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
- 238000005498 polishing Methods 0.000 title claims abstract description 247
- 239000000463 material Substances 0.000 title claims abstract description 10
- 238000007517 polishing process Methods 0.000 title claims description 7
- 239000002245 particle Substances 0.000 claims abstract description 91
- 229920005989 resin Polymers 0.000 claims abstract description 75
- 239000011347 resin Substances 0.000 claims abstract description 75
- 229920005862 polyol Polymers 0.000 claims abstract description 51
- 150000003077 polyols Chemical class 0.000 claims abstract description 51
- 239000011159 matrix material Substances 0.000 claims abstract description 49
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 38
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 229920000768 polyamine Polymers 0.000 claims abstract description 25
- 239000008119 colloidal silica Substances 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 5
- 239000006061 abrasive grain Substances 0.000 claims description 109
- 239000007788 liquid Substances 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004088 foaming agent Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 229910021485 fumed silica Inorganic materials 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001680 bayerite Inorganic materials 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 229910003460 diamond Inorganic materials 0.000 claims description 4
- 239000010432 diamond Substances 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 230000007774 longterm Effects 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 description 29
- 229920002635 polyurethane Polymers 0.000 description 16
- 239000004814 polyurethane Substances 0.000 description 16
- 235000012431 wafers Nutrition 0.000 description 15
- 239000010808 liquid waste Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000003381 stabilizer Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- -1 polyoxyethylene Polymers 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 229920005749 polyurethane resin Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 239000004359 castor oil Chemical class 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Chemical class CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000007665 sagging Methods 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002323 Silicone foam Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007688 edging Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000013514 silicone foam Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- ZXUJWPHOPHHZLR-UHFFFAOYSA-N 1,1,1-trichloro-2-fluoroethane Chemical compound FCC(Cl)(Cl)Cl ZXUJWPHOPHHZLR-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SGMXQYKVIAEVKN-UHFFFAOYSA-N 1-n'-(2-aminoethyl)ethane-1,1-diamine Chemical compound CC(N)NCCN SGMXQYKVIAEVKN-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- ROFCYGFJWHTQIY-UHFFFAOYSA-N 2-methylbenzene-1,3,5-triamine;trihydrochloride Chemical compound Cl.Cl.Cl.CC1=C(N)C=C(N)C=C1N ROFCYGFJWHTQIY-UHFFFAOYSA-N 0.000 description 1
- LVHOAHHFUNMKQA-UHFFFAOYSA-N 3,3-dihydroxy-2,2,5,5-tetramethyl-4-oxohexanoic acid Chemical compound CC(C)(C)C(=O)C(O)(O)C(C)(C)C(O)=O LVHOAHHFUNMKQA-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- YHTLGFCVBKENTE-UHFFFAOYSA-N 4-methyloxan-2-one Chemical compound CC1CCOC(=O)C1 YHTLGFCVBKENTE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 102100032341 PCNA-interacting partner Human genes 0.000 description 1
- 101710196737 PCNA-interacting partner Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 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
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
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 materials, and (2) a particle containing a predetermined amount of a hydroxyl group and/or colloidal silica and the like as an abrasive particle(s), by a polymerization reaction, the matrix resin being a resin having an urethane bond and/or an urea bond.
The abrasive enables long-term continuous polishing of a workpiece to be polished without exerting a bad influence upon the environment.
Description
- 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.
- There has been known CMP (Chemical Mechanical Polishing) method using a nonwoven fabric polishing pad and an abrasive liquid containing free abrasive grains. In recent years, ecological CMP has been desired to reduce the cost of polishing treatment and solve a problem such as the disposal of abrasive liquid waste.
- The above CMP using an abrasive liquid which contains free abrasive grains has a problem that a simple liquid waste disposal method cannot be employed because most of the used free abrasive grains (such as silica or the like) are discharged into liquid waste. In general, consumption of the abrasive grains consumed by wear during polishing is about 3 to 4 wt % of the total, and most of the abrasive grains are wasted without directly contributing to polishing. Therefore, with CMP using an abrasive liquid which contains free abrasive grains, it has been difficult to reduce the cost of processing and take measures for environmental preservation.
- In view of the above situation, studies have been being made on the improvement of CMP using a polishing pad containing abrasive grains without using an abrasive liquid containing free abrasive grains. In this improved CMP, since most abrasive grains (such as silica or the like) are worn away and consumed by contributing to polishing, the amount of abrasive grains to be discharged into abrasive liquid waste can be reduced and therefore the abrasive liquid which has been used for polishing can be recycled by filtration. Since the abrasive grains are not wasted, a great reduction in the running cost of the polishing step can be expected.
- However, as the conventional fixed abrasive grain polishing pad does not exhibit a spontaneous edging function, the polishing efficiency (polishing rate) lowers in a relatively short period of time, thereby making it impossible to carry out long-term continuous polishing. Therefore, abrasive grains must be dressed frequently, thereby causing a reduction in productivity.
- For example, 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. Although 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.
- Further, 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. However, the continuous polishing can not be done still for a long time, and dressing must be carried out regularly.
- In view of the above situation, in order to carry out continuous polishing for a long time, an abrasive liquid containing free abrasive grains had to be used to polish a workpiece to be polished.
- In general, as for requirements for an abrasive for polishing a compound semiconductor wafer or the like, 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.
- Further, 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.
- It is therefore an object of the present invention to provide 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; and a fixed abrasive grain polishing pad comprising the above abrasive.
- It is another object of the present invention to provide a method of polishing a workpiece to be polished using the above abrasive.
- 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.
- That is, according to a first aspect of the present invention, there is provided 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 E1) 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 E2) selected from fumed silica, colloidal silica, fumed alumina, colloidal alumina, boehmite and bayerite.
- In the first aspect of the present invention, it is desired that
- (1) the matrix resin (resin F) should be a resin having at least an urethane bond,
- (2) 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),
- (3) 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),
- (4) the matrix resin (resin F) should be a resin having at least one of urethane bond, urea bond and amide bond,
- (5) the expansion ratio should be 1.1 to 5,
- (6) the particle (component E) should be colloidal silica,
- (7) the amount of the hydroxyl group in the particle (component E1) should be 0.01 to 6 mmol/g,
- (8) the particle (component E1) 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,
- (9) the matrix resin (resin F) should be contained in the abrasive in an amount of 60 to 95 wt %,
- (10) 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,
- (11) 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
- (12) 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.
- According to a second aspect of the present invention, there is provided 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 abrasive grain polishing pad (polishing pad G) and the workpiece.
- In the second aspect of the present invention, it is desired that
- (1) the fixed abrasive grain polishing pad (polishing pad G) should have grooves extending radially from the center point toward the circumferential direction, and
- (2) the fixed abrasive grain polishing pad (polishing pad G) should have lattice-like grooves.
- According to a third aspect of the present invention, there is provided 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.
- In the third aspect of the present invention, it is desired that
- (1) the abrasive liquid (abrasive liquid H) should be an alkaline aqueous solution, and
- (2) the above alkaline aqueous solution should have a pH of 10 or higher.
- Even when the workpiece is continuously polished with the abrasive of the present invention for a long time, the polishing function of the abrasive rarely lowers. Further, although 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 concrete mechanism of the long-term continuous polishing of the workpiece by using the abrasive of the present invention is not made clear but it is assumed that chemical bonding force is developed between the isocyanate group (—CNO) of the organic polyisocyanate (component A) and the hydroxyl group of the particle (component E) when the abrasive of the present invention is cured and molded by a polymerization reaction.
- That is, it is assumed that 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), and 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)].
- It is presumed that with the consequence of the development of the chemical bond between the matrix resin (resin F) and the abrasive grains (abrasive grains I), the amount of the abrasive grains (abrasive grains I) which fall off in the matrix resin (resin F) is greatly reduced, thereby making long-term continuous polishing possible.
- It is assumed that in the abrasive of the prior art, the hydroxyl group rarely existed or existed in very small quantities in the particle used and hence, abrasive grains were merely held in the matrix resin physically, whereby most of the abrasive grains easily fell off.
- Since chemical bonding force develops at the boundary between the matrix resin (resin F) and the abrasive grains (abrasive grains I), not only the abrasive grains (abrasive grains I) existent on the polishing surface of the abrasive but also the entire surface of the abrasive become treated surfaces. Accordingly, it is considered that the polishing rate does not lower even in the case of long-term continuous polishing.
- Owing to these reasons, long-term continuous polishing is made possible even when the spontaneous edging function of the abrasive is not exhibited.
- [First Aspect of the Present Invention]
- 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).
- 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.
- 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.
- These organic polyisocyanate compounds (component A) may be used alone or in combination of two or more.
- Out of these, tolylene diisocyanate (TDI) and 4,4-diphenylmethane diisocyanate (MDI) are preferred.
- As the 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 ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether; polyester polyols obtained by the cocondensation of at least one of the above polyhydric alcohols and a polycarboxylic acid such as succinic acid, maleic acid, adipic acid, glutaric acid, pimellic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthailc acid or terephthalic acid; lactone-based polyester polyols obtained by the polycondensation reaction of at least one of the above polyhydric alcohols and a lactone such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone; epoxy-modified polyester polyols obtained by using at least one epoxy compound such as bisphenol A epoxy compound, hydrogenated bisphenol A epoxy compound, glycidyl ether of monohydric and/or polyhydric alcohol(s) or glycidyl ester of a monobasic acid and/or polybasic acid at the time of synthesizing a polyester polyol; polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives and hydroxyl group-containing acryl copolymers.
- 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 (component B) 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]).
- In the present invention, 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′-diaminodiphenylmethane, hydrogenated 4,4′-diaminodiphenylmethane and derivatives of these polyamine monomers.
- 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.
- Further, in the present invention, an organic polycarboxylic acid (component J) may be used in place of the above organic polyol (component B) and/or organic polyamine (component C). In this case, the matrix resin (resin F) becomes a resin having at least one of urethane bond, urea bond and amide bond.
- Examples of the organic polycarboxylic acid (component J) 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.
- The term “expansion ratio” as used herein is represented by D1/D2 wherein D1 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 D2 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).
- Although 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.
- On the other hand, 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. Examples of the amine-based catalyst include triethylenediamine, triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, N-methylmorpholine and N-ethylmorpholine. Examples of 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).
- As the foam stabilizer may be used a conventionally known organosilicone-based surfactant. Examples of the 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.
- Optionally, 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.
- In the present invention, as the abrasive particle (component E) may be used (a) a particle having a hydroxyl group in an amount of 0.001 mmol/g (component E1) and/or (b) at least one member (component E2) selected from fumed silica, colloidal silica, fumed alumina, colloidal alumina, boehmite and bayerite.
- When the above particle (component E1) is used as the abrasive particle, the amount of the hydroxyl group of the particle having a hydroxyl group (component E1) is 0.001 mmol/g or more when measured by the following neutralization titration. When 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.
- Although there is no upper limit to the amount of the hydroxyl group of the particle (component E1), when it is too large, the particle (component E1) is apt to be covered with the matrix resin and hence, an effect obtained by increasing the amount of the hydroxyl group cannot be expected. The amount of the hydroxyl group of the particle (component E1) 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 (component E) 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.
- X=[(B−A)×0.05×8]/W
- 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). In the present invention, since 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 (component E1) 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 E1) 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.
- As the abrasive particle (component E2) may be used at least one member selected from fumed silica, colloidal silica, fumed alumina, colloidal alumina, boehmite and bayerite.
- Since these abrasive particles (component E2) 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 E1). Out of these, colloidal silica is preferred.
- When 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. For example, 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).
- Preferably, these abrasive particles (component E) 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 μm. When the particle diameter is smaller than 0.005 μm, it is difficult to obtain the high polishing speed, while when the particle diameter is larger than 50 μm, 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).
- When 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. When 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).
- As described above, 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.
- [Second Aspect of the Present Invention]
- 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.
- When an abrasive liquid is used, 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).
- [Third Aspect of the Present Invention]
- 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 (abrasive liquid H) 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.
- 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.
- Since 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; and
- FIG. 3 is a graph showing the relationship between polishing time and polishing efficiency in Example 1.
- (First Embodiment)
- 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.
- In this case, it is particularly preferred that 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.
- It is also preferred that 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.
- When a reaction injection molding method is employed, a mixture of the raw materials is injected into the mold from a resin gate and cured in the mold by heating for a relatively short period of time to obtain a molded product.
- 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. When 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).
- (Second Embodiment)
- As shown in FIG. 2,
grooves 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. For example, radial grooves as shown in FIG. 2(A) and lattice type grooves as shown in FIG. 2(B) can be formed. - To form the
radial grooves 16 a in the fixed abrasivegrain polishing pad 16 as shown in FIG. 2(A), the fixed abrasivegrain 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). Preferably, 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 thegrooves 16 a around the center of the fixed abrasivegrain polishing pad 16. - To form the lattice-
like grooves 16 b in the fixed abrasivegrain polishing pad 16 as shown in FIG. 2(B), the grooves are preferably formed at intervals of, for example, 15 to 30 mm. - In the above embodiment, the formation of radial or lattice type grooves in the fixed abrasive grain polishing pad is exemplified, but the present invention is not limited to these examples. Hexagonal, wavy grooves and the like may be suitably formed. While the sectional form of each groove has been described as square (rectangular), it may be circular, V-shaped or U-shaped.
- (Third Embodiment)
- A preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. In this specification and drawings, constituent elements having substantially the same functions are given the same reference symbols to avoid the repetitions of their descriptions.
- With reference to FIG. 1, the constitution of a polishing apparatus comprising a fixed abrasive grain polishing pad according to the third embodiment will be first described. FIG. 1 is a perspective view showing the constitution of the polishing apparatus comprising a fixed abrasive grain polishing pad according to this embodiment.
- As shown in FIG. 1, 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 amotor 12, a fixed abrasivegrain polishing pad 16 mounted on the polishing table 14, asubstrate holding portion 20 for pressing the surface to be polished of the heldsubstrate 30 against the fixed abrasivegrain polishing pad 16, a substrate holding portion drive means 18 for rotating and driving under pressure thesubstrate holder portion 20 and an abrasiveliquid supply port 24 for supplying anabrasive liquid 25 to the polishing table 14. - The polishing table14 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 aspindle 26 and a transmission (not shown). - 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 thesubstrate 30 as the polishing table 14 is rotated, whereby the polishing surface of thesubstrate 30 is polished by the aid of theabrasive liquid 25 supplied from the abrasiveliquid supply port 24. A detailed description of the fixed abrasivegrain polishing pad 16 will be given hereinafter. - The substrate holding portion drive means18 rotates the
substrate holding portion 20 while applying pressure to the portion through arod 28, and is, for example, composed of a motor, cylinder and the like (not shown). That is, thesubstrate holding portion 20 holding thesubstrate 30 can be pressed against the fixed abrasivegrain 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 thesubstrate 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 therod 28 and has a ring (retainer ring) for preventing a horizontal slide of thesubstrate 30 on the under surface. - At the time of regular polishing, the
substrate holding portion 20 presses the surface to be polished of thesubstrate 30 against the fixed abrasivegrain polishing pad 16 while rotating in a state of holding thesubstrate 30. Thesubstrate 30 which is thus pressed against the fixed abrasivegrain polishing pad 16 is rubbed bi-directionally with the fixed abrasivegrain 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 theabrasive liquid 25 to the rotating fixed abrasivegrain polishing pad 16 at the time of polishing thesubstrate 30. Theabrasive liquid 25 is a solution containing a chemically reactive substance, and enters the gap between thesubstrate 30 and the fixed abrasivegrain polishing pad 16 during polishing to smooth the polishing surface of thesubstrate 30 with high accuracy while it chemically reacts with the surface to be polished. - In the polishing apparatus of this embodiment, 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. When an abrasive liquid having a pH lower than 10 is used as shown in Example 2, the polishing rate greatly lowers.
- As 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. For example, when an alkaline solution prepared from sodium hydroxide or potassium hydroxide is used, 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. Preferably, 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.
- The polishing rate and the like of a workpiece to be polished (silicon wafer) 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 raw material compositions and physical properties of the polishing pads in Example 1 and Comparative Example 1 are shown in Table 1.
TABLE 1 Ex. 1 Comp. Ex. 1 Raw material Organic polyol A 48.5 48.5 composition of Organic polyol B 31.5 31.5 matrix resin Organic polyisocyanate 38.5 38.3 (parts by Water 0.2 0.2 weight) Catalyst 0.7 0.7 Silicone foam stabilizer 0.5 0.5 Abrasive Colloidal silica 88.7 0 particle Alumina 0 88.7 (parts by weight) Physical Content of abrasive grain 30 30 properties of Average molecular weigh 1500 1500 polishing pad of polyol Expansion ratio (times) 2 2 Hardness at 20° C. (Shore 40 39 D) - As shown in Table 1, 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 polishing pad used in Comparative Example 1 was obtained in the same manner as in Example 1 except that alumina was used in place of colloidal silica in Example 1.
- As shown in FIG. 1, 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.
- The polishing conditions are given below.
- Polishing pressure: 300 g/cm2
- Revolution of table: 40 rpm.
- 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 D1/D2 wherein D, is the density of a non-foamed cured product and D2 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).
- As for the evaluation of liquid waste, the liquid waste was filtered with a qualitative filter having a retained particle diameter of 1 μm 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.
- The evaluation results are shown in FIG. 3 and Table 2.
TABLE 2 Ex. 1 Comp. Ex. 1 Comp. Ex. 2 polishing 333 80 10 possible time Polishing rate Polishing rate Polishing rate Polishing rate remains almost lowers each greatly lowers unchanged even time polishing each time after 333 is carried polishing is hours of out. carried out. continuous Polishing Polishing polishing. becomes becomes impossible impossible after 80 hours after 10 hours of continuous of continuous polishing. polishing. State of No abrasive Abrasive Abrasive abrasive grains fall grains fall grains fall grains off. off. off. - As shown in FIG. 3 and Table 2, in the case of the polyurethane polishing pad containing silica abrasive grains of the present invention, even after 333 hours of continuous polishing, the polishing rate was constant. It could not be confirmed whether abrasive grains fell off at the time of polishing. Since the polishing time of one silicon wafer is generally 10 minutes, when continuous polishing is carried out for 333 hours, about 2,000 silicon wafers can be polished continuously.
- The evaluation result of the liquid waste was satisfactory.
- In the case of the polyurethane polishing pad containing alumina abrasive grains of Comparative Example 1, the polishing rate lowered with the passage of the polishing time, and polishing became impossible after 80 hours. The first silicon wafer could be polished normally but the polishing rate of the second silicon extremely lowered.
- In the case of the conventional fixed abrasive grain polishing pad of Comparative Example 2, instantaneous with start of polishing, the polishing rate sharply dropped and polishing became impossible after 10 hours. The first silicon wafer could be polished normally but the polishing rate of the second silicon wafer was almost null.
- When a fixed abrasive grain polishing pad produced by using colloidal silica as an abrasive particle material and urethane as a matrix resin was used in the above Example 1, it was confirmed that the polishing rate was maintained at a constant level even after 333 hours of continuous polishing. When it is taken into consideration that dressing is necessary after 10 minutes of polishing in the method using the conventional fixed abrasive grain polishing pad, it is understood that the continuous polishing time is sharply improved. Further, the thickness of the fixed abrasive grain polishing pad was not reduced and the abrasive grains did not fall off at all. Therefore, since only silicon as the material of the workpiece to be polished and the alkaline solution were discharged into the liquid waste after polishing, the disposal of the liquid waste could be carried out easily without exerting any bad influence upon the environment.
- 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, and organic polyisocyanate (manufactured by Dow Polyurethane Systems Co., Ltd., under the trade name of PARI 135) were used, and 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) and 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 a casting method to obtain an abrasive. The expansion ratio, hardness and roughness of the obtained abrasive are shown in Table 3.
- The workpiece (silicon wafer) to be polished was polished by the aid of an abrasive liquid having a pH of 9.5 to 13.5 under the following conditions. The results are shown in Table 3.
- The polishing conditions were given below.
- Polishing pressure: 300 g/cm2
- Revolution of table: 40 rpm.
TABLE 3 Example No. Ex. 2 Raw material Organic polyol A 71.6 composition of Organic polyol B 8.4 matrix resin (parts Organic polyisocyanate 52.5 by weight) Water 0.2 Catalyst 0.7 Silicone foam stabilizer 0.5 Abrasive particle colloidal silica 90.1 (parts by weight) Physical properties Content of abrasive grains 30 of polishing pad Expansion ratio (times) 2 Hardness at 20° C. (Shore D) 70 Roughness (Ry) [nm] 30 polishing pH of abrasive liquid rate Polishing rate 9.5 0.01 10 0.1 10.5 0.15 11 0.2 11.5 0.3 12 0.4 12.5 0.45 13 0.47 13.5 0.48 - It is understood from Table 3 that the pH of the abrasive liquid is preferably 10 or higher. When an abrasive liquid having a pH lower than 10 is used, the polishing rate greatly lowers.
- The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. It is obvious to those skilled in the art that changes and modifications will occur without departing from the scope of the technical idea set forth in the appended claims and it is to be understood as a matter of course that they are included in the technical scope of the present invention.
- Since chemical bonding exists between the matrix resin and the abrasive grains in the abrasive of the present invention, bonding force between the matrix resin and the abrasive grains greatly improves and as a result, the abrasive grains rarely fall off from the matrix resin. This makes possible long-term continuous polishing without obtaining the spontaneous edging function of the abrasive. Even when polishing is continuously carried out for a long time, the abrasive grains are hardly wasted and contained in liquid waste (abrasive liquid). Therefore, the abrasive liquid can be easily recycled by simple filtration means without exerting a bad influence upon the environment.
Claims (19)
1. An abrasive 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 E1) containing a hydroxyl group in an amount of 0.001 mmol/g or more (measured by neutralization titration) and/or (b) at least one member (component E2) selected from fumed silica, colloidal silica, fumed alumina, colloidal alumina, boehmite and bayerite.
2. The abrasive according to claim 1 , wherein the matrix resin (resin F) is a resin having at least an urethane bond.
3. The abrasive according to claim 1 or 2, wherein the matrix resin raw materials include 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).
4. The abrasive according to claim 1 or 2, wherein the matrix resin raw materials are 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).
5. The abrasive according to claim 1 or 2, wherein the matrix resin (resin F) is a resin having at least one of urethane bond, urea bond and amide bond.
6. The abrasive according to claim 1 or 2, which has an expansion ratio of 1.1 to 5.
7. The abrasive according to claim 1 or 2, wherein the particle (component E) is colloidal silica.
8. The abrasive according to claim 1 or 2, wherein the amount of the hydroxyl group of the particle (component E1) is 0.01 to 6 mmol/g (measured by neutralization titration).
9. The abrasive according to claim 1 or 2, wherein the particle having a hydroxyl group (component E1) is 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.
10. The abrasive according to claim 1 or 2, wherein the matrix resin (resin F) is contained in the abrasive in an amount of 60 to 95 wt %.
11. The abrasive according to claim 1 or 2, which is a foamed material obtained by curing raw materials containing 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.
12. The abrasive according to claim 1 , which is 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 resulting mixture by a polymerization reaction.
13. The abrasive according to claim 11 , which is obtained by adding a mixture of at least one member selected from an organic polyol (component B) and an 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, stirring and mixing them together, and curing and molding the resulting mixture by a polymerization reaction.
14. A fixed abrasive grain polishing pad (polishing pad G) that is composed of the abrasive according to claims 12 and 12 and is mounted on a polishing table, which is used for polishing a workpiece to be polished by the relative movements of the fixed abrasive grain polishing pad and the workpiece while pressing the workpiece between the fixed abrasive grain polishing pad (polishing pad) and a workpiece holding portion and supplying an abrasive liquid (abrasive liquid H) between the fixed abrasive grain polishing pad and the workpiece.
15. The fixed abrasive grain polishing pad according to claim 14 which has grooves extending radially from its center point toward its circumferential direction.
16. The fixed abrasive grain polishing pad according to claim 14 which has lattice type grooves.
17. A method of polishing a workpiece to be polished, comprising the steps of:
mounting a fixed abrasive grain polishing pad (polishing pad G) composed of the abrasive of claims 12 and 12 on a polishing table;
pressing the workpiece between the fixed abrasive grain polishing pad (polishing pad G) and a workpiece holding portion;
polishing the workpiece by the relative movements of the fixed abrasive grain polishing pad (polishing pad G) and the workpiece while an abrasive liquid (abrasive liquid H) is supplied between the fixed abrasive grain polishing pad (polishing pad G) and the workpiece.
18. The method of polishing a workpiece to be polished according to claim 17 , wherein the abrasive liquid (abrasive liquid H) is an alkaline aqueous solution.
19. The method of polishing a workpiece to be polished according to claim 18 , wherein the alkaline aqueous solution has a pH of 10 or higher.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-162631 | 2002-06-04 | ||
JP2002162631 | 2002-06-04 | ||
PCT/JP2003/006858 WO2003101668A1 (en) | 2002-06-04 | 2003-05-30 | Polishing material and method of polishing therewith |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040209554A1 true US20040209554A1 (en) | 2004-10-21 |
Family
ID=29706609
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/485,297 Abandoned US20040209554A1 (en) | 2002-06-04 | 2003-05-30 | Polishing material and method of polishing therewith |
Country Status (6)
Country | Link |
---|---|
US (1) | US20040209554A1 (en) |
JP (1) | JPWO2003101668A1 (en) |
KR (1) | KR20050005392A (en) |
AU (1) | AU2003242004A1 (en) |
DE (1) | DE10392153T5 (en) |
WO (1) | WO2003101668A1 (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US20060046064A1 (en) * | 2004-08-25 | 2006-03-02 | Dwaine Halberg | Method of improving removal rate of pads |
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 (en) | 2006-02-17 | 2007-08-22 | SUMCO Corporation | Wafer and method for producing the same |
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 (en) * | 2012-12-17 | 2014-06-26 | Centro De Tecnologia Mineral - Cetem | Method for producing a composite material consisting of a polymer of vegetable origin, a mineral filler and an abrasive material, and use of the resulting composition for polishing stone |
US20150047266A1 (en) * | 2013-08-16 | 2015-02-19 | San Fang Chemical Industry Co., Ltd. | Methods for manufacturing polishing pad and polishing apparatus |
CN104788701A (en) * | 2015-04-03 | 2015-07-22 | 衢州学院 | Nano-silica polishing film adopting modified organosilicone binder and preparation process of nano-silica polishing film |
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 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4729896B2 (en) * | 2004-09-17 | 2011-07-20 | ソニー株式会社 | Semiconductor thin film surface treatment method |
JP5024305B2 (en) * | 2009-02-04 | 2012-09-12 | 住友電気工業株式会社 | Polishing method of GaN substrate |
KR101255523B1 (en) * | 2011-04-08 | 2013-04-23 | 노태욱 | Urethane form polishing pad and method of manufacturing the same |
JP6411759B2 (en) * | 2014-03-27 | 2018-10-24 | 株式会社フジミインコーポレーテッド | Polishing composition, method for using the same, and method for producing a substrate |
CN106392911A (en) * | 2016-12-14 | 2017-02-15 | 方彩燕 | Composite grinding wheel |
TWI639486B (en) * | 2018-05-31 | 2018-11-01 | 國立清華大學 | Omni-directional integrated conditioner device |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5391210A (en) * | 1993-12-16 | 1995-02-21 | Minnesota Mining And Manufacturing Company | Abrasive article |
US6165061A (en) * | 1995-04-10 | 2000-12-26 | Dai Nippon Printing Co. | Abrasive tape, process for producing it, and coating agent for abrasive tape |
US20030045213A1 (en) * | 2001-05-22 | 2003-03-06 | Keipert Steven J. | Cellular abrasive article |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11347952A (en) * | 1998-06-10 | 1999-12-21 | Hitachi Chem Co Ltd | Resin grinding wheel for grinding semi-conductor wafer, and its manufacture |
JP4597395B2 (en) * | 2001-02-07 | 2010-12-15 | 大日本印刷株式会社 | Polishing film and method for producing the same |
-
2003
- 2003-05-30 WO PCT/JP2003/006858 patent/WO2003101668A1/en active Application Filing
- 2003-05-30 AU AU2003242004A patent/AU2003242004A1/en not_active Abandoned
- 2003-05-30 US US10/485,297 patent/US20040209554A1/en not_active Abandoned
- 2003-05-30 JP JP2004509005A patent/JPWO2003101668A1/en active Pending
- 2003-05-30 KR KR10-2004-7001746A patent/KR20050005392A/en not_active Application Discontinuation
- 2003-05-30 DE DE10392153T patent/DE10392153T5/en not_active Ceased
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5391210A (en) * | 1993-12-16 | 1995-02-21 | Minnesota Mining And Manufacturing Company | Abrasive article |
US6165061A (en) * | 1995-04-10 | 2000-12-26 | Dai Nippon Printing Co. | Abrasive tape, process for producing it, and coating agent for abrasive tape |
US20030045213A1 (en) * | 2001-05-22 | 2003-03-06 | Keipert Steven J. | Cellular abrasive article |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060046064A1 (en) * | 2004-08-25 | 2006-03-02 | Dwaine Halberg | Method of improving removal rate of pads |
WO2006026343A1 (en) * | 2004-08-25 | 2006-03-09 | J.H. Rhodes, Inc. | Polishing pad and methods of improving pad removal rates and planarization |
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 |
US20060099891A1 (en) * | 2004-11-09 | 2006-05-11 | Peter Renteln | Method of chemical mechanical polishing, and a pad provided therefore |
US7255631B2 (en) * | 2005-03-02 | 2007-08-14 | Extrude Hone Corporation | Orbital polishing apparatus and method |
WO2006094157A2 (en) * | 2005-03-02 | 2006-09-08 | Extrude Hone Corporation | Orbital polishing apparatus and method |
US20060229003A1 (en) * | 2005-03-02 | 2006-10-12 | Extrude Hone Corporation | Orbital polishing apparatus and method |
WO2006094157A3 (en) * | 2005-03-02 | 2007-06-21 | Extrude Hone Corp | Orbital polishing apparatus and method |
US7303691B2 (en) * | 2005-09-06 | 2007-12-04 | Sumco Techxiv Corporation | Polishing method for semiconductor wafer |
US20070059935A1 (en) * | 2005-09-06 | 2007-03-15 | Komatsu Electronic Metals Co., Ltd. | Polishing method for semiconductor wafer |
US7951716B2 (en) * | 2006-02-17 | 2011-05-31 | Sumco Corporation | Wafer and method of producing the same |
US20070197035A1 (en) * | 2006-02-17 | 2007-08-23 | Sumco Corporation | Wafer and method of producing the same |
EP1820603A3 (en) * | 2006-02-17 | 2007-11-28 | SUMCO Corporation | Wafer and method for producing the same |
EP1820603A2 (en) | 2006-02-17 | 2007-08-22 | SUMCO Corporation | Wafer and method for producing the same |
US9325403B2 (en) | 2008-12-23 | 2016-04-26 | Elta Systems Ltd. | Digital retro-directive communication system and method thereof |
US8523968B2 (en) | 2008-12-23 | 2013-09-03 | Saint-Gobain Abrasives, Inc. | Abrasive article with improved packing density and mechanical properties and method of making |
US9143220B2 (en) | 2008-12-23 | 2015-09-22 | Elta Systems Ltd. | Digital retro-directive communication system and method thereof |
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 |
US9156127B2 (en) * | 2008-12-26 | 2015-10-13 | Toyo Tire & Rubber Co., Ltd. | Polishing pad and method for producing same |
WO2014094092A1 (en) * | 2012-12-17 | 2014-06-26 | Centro De Tecnologia Mineral - Cetem | Method for producing a composite material consisting of a polymer of vegetable origin, a mineral filler and an abrasive material, and use of the resulting composition for polishing stone |
US20150047266A1 (en) * | 2013-08-16 | 2015-02-19 | San Fang Chemical Industry Co., Ltd. | Methods for manufacturing polishing pad and polishing apparatus |
CN104788701A (en) * | 2015-04-03 | 2015-07-22 | 衢州学院 | Nano-silica polishing film adopting modified organosilicone binder and preparation process of nano-silica polishing film |
US20200091013A1 (en) * | 2018-09-19 | 2020-03-19 | Taiwan Semiconductor Manufacturing Co., Ltd. | Thickness measurement system and method |
CN110926398A (en) * | 2018-09-19 | 2020-03-27 | 台湾积体电路制造股份有限公司 | Thickness measurement system and method |
US11177183B2 (en) | 2018-09-19 | 2021-11-16 | Taiwan Semiconductor Manufacturing Co., Ltd. | Thickness measurement system and method |
Also Published As
Publication number | Publication date |
---|---|
JPWO2003101668A1 (en) | 2005-09-29 |
AU2003242004A1 (en) | 2003-12-19 |
DE10392153T5 (en) | 2004-08-19 |
WO2003101668A1 (en) | 2003-12-11 |
KR20050005392A (en) | 2005-01-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20040209554A1 (en) | Polishing material and method of polishing therewith | |
KR101186531B1 (en) | Polyurethane porous product and manufacturing method thereof and Polishing pad having Polyurethane porous product | |
TWI765938B (en) | Polishing pad for polishing substrate | |
US7470170B2 (en) | Polishing pad and method for manufacture of semiconductor device using the same | |
JP4313761B2 (en) | Method for producing polyurethane foam containing fine pores and polishing pad produced therefrom | |
CN101253022B (en) | Polishing pad | |
KR101141880B1 (en) | Polyurethane polishing pad | |
EP2151299B1 (en) | Chemical mechanical polishing pad | |
JP7197330B2 (en) | High Removal Rate Chemical Mechanical Polishing Pads from Amine Initiated Polyol Containing Hardeners | |
WO2006123559A1 (en) | Polishing pad | |
US9079289B2 (en) | Polishing pad | |
KR102283399B1 (en) | Composition for polishing pad, polishing pad and preparation method thereof | |
US20140342641A1 (en) | Polishing pad | |
CN101180158A (en) | Polishing pad | |
KR102202076B1 (en) | Composition for polishing pad, polishing pad and preparation method thereof | |
JP2003171433A (en) | Method for producing expanded polyurethane polishing pad | |
TW200819513A (en) | Polishing pad | |
JP2017132012A (en) | Manufacturing method for polishing pad | |
TW202116845A (en) | Polishing pad, process for preparing the same, and process for preparing a semiconductor device using the same | |
TWI833693B (en) | Polishing pad, manufacturing method of polishing pad, method of polishing the surface of optical material or semiconductor material, and method of reducing scratches when polishing the surface of optical material or semiconductor material | |
JP2004337992A (en) | Fixed abrasive grain polishing pad, and method of polishing silicon wafer using fixed abrasive grain polishing pad | |
JP2009090397A (en) | Polishing pad | |
JP7349774B2 (en) | Polishing pad, method for manufacturing a polishing pad, method for polishing the surface of an object to be polished, method for reducing scratches when polishing the surface of an object to be polished | |
JP4636787B2 (en) | Fixed abrasive polishing pad, polishing equipment | |
JP2017132013A (en) | Polishing pad |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: DISCO CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TSUMAGARI, AKIO;ISHIKAWA, KAZUNORI;MIYAZAKI, KAZUYA;AND OTHERS;REEL/FRAME:015500/0447 Effective date: 20040113 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |