrix resin (resin F) after the polymerization reaction and are existent as the abrasive grains (abrasive grains I)
- the abrasive grains (abrasive grains I) are rarely worn away. Since the amount of the abrasive grains (abrasive grains I) discharged into the abrasive liquid waste is greatly reduced, the abrasive liquid can be recycled by simple filtration means or the like without exerting a bad influence upon the environment.
- the hydrogen atom of the hydroxyl group of the particle (component E) acts on the isocyanate group of the organic polyisocyanate (component A) as active hydrogen
- the active hydrogen atom is added to the nitrogen atom of the isocyanate group (—CNO)
- the oxygen atom of the hydroxyl group devoid of the hydrogen atom is bonded to the carbon atom of the isocyanate group (—CNO) to produce a chemical bond [(matrix resin side) —NH—CO—O— (abrasive grain side)].
- the abrasive of the present invention is an abrasive obtained by curing raw materials containing at least an organic polyisocyanate (component A) and at least one member selected from an organic polyol (component B) and an organic polyamine (component C) as matrix resin raw materials and the above particle (component E) as an abrasive particle, by a polymerization reaction, the matrix resin (resin F) having an urethane bond and/or an urea bond.
- the matrix resin raw materials may optionally contain a foaming agent (component D), a catalyst or a foam stabilizer in addition to the organic polyisocyanate (component A), organic polyol (component B) and organic polyamine (component C).
- a foaming agent component D
- a catalyst or a foam stabilizer in addition to the organic polyisocyanate (component A), organic polyol (component B) and organic polyamine (component C).
- the particle (component E) used as an abrasive particle material may be a particle having a specific amount of a hydroxyl group, a particle having a hydroxyl group such as colloidal silica or the like which will be described later, or zirconia provided with a hydroxyl group.
- the organic polyisocyanate compound (component A) which is one of the matrix resin raw materials is a compound having two or more isocyanate groups in the molecular, and a polyisocyanate that is generally used to produce a polyurethane resin may be used without restriction.
- Illustrative examples of the organic polyisocyanate compound (component A) include tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), polymeric MDI, xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), paraphenylene diisocyanate (PPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), lysine diisocyanate (LDI), tolysine diisocyanate (TODI), hydrogenated xylylene diisocyanate, modified products of these polyisocyanates and prepolymers obtained by reacting a polyol with polyisocyanate beforehand so that an isocyanate group remains at the terminal.
- TDI tolylene diisocyanate
- MDI 4,4-diphenyl
- the content of the NCO group of the organic polyisocyanate compound (component A) is preferably 20 to 48 wt %, more preferably 20 to 40 wt %, much more preferably 25 to 38 wt %. Within this range, an abrasive having excellent durability and abrasion resistance can be obtained.
- organic polyisocyanate compounds (component A) may be used alone or in combination of two or more.
- tolylene diisocyanate (TDI) and 4,4-diphenylmethane diisocyanate (MDI) are preferred.
- organic polyol (component B) may be used any organic compound having two or more hydroxyl groups in the molecule such as a polyhydric alcohol, polyether-based polyol, polyester polyol or polymer polyols.
- Illustrative examples of the organic polyol (component B) include polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 4-bis (hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerine and hexanetriol; polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene, polyoxypropylene and polyoxytetramethylene glycol; modified polyether polyols obtained by the ring-opening polymerization of the above polyhydric alcohol and
- the above organic polyol (component B) has a hydroxyl value of preferably 100 to 1,800, particularly preferably 200 to 1,200.
- the above organic polyols may be used alone or in combination of two or more.
- the blend ratio of the organic polyisocyanate compound (component A) to the organic polyol (component B) is 0.8 to 1.2, preferably 1 to 1.2 in terms of functional group ratio ([active hydrogen-containing compound]/[isocyanate]).
- the organic polyamine (component C) may be used in place of part or all of the organic polyol (component B).
- the polyamine which can be used is a known diamine, triamine or a mixture thereof which is generally used to produce a polyurethane resin.
- Typical examples thereof include 1,2-ethylenediamine, bis-(3-aminopropyl)-amine, hydrazine, hydrazine-2-ethanol, bis-(2-methylaminoethyl)-methylamine, 1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-methyl-bis-(3-aminopropyl)-amine, tetraethylenediamine, hexamethylenediamine, 1-aminoethyl-1,2-ethylenediamine, bis-(N,N′-aminoethyl)-1,2-ethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, phenylenediamine, toluylenediamine, 2,4,6-triaminotoluene trihydrochloride, 1,3,6-triaminonaphthalene, isophoronediamine, xylylenediamine, 4,4′
- the organic polyamine (component C) has an amine value of preferably 56 to 560 (mgKOH/g), particularly preferably 80 to 400 (mgKOH/g). Within this range, an abrasive having excellent durability and polishing properties can be obtained.
- an organic polycarboxylic acid (component J) may be used in place of the above organic polyol (component B) and/or organic polyamine (component C).
- the matrix resin (resin F) becomes a resin having at least one of urethane bond, urea bond and amide bond.
- organic polycarboxylic acid examples include aromatic carboxylic acids such as phthalic acid and aliphatic carboxylic acids such as adipic acid. Preferably, they function as a stabilizer for a curing catalyst and have not odor.
- the foaming agent (component D) which can be used for a reaction between the organic polyisocyanate compound (component A) and at least one member selected from the organic polyol (component B) and the organic polyamine (component C) is a mixture of one or two or more member of water, trichloromonofluoromethane, dichlorodifluoromethane, methylene chloride, trichlorofluoroethane and trichloroethane.
- the expansion ratio at the time when the matrix resin (resin F) is molded is preferably 1.1 to 5.
- expansion ratio is represented by D 1 /D 2 wherein D 1 is a bulk density calculated from the weight and volume of a non-foamed cured product produced without mixing a foaming agent (component D) with raw materials containing the matrix resin raw materials and an abrasive particle (component E) and D 2 is a bulk density calculated from the weight and volume of a foamed cured product produced by mixing a foaming agent (component D) with raw materials containing the same abrasive particle (component E).
- an abrasive having an expansion ratio higher than 5.0 provides a high polishing speed because its bubble structure is rough, it roughens the surface of a workpiece to be polished such as a wafer and reduces the surface smoothness of the workpiece after polishing.
- an abrasive having an expansion ratio lower than 1.1 enhances the surface smoothness of a wafer or the like because its bubble structure is dense but it provides a low polishing speed and reduces productivity at the time of polishing.
- the catalyst which can be used for the reaction between the organic polyisocyanate compound (component A) and the organic polyol (component B) or the like is not particularly limited, and an amine-based catalyst or organic metal-based catalyst may be used.
- the amine-based catalyst include triethylenediamine, triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, N-methylmorpholine and N-ethylmorpholine.
- the organic metal-based catalyst include tin octylate, tin laurate and dibutyltin dilaurate. Out of these, amine-based catalysts are preferred.
- the amount of the catalyst is not particularly limited but generally about 0.01 to 0.5 part by weight based on 100 parts by weight of the total of the organic polyisocyanate compound (component A) and the organic polyol (component B).
- the foam stabilizer may be used a conventionally known organosilicone-based surfactant.
- organosilicone-based surfactant include L-520, L-532, L-540, L-544, L-3550, L-5740S, L-5740M and L-6202 of Nippon Unicar Co., Ltd.; SH-190, SH-192, SH-193, SH-194, SRX-294 and SRX-298 of Toray Silicone Co., Ltd.; and F-114, F-121, F-122, F-230, F-258, F-260B, F-317, F-341, F-601 and F-606 of Shin-Etsu Silicon Co., Ltd.
- a flame retardant, a dehydrator and a weathering agent may be further added to the raw material composition.
- Examples of the flame retardant include aluminum hydroxide, phosphates, melamine, red phosphorus and expanded graphite.
- Examples of the dehydrator include calcium silicate, calcium carbonate, magnesium sulfate and synthetic zeolite.
- Examples of the weathering agent include ultraviolet light absorbers, optical stabilizers and antioxidants which are generally used for polyurethane resins.
- abrasive particle may be used (a) a particle having a hydroxyl group in an amount of 0.001 mmol/g (component E 1 ) and/or (b) at least one member (component E 2 ) selected from fumed silica, colloidal silica, fumed alumina, colloidal alumina, boehmite and bayerite.
- the amount of the hydroxyl group of the particle having a hydroxyl group is 0.001 mmol/g or more when measured by the following neutralization titration.
- the amount of the hydroxyl group is 0.001 mmol/g or more, chemical bonding force can be developed between the matrix resin (resin F) and the abrasive grains (abrasive grains I) after the curing of the matrix resin (resin F), which is the effect of the present invention.
- the amount of the hydroxyl group is preferably 0.01 mmol/g or more, particularly preferably 0.05 mmol/g or more.
- the amount of the hydroxyl group of the particle (component E 1 ) is preferably 20 mmol/g or less, more preferably 10 mmol/g or less, particularly preferably 6 mmol/g or less.
- the method of measuring the amount of the hydroxyl group contained in the abrasive particle is as follows. That is, 2.00 g of the sample particle is weighed (W g) and put in a 100 ml Erlenmeyer flask, 80 ml of a 0.05 N aqueous solution of NaOH is added to this flask, and the flask is tightly sealed with a rubber cap and left as it is under stirring for 12 hours. Thereafter, the particle and the solution are separated from one another by a centrifugal separator, and 10 ml of the solution is put into a pipette from this solution, and titrated with a 0.05 N aqueous solution of HCl for neutralization.
- the amount of the HCl aqueous solution required for neutralization is represented by A ml.
- the same operation is carried out without adding the particle and the amount of an HCl aqueous solution required for neutralization is represented by B ml.
- the amount (X mmol/g) of the OH group per unit weight of the particle is calculated from the following equation.
- the measurement value of the amount of the hydroxyl group is the measurement value of the amount of the hydroxyl group existent relatively near the surface of the particle (component E).
- the hydroxyl group existent relatively near the surface of the particle (component E) makes it possible to actually develop chemical bonding force between the matrix resin (resin F) and the particle, the above measurement method is employed and its measurement value is taken as the amount of the hydroxyl group of the particle (component E) for convenience.
- Illustrative examples of the particle having a hydroxyl group include all particles used in known inorganic abrasive grains, such as silica, alumina or the like. Further, examples of the particle provided with a hydroxyl group (component E 1 ) include metal oxides such as titanium oxide provided with a hydroxyl group by a hydration reaction. Further, there are methods of producing a composite particle by applying mechanical energy to a plurality of different raw material particles to cause a mechanochemical reaction (inserting a hydroxyl group by conjugating a particle having a hydroxyl group with a particle not having a hydroxyl group). Thus, the hydroxyl group can be provided by various methods depending on the type of the particle.
- Examples of the above particle include diamond, cubic boron nitride, zirconia, ceria, manganese oxide, titanium oxide, calcium carbonate, barium carbonate, magnesium oxide, alumina-silica and silicon carbide all of which are provided with a hydroxyl group.
- abrasive particle may be used at least one member selected from fumed silica, colloidal silica, fumed alumina, colloidal alumina, boehmite and bayerite.
- these abrasive particles (component E 2 ) generally have a hydroxyl group on the surface, they may be used alone or in combination without taking into consideration the amount of the hydroxyl group, unlike the above particle (component E 1 ). Out of these, colloidal silica is preferred.
- fumed silica and fumed alumina have a large number of Si—Cl bonds on the surface, they are preferably heated at about 200 to 800° C. in the presence of water to convert these Si—Cl bonds into Si—OH bonds before use.
- the method of producing the above colloidal silica is not particularly limited.
- colloidal silica produced by known production methods disclosed by JP 4-2602A, JP 4-231319A, JP 5-97422A, JP 2003-89786A and JP 2003-100678A may be used.
- the above colloidal silica and fumed silica have a large number of hydroxyl groups in the form of Si—OH (silanol group) on the surface (terminal groups of the structure), which is advantageous when they are chemically bonded to the matrix resin (resin F).
- these abrasive particles are uniform in diameter and have a small diameter in order to prevent the surface of the workpiece from being scratched by abrasion grains and to prevent a change in composition caused by precipitation during storage.
- the particle diameter of the abrasive particle (component E) can be observed through a scanning electron microscope.
- the particle diameter is preferably in the range of 0.005 to 50 ⁇ m. When the particle diameter is smaller than 0.005 ⁇ m, it is difficult to obtain the high polishing speed, while when the particle diameter is larger than 50 ⁇ m, the surface of the workpiece is liable to be scratched disadvantageously.
- the abrasive of the present invention desirably contains 60 to 95 wt % of the matrix resin (resin F).
- the content of the matrix resin (resin F) in the abrasive is higher than 95 wt % (i.e., the content of the abrasive particle is lower than 5 wt %), the polishing speed becomes low and high productivity cannot be maintained.
- the content is lower than 60 wt % (i.e., the content of the abrasive particle is higher than 40 wt %), the fluidity of a liquid polyurethane resin as a matrix greatly lowers at the time of producing an abrasive, thereby making molding difficult.
- the abrasive of the present invention is obtained by the polymerization reaction of raw materials containing an organic polyisocyanate (component A), at least one member selected from an organic polyol (component B) and an organic polyamine (component C) (in some case, an organic polycarboxylic acid is added as required) as matrix resin raw materials and an abrasive particle (component E).
- a catalyst, a foaming agent (component D) and a foam stabilizer may be optionally blended.
- a mixture of the above raw materials can be cured and molded by a polymerization reaction in accordance with a reaction injection method or casting method.
- the fixed abrasive grain polishing pad (polishing pad G) composed of the above abrasive is mounted on the polishing table, and the workpiece is pressed against the surface of the fixed abrasive grain polishing pad (polishing pad G) and polished by the relative movements of the fixed abrasive grain polishing pad (polishing pad G) and the workpiece.
- grooves are desirably provided in the fixed abrasive grain polishing pad (polishing pad G) radially from the center point toward the circumferential direction or in a lattice form to uniformly spread the abrasive liquid all over the surface of the fixed abrasive grain polishing pad (polishing pad G).
- the third aspect of the present invention is a method of polishing a workpiece, comprising mounting the above fixed abrasive grain polishing pad (polishing pad G) composed of the abrasive on a polishing table, pressing a workpiece between the fixed abrasive grain polishing pad (polishing pad G) and a workpiece holding portion, and polishing the workpiece by the relative movements of the fixed abrasive grain polishing pad (polishing pad G) and the workpiece while supplying the abrasive liquid (abrasive liquid H) between the fixed abrasive grain polishing pad (polishing pad G) and the workpiece.
- the above polishing method makes possible chemical mechanical polishing, provides a high polishing speed and makes it possible to obtain a workpiece having highly accurate surface smoothness when an alkali aqueous solution is used as the abrasive liquid (abrasive liquid H).
- the above abrasive liquid is an aqueous solution of sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like and preferably has a pH of 10 or higher to obtain a chemical polishing function.
- polishing method of the present invention By employing the polishing method of the present invention, a reduction in polishing rate can be suppressed even when polishing is continuously carried out for a long time.
- abrasive liquid H an alkaline aqueous solution is used as the abrasive liquid (abrasive liquid H) and the amount of abrasive grains (abrasive grains I) falling off from the abrasive is extremely small, the abrasive liquid (abrasive liquid H) can be recycled merely by filtering it with a simple regenerating apparatus.
- FIG. 1 is a perspective view showing the outline of a polishing apparatus using an abrasive according to a first embodiment as a fixed abrasive grain polishing pad;
- FIG. 2 is a perspective view showing the constitution of a fixed abrasive grain polishing pad according to a second embodiment
- FIG. 3 is a graph showing the relationship between polishing time and polishing efficiency in Example 1.
- the abrasive of the present invention can be manufactured as follows.
- a mixture of the above-described organic polyisocyanate compound (component A), organic polyol (component B), foaming agent (component D), catalyst and foam stabilizer and the particle (component E) is stirred to disperse the particle (component E) into the raw material liquid composition uniformly.
- the organic polyisocyanate compound (component A) be added to a mixture of the organic polyol having an average molecular weight of 250 to 4,000 (component B), foaming agent (component D), catalyst, foam stabilizer and particle (component E), and stirred and mixed together.
- the raw materials excluding the particle (component E) and the organic polyol (component B) be blended together in predetermined amounts to prepare a liquid composition and that a mixed solution prepared by fully mixing and stirring together the chemically stable organic polyol (component B) and the particle (component E) be added to the above composition.
- the raw material composition is then put into a mold having predetermined size and shape, and heated for a predetermined period of time.
- the raw material composition is foamed and cured at the same time. After curing, the foamed abrasive is taken out from the mold to obtain the abrasive of the present invention.
- the Shore D surface hardness specified in JIS K6253-1997/IS07619 of 20 to 85 at a temperature range of 20 to 150° C. is suitable to the abrasive.
- the Shore D hardness is lower than 20, the polishing rate worsens and when it is higher than 85, scratching is liable to occur (due to roughness).
- grooves 16 a or 16 b are formed on the surface of the fixed abrasive grain polishing pad 16 according to the second embodiment. These grooves are formed in order to spread the abrasive liquid over the whole surface (the center portion in particular) of the fixed abrasive grain polishing pad efficiently and uniformly. This makes it possible to flatten the surface of a wafer, improve the polishing rate and prevent thermal expansion caused by a local temperature rise.
- radial grooves as shown in FIG. 2(A) and lattice type grooves as shown in FIG. 2(B) can be formed.
- the fixed abrasive grain polishing pad 16 is preferably divided into 16 to 32 sections radially starting from the center point (at a center angle of 22.5 to 11.250).
- the width of each groove is, for example, about 1 to 2 mm and the depth of each groove is, for example, about 1 to 2 mm. It is preferred that grooves should not be formed in a predetermined range (for example, 100 mm or less from the center) from the center to prevent the excessive concentration of the grooves 16 a around the center of the fixed abrasive grain polishing pad 16 .
- the grooves 16 b are preferably formed at intervals of, for example, 15 to 30 mm.
- each groove has been described as square (rectangular), it may be circular, V-shaped or U-shaped.
- FIG. 1 is a perspective view showing the constitution of the polishing apparatus comprising a fixed abrasive grain polishing pad according to this embodiment.
- the polishing apparatus 10 using a fixed abrasive grain polishing pad related to this embodiment is constituted by a polishing table 14 which can be rotated by a motor 12 , a fixed abrasive grain polishing pad 16 mounted on the polishing table 14 , a substrate holding portion 20 for pressing the surface to be polished of the held substrate 30 against the fixed abrasive grain polishing pad 16 , a substrate holding portion drive means 18 for rotating and driving under pressure the substrate holder portion 20 and an abrasive liquid supply port 24 for supplying an abrasive liquid 25 to the polishing table 14 .
- the polishing table 14 is a substantially disk-like table formed from stainless steel or ceramic and has a smooth horizontal top surface. This polishing table 14 rotates at a predetermined speed (for example, 40 rpm) in a direction shown by a bold arrow in FIG. 1 when, for example, the drive force of the motor 12 provided in the apparatus below the table is transmitted via a spindle 26 and a transmission (not shown).
- a predetermined speed for example, 40 rpm
- the fixed abrasive grain polishing pad 16 is stuck on the polishing table 14 in such a manner that it becomes as flat as possible, and rotationally moved relative to the substrate 30 as the polishing table 14 is rotated, whereby the polishing surface of the substrate 30 is polished by the aid of the abrasive liquid 25 supplied from the abrasive liquid supply port 24 .
- a detailed description of the fixed abrasive grain polishing pad 16 will be given hereinafter.
- the substrate holding portion drive means 18 rotates the substrate holding portion 20 while applying pressure to the portion through a rod 28 , and is, for example, composed of a motor, cylinder and the like (not shown). That is, the substrate holding portion 20 holding the substrate 30 can be pressed against the fixed abrasive grain polishing pad 16 in a vertical direction for example, by the cylinder as a pressurizing unit and at the same time, is rotated in a direction shown by a thin arrow in FIG. 1 by the motor as a rotary unit.
- the substrate holding portion drive means 18 may be so constituted that the substrate holding portion 20 can be swung in any substantially horizontal direction.
- the substrate holding portion (also called “polishing head or carrier”) 20 has a substantially columnar shape as a whole and is rotatably installed above the polishing table 14 .
- the substrate holding portion 20 is connected to the holding portion drive means 18 via the rod 28 and has a ring (retainer ring) for preventing a horizontal slide of the substrate 30 on the under surface.
- the substrate holding portion 20 presses the surface to be polished of the substrate 30 against the fixed abrasive grain polishing pad 16 while rotating in a state of holding the substrate 30 .
- the substrate 30 which is thus pressed against the fixed abrasive grain polishing pad 16 is rubbed bi-directionally with the fixed abrasive grain polishing pad 16 which rotates in the opposite direction, so that its entire polishing surface is uniformly polished.
- the abrasive liquid supply nozzle 24 supplies the abrasive liquid 25 to the rotating fixed abrasive grain polishing pad 16 at the time of polishing the substrate 30 .
- the abrasive liquid 25 is a solution containing a chemically reactive substance, and enters the gap between the substrate 30 and the fixed abrasive grain polishing pad 16 during polishing to smooth the polishing surface of the substrate 30 with high accuracy while it chemically reacts with the surface to be polished.
- the substrate holding portion (polishing head) 20 , the polishing table 14 and the abrasive liquid supply nozzle 24 are each provided with a temperature regulator (not shown) and the temperature of each of the above units is suitably adjusted to a preferred value to carry out polishing in a more preferred manner.
- the abrasive liquid is preferably an alkaline aqueous solution having a pH of 10 or higher.
- an abrasive liquid having a pH lower than 10 is used as shown in Example 2, the polishing rate greatly lowers.
- the alkaline solution is thus used as the abrasive liquid in this embodiment, it can be recycled merely by filtering with a simple regeneration apparatus.
- a neutralizing apparatus is used to carry out the disposal of liquid waste more easily. Since the recycling of the abrasive liquid is easily realized as described above, it can contribute to environmental preservation.
- the abrasive liquid (alkaline solution) of this embodiment can be prepared from, for example, sodium hydroxide, potassium hydroxide, amine, ammonia and the like.
- the abrasive liquid is prepared at a temperature range of 20 to 150° C. and used for polishing at a temperature range of 20 to 150° C.
- polishing rate and the like of a workpiece to be polished were evaluated by preparing various polyurethane polishing pads and using various abrasive liquids based on the above embodiments, and will be specifically described hereinbelow.
- a polyurethane polishing pad of the present invention was used in Example 1, a polyurethane polishing pad containing alumina abrasive grains was used in Comparative Example 1, and a conventional commercially available fixed abrasive grain polishing pad was used in Comparative Example 2 as the fixed abrasive grain polishing pad.
- the polishing particle used in Example 1 was colloidal silica (manufactured by Fuso Chemical Co., Ltd., under the trade name of Quartron SP-4B), and the polishing particle used in Comparative Example 1 was alumina (manufactured by Fujimi Incorporated, under the trade name of WA#3000).
- the commercially available fixed abrasive grain polishing pad of Comparative Example 2 was manufactured by Noritake Co., Ltd., (trade name: FARD pad).
- the polyether polyol having a molecular weight of 250 to 5,000 and 2 to 3 functional groups (manufactured by Sanyo Kasei Co., Ltd., under the trade name of Sanix), polyisocyanate (content of NCO group: 31 wt %, manufactured by Dow Polyurethane Systems Co., Ltd., under the trade name of PAPI 135), water, amine-based catalyst (manufactured by Tosoh Corporation, under the trade name of TOYOCAT-ET), silicone foam stabilizer (manufactured by Nippon Unicar co., Ltd., under the trade name of L-5309) and the above abrasive particle material were mixed together in a ratio (parts by weight) shown in Table 1 to prepare a liquid mixture. This liquid mixture was injected into a mold and left at 20 to 30° C. for 24 hours to be foamed and cured in order to produce a polyurethane polishing pad.
- This polyurethane polishing pad was stuck on the table of a polishing machine by an adhesive tape, and the surface of the polyurethane polishing pad was corrected with a correction ring having diamond electrodeposited to obtain a 9 mm-thick polyurethane polishing pad having foamed structure exposed on its surface.
- the workpiece (silicon wafer) to be polished was pressed against the polyurethane polishing pad and polished by the relative movements of the polyurethane polishing pad and the workpiece (silicon wafer) while supplying the abrasive liquid between the polyurethane polishing pad and the workpiece.
- Polishing pressure 300 g/cm 2
- the hardness of the polyurethane polishing pad was measured with a Shore D hardness meter specified in JIS K6253-1997/IS07619.
- the expansion ratio was represented by D 1 /D 2 wherein D, is the density of a non-foamed cured product and D 2 is the density of the polyurethane polishing pad produced in Example 1.
- the polishing rate was calculated from a change in thickness obtained by measuring a weight change per minute during polishing.
- the surface roughness was measured with a surface roughness meter (manufactured by Kosaka Laboratory Ltd., under the trade name of Surfcoder SE 3500 K).
- the liquid waste was filtered with a qualitative filter having a retained particle diameter of 1 ⁇ m to observe the state of the filtered liquid waste.
- the filtered liquid waste was put into a test tube having a diameter of 10 mm and evaluated as satisfactory when characters on newspaper could be read from the opposite side and unsatisfactory when they could not be read.
- a glycerin-based polyether polyol having a molecular weight of 600 (manufactured by Sanyo Kasei Co., Ltd., under the trade name of GP-600) as polyol A
- glycerin-based polyether polyol having a molecular weight of 3,000 (manufactured by Sanyo Kasei Co., Ltd., under the trade name of GP-3000) as polyol B
- organic polyisocyanate manufactured by Dow Polyurethane Systems Co., Ltd., under the trade name of PARI 135) were used
- catalyst manufactured by Tosoh Corporation, under the trade name of TOYOCAT-ET
- foam stabilizer manufactured by Nippon Unicar Co., Ltd., under the trade name of L-5309
- the same colloidal silica as in Example 1 as an abrasive particle were used. These were mixed together in a ratio shown in Table 3 and cured at normal temperature by
- Polishing pressure 300 g/cm 2
- the pH of the abrasive liquid is preferably 10 or higher.
- the polishing rate greatly lowers.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP2002162631 | 2002-06-04 | ||
JP2002-162631 | 2002-06-04 | ||
PCT/JP2003/006858 WO2003101668A1 (fr) | 2002-06-04 | 2003-05-30 | Materiau de polissage et procede de polissage associe |
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US20040209554A1 true US20040209554A1 (en) | 2004-10-21 |
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US10/485,297 Abandoned US20040209554A1 (en) | 2002-06-04 | 2003-05-30 | Polishing material and method of polishing therewith |
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US (1) | US20040209554A1 (de) |
JP (1) | JPWO2003101668A1 (de) |
KR (1) | KR20050005392A (de) |
AU (1) | AU2003242004A1 (de) |
DE (1) | DE10392153T5 (de) |
WO (1) | WO2003101668A1 (de) |
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US20060046064A1 (en) * | 2004-08-25 | 2006-03-02 | Dwaine Halberg | Method of improving removal rate of pads |
US20060046627A1 (en) * | 2004-08-25 | 2006-03-02 | Peter Renteln | Method of improving planarization of urethane polishing pads, and urethane polishing pad produced by the same |
WO2006026343A1 (en) * | 2004-08-25 | 2006-03-09 | J.H. Rhodes, Inc. | Polishing pad and methods of improving pad removal rates and planarization |
US20060099891A1 (en) * | 2004-11-09 | 2006-05-11 | Peter Renteln | Method of chemical mechanical polishing, and a pad provided therefore |
WO2006094157A2 (en) * | 2005-03-02 | 2006-09-08 | Extrude Hone Corporation | Orbital polishing apparatus and method |
US20070059935A1 (en) * | 2005-09-06 | 2007-03-15 | Komatsu Electronic Metals Co., Ltd. | Polishing method for semiconductor wafer |
EP1820603A2 (de) | 2006-02-17 | 2007-08-22 | SUMCO Corporation | Wafer und Herstellungsverfahren dafür |
US20100154316A1 (en) * | 2008-12-23 | 2010-06-24 | Saint-Gobain Abrasives, Inc. | Abrasive article with improved packing density and mechanical properties and method of making |
WO2014094092A1 (pt) * | 2012-12-17 | 2014-06-26 | Centro De Tecnologia Mineral - Cetem | Processo para obtenção de material compósito constituído por polímero de origem vegetal, carga mineral e material abrasivo e uso da composição obtida para o polimento de rochas |
US20150047266A1 (en) * | 2013-08-16 | 2015-02-19 | San Fang Chemical Industry Co., Ltd. | Methods for manufacturing polishing pad and polishing apparatus |
CN104788701A (zh) * | 2015-04-03 | 2015-07-22 | 衢州学院 | 一种采用改性有机硅结合剂的纳米二氧化硅抛光薄膜及其制作工艺 |
US9143220B2 (en) | 2008-12-23 | 2015-09-22 | Elta Systems Ltd. | Digital retro-directive communication system and method thereof |
US9156127B2 (en) * | 2008-12-26 | 2015-10-13 | Toyo Tire & Rubber Co., Ltd. | Polishing pad and method for producing same |
US20200091013A1 (en) * | 2018-09-19 | 2020-03-19 | Taiwan Semiconductor Manufacturing Co., Ltd. | Thickness measurement system and method |
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JP4729896B2 (ja) * | 2004-09-17 | 2011-07-20 | ソニー株式会社 | 半導体薄膜の表面処理方法 |
JP5024305B2 (ja) * | 2009-02-04 | 2012-09-12 | 住友電気工業株式会社 | GaN基板の研磨方法 |
KR101255523B1 (ko) * | 2011-04-08 | 2013-04-23 | 노태욱 | 우레탄폼 연마패드 및 그 제조방법 |
JP6411759B2 (ja) * | 2014-03-27 | 2018-10-24 | 株式会社フジミインコーポレーテッド | 研磨用組成物、その使用方法、及び基板の製造方法 |
CN106392911A (zh) * | 2016-12-14 | 2017-02-15 | 方彩燕 | 复合打磨轮 |
TWI639486B (zh) * | 2018-05-31 | 2018-11-01 | 國立清華大學 | 全向整合式調節裝置 |
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- 2003-05-30 KR KR10-2004-7001746A patent/KR20050005392A/ko not_active Application Discontinuation
- 2003-05-30 US US10/485,297 patent/US20040209554A1/en not_active Abandoned
- 2003-05-30 AU AU2003242004A patent/AU2003242004A1/en not_active Abandoned
- 2003-05-30 JP JP2004509005A patent/JPWO2003101668A1/ja active Pending
- 2003-05-30 DE DE10392153T patent/DE10392153T5/de not_active Ceased
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Also Published As
Publication number | Publication date |
---|---|
DE10392153T5 (de) | 2004-08-19 |
WO2003101668A1 (fr) | 2003-12-11 |
KR20050005392A (ko) | 2005-01-13 |
JPWO2003101668A1 (ja) | 2005-09-29 |
AU2003242004A1 (en) | 2003-12-19 |
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