JP5362319B2 - Polishing liquid composition - Google Patents
Polishing liquid composition Download PDFInfo
- Publication number
- JP5362319B2 JP5362319B2 JP2008271252A JP2008271252A JP5362319B2 JP 5362319 B2 JP5362319 B2 JP 5362319B2 JP 2008271252 A JP2008271252 A JP 2008271252A JP 2008271252 A JP2008271252 A JP 2008271252A JP 5362319 B2 JP5362319 B2 JP 5362319B2
- Authority
- JP
- Japan
- Prior art keywords
- polishing
- weight
- abrasive
- liquid composition
- wafer
- 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.)
- Expired - Fee Related
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 142
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 239000007788 liquid Substances 0.000 title claims abstract description 50
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 30
- 239000010703 silicon Substances 0.000 claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 235000012431 wafers Nutrition 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008119 colloidal silica Substances 0.000 claims description 10
- 239000011164 primary particle Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 abstract description 17
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract description 3
- -1 2-oxazoline compound Chemical class 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229920003169 water-soluble polymer Polymers 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000012736 aqueous medium Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 7
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 150000007514 bases Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- BYVSMDBDTBXASR-UHFFFAOYSA-N 5,6-dihydro-4h-oxazine Chemical class C1CON=CC1 BYVSMDBDTBXASR-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000011362 coarse particle Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 239000006061 abrasive grain Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 150000000376 2-oxazolines Chemical class 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- UGFGNNNVFDQQFE-UHFFFAOYSA-N 2-anthracen-2-yl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=C(C=C2C(C=CC=C2)=C2)C2=C1 UGFGNNNVFDQQFE-UHFFFAOYSA-N 0.000 description 1
- GKPDXYQIQIJZJT-UHFFFAOYSA-N 2-benzyl-4,5-dihydro-1,3-oxazole Chemical compound C=1C=CC=CC=1CC1=NCCO1 GKPDXYQIQIJZJT-UHFFFAOYSA-N 0.000 description 1
- VERUITIRUQLVOC-UHFFFAOYSA-N 2-butyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCC1=NCCO1 VERUITIRUQLVOC-UHFFFAOYSA-N 0.000 description 1
- NUNKLRNANFBFIP-UHFFFAOYSA-N 2-decyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCC1=NCCO1 NUNKLRNANFBFIP-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- AHWWSAKLCQMNOS-UHFFFAOYSA-N 2-docosyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCCCCCCCCC1=NCCO1 AHWWSAKLCQMNOS-UHFFFAOYSA-N 0.000 description 1
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 1
- UYYJMFSHINHDLB-UHFFFAOYSA-N 2-henicosyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCCCCCCCC1=NCCO1 UYYJMFSHINHDLB-UHFFFAOYSA-N 0.000 description 1
- GIGOAOBKJCQHSF-UHFFFAOYSA-N 2-heptadecyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCCCC1=NCCO1 GIGOAOBKJCQHSF-UHFFFAOYSA-N 0.000 description 1
- BWDVBMJUJCPESR-UHFFFAOYSA-N 2-heptyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCC1=NCCO1 BWDVBMJUJCPESR-UHFFFAOYSA-N 0.000 description 1
- XGBNRVRKSGTHJT-UHFFFAOYSA-N 2-hexadecyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCCC1=NCCO1 XGBNRVRKSGTHJT-UHFFFAOYSA-N 0.000 description 1
- AADZRTSFCAMLBV-UHFFFAOYSA-N 2-hexyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCC1=NCCO1 AADZRTSFCAMLBV-UHFFFAOYSA-N 0.000 description 1
- KPJOKFYBBIDEGF-UHFFFAOYSA-N 2-icosyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCCCCCCC1=NCCO1 KPJOKFYBBIDEGF-UHFFFAOYSA-N 0.000 description 1
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 1
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- JBPBWSKDBJRSAU-UHFFFAOYSA-N 2-naphthalen-2-yl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=C(C=CC=C2)C2=C1 JBPBWSKDBJRSAU-UHFFFAOYSA-N 0.000 description 1
- NZRAZDNOFLBJCI-UHFFFAOYSA-N 2-nonadecyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCCCCCC1=NCCO1 NZRAZDNOFLBJCI-UHFFFAOYSA-N 0.000 description 1
- OQWAVMKUNIQCFD-UHFFFAOYSA-N 2-nonyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCC1=NCCO1 OQWAVMKUNIQCFD-UHFFFAOYSA-N 0.000 description 1
- ZWXOPTQPMFPVNA-UHFFFAOYSA-N 2-octadecyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCCCCC1=NCCO1 ZWXOPTQPMFPVNA-UHFFFAOYSA-N 0.000 description 1
- LRTZAUAUUUURAF-UHFFFAOYSA-N 2-octyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCC1=NCCO1 LRTZAUAUUUURAF-UHFFFAOYSA-N 0.000 description 1
- BJQFPPVYNUKSCM-UHFFFAOYSA-N 2-pentadecyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCC1=NCCO1 BJQFPPVYNUKSCM-UHFFFAOYSA-N 0.000 description 1
- SNIKIBGVTOUZMH-UHFFFAOYSA-N 2-perylen-1-yl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=C(C=CC=C23)C2=C1C1=C2C3=CC=CC2=CC=C1 SNIKIBGVTOUZMH-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- GXCJLVVUIVSLOQ-UHFFFAOYSA-N 2-propyl-4,5-dihydro-1,3-oxazole Chemical compound CCCC1=NCCO1 GXCJLVVUIVSLOQ-UHFFFAOYSA-N 0.000 description 1
- VMVPDYSFBINHRI-UHFFFAOYSA-N 2-pyren-1-yl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=C(C=C2)C3=C4C2=CC=CC4=CC=C13 VMVPDYSFBINHRI-UHFFFAOYSA-N 0.000 description 1
- SDADDJBCSSCSPN-UHFFFAOYSA-N 2-tetradecyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCC1=NCCO1 SDADDJBCSSCSPN-UHFFFAOYSA-N 0.000 description 1
- AXTWULOROZCMFV-UHFFFAOYSA-N 2-tridecyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCC1=NCCO1 AXTWULOROZCMFV-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- JCNUTCOYVIACDJ-UHFFFAOYSA-N C(CCCCCCCCCCC)C=1OCCN1.C(CCCCCCCCCC)C=1OCCN1 Chemical compound C(CCCCCCCCCCC)C=1OCCN1.C(CCCCCCCCCC)C=1OCCN1 JCNUTCOYVIACDJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
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- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000005119 centrifugation Methods 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- VXZOOXXSYPYWEP-UHFFFAOYSA-H hexasodium hexaacetate Chemical compound C(C)(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] VXZOOXXSYPYWEP-UHFFFAOYSA-H 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- DEIVNMVWRDMSMJ-UHFFFAOYSA-N hydrogen peroxide;oxotitanium Chemical compound OO.[Ti]=O DEIVNMVWRDMSMJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 229960003506 piperazine hexahydrate Drugs 0.000 description 1
- AVRVZRUEXIEGMP-UHFFFAOYSA-N piperazine;hexahydrate Chemical compound O.O.O.O.O.O.C1CNCCN1 AVRVZRUEXIEGMP-UHFFFAOYSA-N 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
本発明は研磨液組成物およびこれを用いた半導体基板の製造方法並びにシリコンウエハの研磨方法に関する。 The present invention relates to a polishing liquid composition, a method for producing a semiconductor substrate using the same, and a method for polishing a silicon wafer.
半導体基板の製造に用いられるシリコンウエハ(「ベアウエハ」ともいう)の研磨に用いられる研磨液組成物として、シリカ粒子を含有する研磨液組成物が知られている。しかし、この種の研磨液組成物においては、シリカ粒子の凝集によりもたらされる弊害、例えば、研磨されたシリコンウエハに表面欠陥(LPD:Light point defects)が多く発生していること等が問題となっている。また、研磨液組成物を循環使用する場合には、使用後の研磨液組成物中の研磨屑を取り除くために使用されるフィルターがすぐに目詰まりすることが問題となっている(例えば、特許文献1および特許文献2等参照)。
LPDの低減のために、例えば、使用前の研磨液組成物に粗大粒子が含まれる場合、粗大粒子はフィルター等を用いて除去されるべきである。しかし、現行のヒドロキシエチルセルロース(HEC)を含む研磨液組成物(例えば、上記特許文献3参照)では、HECがシリカ粒子とネットワークを形成する為、粗大粒子のフィルターによるろ過が行えず、LPDの発生を十分に抑制できない。 In order to reduce LPD, for example, when coarse particles are contained in the polishing composition before use, the coarse particles should be removed using a filter or the like. However, in the polishing composition containing the current hydroxyethyl cellulose (HEC) (see, for example, Patent Document 3 above), HEC forms a network with silica particles, so filtration of coarse particles cannot be performed and LPD is generated. Cannot be suppressed sufficiently.
特許文献1では、フィルターの目詰まりを防止することを目的として、コロイダシリカと水酸化カリウムと炭酸水素カリウムとを含有する研磨液組成物が提案されている。しかし、この研磨液組成物にはナトリウムイオンやカリウムイオンが含まれているので、ウエハ表面に砥粒が付着しやすくなり、その結果、ウエハ表面に欠陥が生じやすくなるという問題がある。 Patent Document 1 proposes a polishing liquid composition containing colloidal silica, potassium hydroxide, and potassium bicarbonate for the purpose of preventing clogging of the filter. However, since this polishing liquid composition contains sodium ions and potassium ions, there is a problem that abrasive grains easily adhere to the wafer surface, and as a result, defects are likely to occur on the wafer surface.
特許文献2では、LPDを低減することを目的として、ポリビニルピロリドン及びポリN−ビニルホルムアミドから選ばれる少なくとも一種類の水溶性高分子とアルカリとを含有する研磨液組成物が提案されている。しかし、この研磨液組成物を用いた研磨では、研磨速度が十分とはいえない。 Patent Document 2 proposes a polishing composition containing at least one water-soluble polymer selected from polyvinyl pyrrolidone and poly N-vinylformamide and an alkali for the purpose of reducing LPD. However, polishing using this polishing composition is not sufficient in polishing rate.
本発明では、シリコンウエハを高速研磨でき、しかも、フィルターの目詰まりも低減できる研磨液組成物、および当該研磨液組成物を用いた半導体基板の製造方法並びにシリコンウエハの研磨方法を提供する。 The present invention provides a polishing composition that can polish a silicon wafer at high speed and reduce clogging of a filter, a method for manufacturing a semiconductor substrate using the polishing composition, and a method for polishing a silicon wafer.
本発明の研磨液組成物は、
下記一般式(1)
The following general formula (1)
本発明の半導体基板の製造方法は、本発明の研磨液組成物を用いてシリコンウエハを研磨する工程を含む。 The manufacturing method of the semiconductor substrate of this invention includes the process of grind | polishing a silicon wafer using the polishing liquid composition of this invention.
本発明のシリコンウエハの研磨方法は、本発明の研磨液組成物を用いてシリコンウエハを研磨する工程を含む。 The silicon wafer polishing method of the present invention includes a step of polishing a silicon wafer using the polishing composition of the present invention.
本発明によれば、シリコンウエハを高速研磨でき、しかも、フィルターの目詰まりも低減できる研磨液組成物、および当該研磨液組成物を用いた半導体基板の製造方法並びにシリコンウエハの研磨方法を提供できる。 According to the present invention, it is possible to provide a polishing composition that can polish a silicon wafer at high speed and reduce clogging of the filter, a method for manufacturing a semiconductor substrate using the polishing composition, and a method for polishing a silicon wafer. .
本発明は、下記一般式(1)で表される重合体を含むことにより、使用後の研磨液組成物中の研磨屑等の除去に用いられるフィルターの目詰まりを低減でき、かつ、高い研磨速度でシリコンウエハの研磨が行えるという知見に基づく。 By including a polymer represented by the following general formula (1), the present invention can reduce clogging of a filter used for removing polishing debris in a polishing liquid composition after use, and high polishing. Based on the knowledge that silicon wafers can be polished at high speed.
本発明の研磨液組成物に含まれる重合体は、下記一般式(1)
(重合体)
本発明の研磨液組成物に含まれる重合体は、2−オキサゾリン系化合物又は2−オキサジン系化合物等を重合して得ることができる(例えば、特開平6−293829号公報、特開平10−306163号公報等参照)。上記重合体の製造に用いられる好ましいモノマーとしては、置換もしくは無置換の2−オキサゾリン系化合物や置換もしくは無置換の2−オキサジン系化合物が挙げられる。
(Polymer)
The polymer contained in the polishing composition of the present invention can be obtained by polymerizing a 2-oxazoline compound or a 2-oxazine compound (for example, JP-A-6-2933829, JP-A-10-306163). No. publication etc.). Preferred monomers used for the production of the polymer include substituted or unsubstituted 2-oxazoline compounds and substituted or unsubstituted 2-oxazine compounds.
2−オキサゾリン系化合物としては、例えば2−オキサゾリン、2−メチル−2−オキサゾリン、2−エチル−2−オキサゾリン、2−プロピル−2−オキサゾリン、2−ブチル−2−オキサゾリン、2−ペンチル−2−オキサゾリン、2−ヘキシル−2−オキサゾリン、2−ヘプチル−2−オキサゾリン、2−オクチル−2−オキサゾリン、2−ノニル−2−オキサゾリン、2−デシル−2−オキサゾリン、2−ウンデシル−2−オキサゾリン、2−ドデシル−2−オキサゾリン、2−トリデシル−2−オキサゾリン、2−テトラデシル−2−オキサゾリン、2−ペンタデシル−2−オキサゾリン、2−ヘキサデシル−2−オキサゾリン、2−ヘプタデシル−2−オキサゾリン、2−オクタデシル−2−オキサゾリン、2−ノナデシル−2−オキサゾリン、2−エイコシル−2−オキサゾリン、2−ヘンエイコシル−2−オキサゾリン、2−ドコシル−2−オキサゾリン、2−ベンジル−2−オキサゾリン、2−フェニル−2−オキサゾリン、2−ナフチル−2−オキサゾリン、2−アンスリル−2−オキサゾリン、2−ピレニル−2−オキサゾリン、2−ペリレニル−2−オキサゾリン等が挙げられる。 Examples of 2-oxazoline compounds include 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2-oxazoline, and 2-pentyl-2. -Oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-undecyl-2-oxazoline 2-dodecyl-2-oxazoline, 2-tridecyl-2-oxazoline, 2-tetradecyl-2-oxazoline, 2-pentadecyl-2-oxazoline, 2-hexadecyl-2-oxazoline, 2-heptadecyl-2-oxazoline, 2 -Octadecyl-2-oxazoline, 2-nonadecyl-2 Oxazoline, 2-eicosyl-2-oxazoline, 2-heneicosyl-2-oxazoline, 2-docosyl-2-oxazoline, 2-benzyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-naphthyl-2-oxazoline, Examples include 2-anthryl-2-oxazoline, 2-pyrenyl-2-oxazoline, and 2-perylenyl-2-oxazoline.
また、2−オキサジン系化合物としては例えば、2−オキサジン、2−メチル−2−オキサジン、2−エチル−2−オキサジン、2−プロピル−2−オキサジン、2−ブチル−2−オキサジン、2−ペンチル−2−オキサジン、2−ヘキシル−2−オキサジン、2−ヘプチル−2−オキサジン、2−オクチル−2−オキサジン、2−ノニル−2−オキサジン、2−デシル−2−オキサジン、2−ウンデシル−2−オキサジン、2−ドデシル−2−オキサジン、2−トリデシル−2−オキサジン、2−テトラデシル−2−オキサジン、2−ペンタデシル−2−オキサジン、2−ヘキサデシル−2−オキサジン、2−ヘプタデシル−2−オキサジン、2−オクタデシル−2−オキサジン、2−ノナデシル−2−オキサジン、2−エイコシル−2−オキサジン、2−ヘンエイコシル−2−オキサジン、2−ドコシル−2−オキサジン、2−ベンジル−2−オキサジン、2−フェニル−2−オキサジン、2−ナフチル−2−オキサジン、2−アンスリル−2−オキサジン、2−ピレニル−2−オキサジン、2−ペリレニル−2−オキサジン等が挙げられる。 Examples of 2-oxazine compounds include 2-oxazine, 2-methyl-2-oxazine, 2-ethyl-2-oxazine, 2-propyl-2-oxazine, 2-butyl-2-oxazine, and 2-pentyl. 2-oxazine, 2-hexyl-2-oxazine, 2-heptyl-2-oxazine, 2-octyl-2-oxazine, 2-nonyl-2-oxazine, 2-decyl-2-oxazine, 2-undecyl-2 -Oxazine, 2-dodecyl-2-oxazine, 2-tridecyl-2-oxazine, 2-tetradecyl-2-oxazine, 2-pentadecyl-2-oxazine, 2-hexadecyl-2-oxazine, 2-heptadecyl-2-oxazine 2-octadecyl-2-oxazine, 2-nonadecyl-2-oxazine, 2-eicosyl-2- Xazine, 2-heneicosyl-2-oxazine, 2-docosyl-2-oxazine, 2-benzyl-2-oxazine, 2-phenyl-2-oxazine, 2-naphthyl-2-oxazine, 2-anthryl-2-oxazine, Examples include 2-pyrenyl-2-oxazine and 2-perylenyl-2-oxazine.
本発明の研磨液組成物に含まれる重合体は、上記の2−オキサゾリン系化合物や2−オキサジン系化合物以外のモノマーに由来の構成単位を本発明の効果を損なわない範囲で含んでいてもよいが、好ましくはポリ(N−アシルアルキレンイミン)であり、置換もしくは無置換の2−オキサゾリン系化合物及び/又は置換もしくは無置換の2−オキサジン系化合物を重合して得られるポリ(N−アシルアルキレンイミン)がより好ましい。 The polymer contained in the polishing composition of the present invention may contain structural units derived from monomers other than the 2-oxazoline-based compound and 2-oxazine-based compound as long as the effects of the present invention are not impaired. Is preferably poly (N-acylalkyleneimine) and is obtained by polymerizing a substituted or unsubstituted 2-oxazoline compound and / or a substituted or unsubstituted 2-oxazine compound. Imine) is more preferred.
本発明の研磨液組成物に含まれる上記重合体の重量平均分子量は、研磨速度を向上させる観点から、1万〜400万が好ましく、より好ましくは1万〜200万、さらに好ましくは1万〜150万、よりいっそう好ましくは1万〜100万、さらにいっそう好ましくは10万〜80万である。重合体の重量平均分子量は、下記の方法により測定される。 The weight average molecular weight of the polymer contained in the polishing composition of the present invention is preferably 10,000 to 4,000,000, more preferably 10,000 to 2,000,000, and still more preferably 10,000 to 10,000, from the viewpoint of improving the polishing rate. It is 1.5 million, more preferably 10,000 to 1,000,000, still more preferably 100,000 to 800,000. The weight average molecular weight of the polymer is measured by the following method.
<重量平均分子量の測定法>
重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)法を下記の条件で適用して得たクロマトグラム中のピークに基づいて算出した値である。
カラム:α−M+α−M(東ソー株式会社)
溶離液:DMF(60mmol/LのH3PO4、50mmol/LのLiBr)
流量:1.0mL/min
カラム温度:40℃
検出器:RI検出器
標準物質:ポリスチレン換算
(分子量(Mw):842万、10.2万、A−500(東ソー株式会社)、90万、3万、4000(西尾工業株式会社))
<Measurement method of weight average molecular weight>
The weight average molecular weight is a value calculated based on a peak in a chromatogram obtained by applying a gel permeation chromatography (GPC) method under the following conditions.
Column: α-M + α-M (Tosoh Corporation)
Eluent: DMF (60 mmol / L H 3 PO 4 , 50 mmol / L LiBr)
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detector: RI detector Standard material: Polystyrene conversion (Molecular weight (Mw): 842,000, 102,000, A-500 (Tosoh Corporation), 900,000, 30,000, 4000 (Nishio Corporation))
本発明の研磨液組成物における重合体の含有量は、ナノスクラッチ等のLPD低減の観点から、好ましくは0.001重量%以上、より好ましくは0.002重量%以上、さらに好ましくは0.003重量%以上、さらにより好ましくは0.004重量%以上である。また、研磨液組成物の安定性の向上と研磨速度の向上の観点から、好ましくは0.5重量%以下、より好ましくは0.1重量%以下、さらに好ましくは0.05重量%以下、さらにより好ましくは0.02重量%以下である。 The content of the polymer in the polishing composition of the present invention is preferably 0.001% by weight or more, more preferably 0.002% by weight or more, and still more preferably 0.003% from the viewpoint of LPD reduction such as nanoscratching. % By weight or more, still more preferably 0.004% by weight or more. In addition, from the viewpoint of improving the stability of the polishing composition and improving the polishing rate, it is preferably 0.5% by weight or less, more preferably 0.1% by weight or less, still more preferably 0.05% by weight or less, More preferably, it is 0.02% by weight or less.
(研磨材)
本発明の研磨液組成物に含まれる研磨材としては、研磨用に一般に使用される砥粒であれば特に制限はないが、例えば、二酸化ケイ素、酸化アルミニウム、酸化セリウム、酸化ジルコニウム、酸化チタン、窒化ケイ素、二酸化マンガン、炭化ケイ素、酸化亜鉛、ダイヤモンド及び酸化マグネシウムを含む粒子が挙げられる。
(Abrasive)
The abrasive contained in the polishing composition of the present invention is not particularly limited as long as it is abrasive grains generally used for polishing. For example, silicon dioxide, aluminum oxide, cerium oxide, zirconium oxide, titanium oxide, Examples thereof include particles containing silicon nitride, manganese dioxide, silicon carbide, zinc oxide, diamond and magnesium oxide.
研磨材の材料の具体例としては、コロイダルシリカ、フュームドシリカ、表面修飾したシリカ等の二酸化ケイ素;α―アルミナ、γ―アルミナ、δ―アルミナ、θ―アルミナ、η―アルミナ、無定型アルミナ、フュームドアルミナ、コロイダルアルミナ等の酸化アルミニウム;酸化数が3価又は4価の酸化セリウム、結晶系が六方晶系、等軸晶系又は面心立方晶系の酸化セリウム、その他の酸化セリウム;結晶系が、単斜晶系、正方晶系、又は非晶質の酸化ジルコニウム、フュームドジルコニウム、その他の酸化ジルコニウム;一酸化チタン、三酸化チタン二チタン、二酸化チタン、フュームドチタニア、その他の酸化チタン;α―窒化ケイ素、β―窒化ケイ素、アモルファス窒化ケイ素、その他の窒化ケイ素;α―二酸化マンガン、β―二酸化マンガン、γ―二酸化マンガン、δ―二酸化マンガン、ε―二酸化マンガン、η―二酸化マンガン、その他の二酸化マンガンが挙げられる。 Specific examples of abrasive materials include colloidal silica, fumed silica, surface-modified silica and other silicon dioxide; α-alumina, γ-alumina, δ-alumina, θ-alumina, η-alumina, amorphous alumina, Aluminum oxides such as fumed alumina and colloidal alumina; trivalent or tetravalent cerium oxide, hexagonal, equiaxed or face-centered cubic cerium oxide, other cerium oxides; crystal Monoclinic, tetragonal, or amorphous zirconium oxide, fumed zirconium, other zirconium oxides; titanium monoxide, titanium trioxide, titanium dioxide, fumed titania, other titanium oxides Α-silicon nitride, β-silicon nitride, amorphous silicon nitride, other silicon nitrides; α-manganese dioxide, β-matrix dioxide Cancer, γ- manganese dioxide, δ- manganese dioxide, ε- manganese dioxide, η- manganese dioxide, other manganese dioxide and the like.
これらの研磨材の中でも、被研磨基板の表面平滑性を向上させる観点から、二酸化ケイ素系が好ましく、コロイダルシリカがより好ましい。これらの研磨材は、単独で又は2種以上を混合して用いてもよい。 Among these abrasives, from the viewpoint of improving the surface smoothness of the substrate to be polished, silicon dioxide is preferable, and colloidal silica is more preferable. These abrasives may be used alone or in admixture of two or more.
研磨材の使用形態としては、操作性の観点からスラリー状であることが好ましい。本発明の研磨液組成物に含まれる研磨材がコロイダルシリカである場合、アルカリ金属やアルカリ土類金属等によるシリコンウエハの汚染を防止する観点から、コロイダルシリカは、アルコキシシランの加水分解物から得たものであると好ましい。アルコキシシランの加水分解物から得られるシリカ粒子は、従来から公知の方法によって作製できる。 The use form of the abrasive is preferably a slurry from the viewpoint of operability. When the abrasive contained in the polishing composition of the present invention is colloidal silica, colloidal silica is obtained from a hydrolyzate of alkoxysilane from the viewpoint of preventing contamination of the silicon wafer by alkali metal or alkaline earth metal. It is preferable that Silica particles obtained from the hydrolyzate of alkoxysilane can be produced by a conventionally known method.
本発明の研磨液組成物に含まれる研磨材の平均一次粒子径は、一定の研磨速度を維持する観点から、好ましくは5nm以上、より好ましくは10nm以上、さらに好ましくは15nm以上である。また、被研磨物表面におけるスクラッチの発生を抑制する観点から、好ましくは50nm以下、より好ましくは45nm以下、さらに好ましくは40nm以下である。 From the viewpoint of maintaining a constant polishing rate, the average primary particle size of the abrasive contained in the polishing composition of the present invention is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 15 nm or more. Further, from the viewpoint of suppressing the occurrence of scratches on the surface of the object to be polished, the thickness is preferably 50 nm or less, more preferably 45 nm or less, and further preferably 40 nm or less.
特に、研磨材としてコロイダルシリカを用いた場合には、研磨速度を向上させる観点から、平均一次粒子径は、5〜50nmが好ましく、より好ましくは10〜45nm、さらに好ましくは15〜40nmである。 In particular, when colloidal silica is used as the abrasive, the average primary particle diameter is preferably 5 to 50 nm, more preferably 10 to 45 nm, and still more preferably 15 to 40 nm from the viewpoint of improving the polishing rate.
本発明の研磨液組成物における研磨材の含有量は、研磨速度の向上の観点から0.05重量%以上であると好ましく、0.1重量%以上であるとより好ましく、0.5重量%以上であるとさらに好ましい。また、研磨液組成物の安定性の向上の観点から10重量%以下であると好ましく、7.5重量%以下であるとより好ましく、5重量%以下であるとさらに好ましい。 The content of the abrasive in the polishing composition of the present invention is preferably 0.05% by weight or more, more preferably 0.1% by weight or more from the viewpoint of improving the polishing rate, and 0.5% by weight. More preferably, the above is true. Further, from the viewpoint of improving the stability of the polishing composition, it is preferably 10% by weight or less, more preferably 7.5% by weight or less, and further preferably 5% by weight or less.
研磨材の平均一次粒子径は、BET(窒素吸着)法によって算出される比表面積S(m2/g)を用いて算出される。比表面積は、例えば、実施例に記載の方法により測定できる。 The average primary particle diameter of the abrasive is calculated using the specific surface area S (m 2 / g) calculated by the BET (nitrogen adsorption) method. A specific surface area can be measured by the method as described in an Example, for example.
研磨材の会合度は、表面粗さの低減の観点から、3.0以下であると好ましく、研磨材の形状はいわゆる球型といわゆるマユ型であると好ましい。更に、表面粗さの低減と研磨速度の向上とを両立させる観点から、研磨材の会合度は、1.1〜3.0であると好ましく、研磨材の形状はいわゆるマユ型であると好ましい。研磨材の会合度は、研磨速度を向上させる観点から、1.8以上であると好ましく、2.0以上であるとより好ましい。また、表面粗さ低減の観点から、2.5以下であると好ましく、2.3以下であるとより好ましい。研磨材がコロイダルシリカである場合、その会合度は、研磨速度をより向上させる観点から、1.1〜3.0であると好ましく、1.8〜2.5であるとより好ましい。 The degree of association of the abrasive is preferably 3.0 or less from the viewpoint of reducing the surface roughness, and the shape of the abrasive is preferably a so-called spherical type and a so-called mayu type. Furthermore, from the viewpoint of achieving both reduction in surface roughness and improvement in the polishing rate, the degree of association of the abrasive is preferably 1.1 to 3.0, and the shape of the abrasive is preferably a so-called mayu type. . The degree of association of the abrasive is preferably 1.8 or more and more preferably 2.0 or more from the viewpoint of improving the polishing rate. Moreover, from a viewpoint of surface roughness reduction, it is preferable in it being 2.5 or less, and it is more preferable in it being 2.3 or less. When the abrasive is colloidal silica, the degree of association is preferably 1.1 to 3.0 and more preferably 1.8 to 2.5 from the viewpoint of further improving the polishing rate.
本発明における研磨材の会合度とは、研磨材の形状を表す係数であり、下記式により算出される。
会合度=平均二次粒子径/平均一次粒子径
研磨材の会合度の調整方法としては、特に限定されないが、例えば、特開平6−2
54383号公報、特開平11−214338号公報、特開平11−60232号公報、特開2005−060217号公報、特開2005−060219号公報等に記載の方法を採用できる。
The association degree of the abrasive in the present invention is a coefficient representing the shape of the abrasive and is calculated by the following formula.
The degree of association = average secondary particle diameter / average primary particle diameter The method for adjusting the degree of association of the abrasive is not particularly limited.
No. 54383, JP-A-11-214338, JP-A-11-60232, JP-A-2005-060217, JP-A-2005-060219, and the like can be employed.
平均二次粒子径は、動的光散乱法によって測定される値であり、例えば、実施例に記載の装置を用いて測定できる。 The average secondary particle diameter is a value measured by a dynamic light scattering method, and can be measured using, for example, the apparatus described in the examples.
(水系媒体)
本実施形態の研磨液組成物に含まれる水系媒体としては、水、または水と溶媒との混合媒体等が挙げられ、上記溶媒としては、水と混合可能な溶媒(例えば、エタノール等のアルコール)が好ましい。水系媒体としては、なかでも、水が好ましく、イオン交換水がより好ましい。
(Aqueous medium)
Examples of the aqueous medium contained in the polishing liquid composition of the present embodiment include water, a mixed medium of water and a solvent, and the solvent includes a solvent that can be mixed with water (for example, alcohol such as ethanol). Is preferred. Among these, water is preferable as the aqueous medium, and ion-exchanged water is more preferable.
本実施形態の研磨液組成物には、本発明の効果が妨げられない範囲で、さらに、水溶性高分子、塩基性化合物、pH調整剤、防腐剤、アルコール類、キレート剤、カチオン性界面活性剤、アニオン性界面活性剤、非イオン性界面活性剤および酸化剤から選ばれる少なくとも1種の任意成分が含まれていてもよい。 In the polishing composition of the present embodiment, a water-soluble polymer, a basic compound, a pH adjuster, an antiseptic, an alcohol, a chelating agent, a cationic surface activity, as long as the effects of the present invention are not hindered. At least one optional component selected from an agent, an anionic surfactant, a nonionic surfactant and an oxidizing agent may be contained.
(水溶性高分子)
水溶性高分子とは、一般に、重量平均分子量が10,000以上、好ましくは100,000以上、の水溶性基を有する高分子化合物をいう。上記水溶性基としては、例えば水酸基、カルボキシル基、カルボン酸エステル基、スルホン酸基等が挙げられる。このような水溶性高分子化合物としては、セルロース誘導体、ポリビニルアルコール、ポリエチレンオキサイド等が例示できる。セルロース誘導体としては、カルボキシメチルセルロ−ス、ヒドロキシエチルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、メチルセルロース、エチルセルロース、エチルヒドロキシエチルセルロース、およびカルボキシメチルエチルセルロース等が挙げられる。これらの水溶性高分子は任意の割合で2種以上を混合して用いてもよい。
(Water-soluble polymer)
The water-soluble polymer generally means a polymer compound having a water-soluble group having a weight average molecular weight of 10,000 or more, preferably 100,000 or more. Examples of the water-soluble group include a hydroxyl group, a carboxyl group, a carboxylic acid ester group, and a sulfonic acid group. Examples of such water-soluble polymer compounds include cellulose derivatives, polyvinyl alcohol, and polyethylene oxide. Examples of the cellulose derivative include carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and carboxymethyl ethyl cellulose. These water-soluble polymers may be used in a mixture of two or more at any ratio.
本発明の研磨液組成物に含まれる水溶性高分子としては、研磨対象の表面の濡れ性向上及び研磨された面へのパーティクル付着低減の観点から、ヒドロキシエチルセルロース、ポリビニルアルコール、およびポリエチレンオキサイドから選ばれる少なくとも1種が好ましく、ヒドロキシエチルセルロースがより好ましい。 The water-soluble polymer contained in the polishing liquid composition of the present invention is selected from hydroxyethyl cellulose, polyvinyl alcohol, and polyethylene oxide from the viewpoint of improving the wettability of the surface to be polished and reducing particle adhesion to the polished surface. At least one selected from the group consisting of hydroxyethyl cellulose is more preferable.
ヒドロキシエチルセルロースの重量平均分子量(ポリエチレングリコール換算)としては、研磨速度の向上、研磨対象の表面の濡れ性向上及び研磨された面へのパーティクル付着低減の観点から、300,000〜4,000,000が好ましく、600,000〜3,000,000がより好ましく、900,000〜2,500,000がさらに好ましい。 The weight average molecular weight (in terms of polyethylene glycol) of hydroxyethyl cellulose is 300,000 to 4,000,000 from the viewpoint of improving the polishing rate, improving the wettability of the surface to be polished and reducing the adhesion of particles to the polished surface. Is preferable, 600,000 to 3,000,000 is more preferable, and 900,000 to 2,500,000 is more preferable.
本実施形態の研磨液組成物における水溶性高分子化合物の量は、研磨速度の向上及び研磨対象の表面の濡れ性向上の観点から、好ましくは0.001〜5重量%、さらに好ましくは0.005〜2重量%、より好ましくは0.01〜0.5重量%である。 The amount of the water-soluble polymer compound in the polishing composition of the present embodiment is preferably 0.001 to 5% by weight, more preferably 0. 0%, from the viewpoint of improving the polishing rate and improving the wettability of the surface to be polished. 005 to 2% by weight, more preferably 0.01 to 0.5% by weight.
(塩基性化合物)
塩基性化合物としては、含窒素塩基性化合物、アルカリ金属およびアルカリ土類金属の、水酸化物、炭酸塩、および炭酸水素塩等が挙げられる。含窒素塩基性化合物としては、アンモニア、水酸化アンモニウム、炭酸アンモニウム、炭酸水素アンモニウム、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、N一メチルエタノールアミン、N−メチル−N,N一ジエタノ−ルアミン、N,N−ジメチルエタノールアミン、N,N−ジエチルエタノールアミン、N,N−ジブチルエタノールアミン、N−(β−アミノエチル)エタノ−ルアミン、モノイソプロパノールアミン、ジイソブロパノールアミン、およびトリイソプロパノールアミン、エチレンジアミン、ヘキサメチレンジアミン、ピペラジン・六水和物、無水ピペラジン、1−(2−アミノエチル)ピペラジン、N−メチルピペラジン、ジエチレントリアミン、および水酸化テトラメチルアンモニウムが挙げられ;アルカリ金属およびアルカリ土類金属の、水酸化物、炭酸塩、および炭酸水素塩としては、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸水素カリウム、炭酸ナトリウムおよび炭酸水素ナトリウムが挙げられる。これらの塩基性化合物は2種以上を混合して用いてもよい。本発明の研磨液組成物に含まれる塩基性化合物としては、研磨速度向上の観点から、含窒素塩基性化合物が好ましく、アンモニア、メチルアミンがより好ましい。
(Basic compound)
Examples of the basic compound include nitrogen-containing basic compounds, alkali metal and alkaline earth metal hydroxides, carbonates, bicarbonates, and the like. Nitrogen-containing basic compounds include ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine. N-methyl-N, N-diethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N- (β-aminoethyl) ethanolamine, mono Isopropanolamine, diisoblopanolamine, and triisopropanolamine, ethylenediamine, hexamethylenediamine, piperazine hexahydrate, anhydrous piperazine, 1- (2-aminoethyl) pi Razine, N-methylpiperazine, diethylenetriamine, and tetramethylammonium hydroxide; alkali metal and alkaline earth metal hydroxides, carbonates, and bicarbonates include potassium hydroxide, sodium hydroxide, Examples include potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate. Two or more of these basic compounds may be mixed and used. The basic compound contained in the polishing composition of the present invention is preferably a nitrogen-containing basic compound, more preferably ammonia or methylamine, from the viewpoint of improving the polishing rate.
本発明の研磨液組成物における塩基性化合物の含有量は、研磨速度向上の観点から、0.001重量%以上であると好ましく、0.01重量%以上であるとより好ましく、0.02重量%以上であるとさらに好ましい。また、半導体基板の腐食防止の観点から10重量%以下であると好ましく、5重量%以下であるとより好ましく、1重量%以下であるとさらに好ましい。 The content of the basic compound in the polishing composition of the present invention is preferably 0.001% by weight or more, more preferably 0.01% by weight or more from the viewpoint of improving the polishing rate, and 0.02% by weight. % Or more is more preferable. Further, from the viewpoint of preventing corrosion of the semiconductor substrate, it is preferably 10% by weight or less, more preferably 5% by weight or less, and further preferably 1% by weight or less.
(pH調整剤)
pH調整剤としては、酸性化合物等が挙げられる。酸性化合物としては、硫酸、塩酸、硝酸またはリン酸等の無機酸、酢酸、シュウ酸、コハク酸、グリコール酸、リンゴ酸、クエン酸または安息香酸等の有機酸等が挙げられる。
(PH adjuster)
Examples of pH adjusters include acidic compounds. Examples of the acidic compound include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and organic acids such as acetic acid, oxalic acid, succinic acid, glycolic acid, malic acid, citric acid and benzoic acid.
(防腐剤)
防腐剤としては、ベンザルコニウムクロライド、ベンゼトニウムクロライド、1,2−ベンズイソチアゾリン−3−オン、(5−クロロ−)2−メチル−4−イソチアゾリン−3−オン、過酸化水素、または次亜塩素酸塩等が挙げられる。
(Preservative)
Examples of preservatives include benzalkonium chloride, benzethonium chloride, 1,2-benzisothiazolin-3-one, (5-chloro-) 2-methyl-4-isothiazolin-3-one, hydrogen peroxide, or hypochlorite Examples include acid salts.
(アルコール類)
アルコール類としては、メタノール、エタノール、プロパノール、ブタノール、イソプロピルアルコール、2-メチル-2-プロパノオール、エチレングリコール、プロピレングリコール、ポリエチレングリコール、グリセリン等が挙げられる。本発明の研磨液組成物におけるアルコール類の含有量は、0.1〜5重量%が好ましい。
(Alcohols)
Examples of alcohols include methanol, ethanol, propanol, butanol, isopropyl alcohol, 2-methyl-2-propanool, ethylene glycol, propylene glycol, polyethylene glycol, and glycerin. The content of alcohol in the polishing composition of the present invention is preferably 0.1 to 5% by weight.
(キレート剤)
キレート剤としては、エチレンジアミン四酢酸、エチレンジアミン四酢酸ナトリウム、ニトリロ三酢酸、ニトリロ三酢酸ナトリウム、ニトリロ三酢酸アンモニウム、ヒドロキシエチルエチレンジアミン三酢酸、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム、トリエチレンテトラミン六酢酸、トリエチレンテトラミン六酢酸ナトリウム等が挙げられる。本発明の研磨液組成物におけるキレート剤の含有量は、0.01〜1重量%が好ましい。
(Chelating agent)
Chelating agents include: ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, nitrilotriacetic acid, sodium nitrilotriacetate, ammonium nitrilotriacetate, hydroxyethylethylenediaminetriacetic acid, sodium hydroxyethylethylenediaminetriacetate, triethylenetetraminehexaacetic acid, triethylenetetramine Examples include sodium hexaacetate. The content of the chelating agent in the polishing composition of the present invention is preferably 0.01 to 1% by weight.
(カチオン性界面活性剤)
カチオン性界面活性剤としては、例えば、脂肪族アミン塩、脂肪族アンモニウム塩等が挙げられる。
(Cationic surfactant)
Examples of the cationic surfactant include aliphatic amine salts and aliphatic ammonium salts.
(アニオン性界面活性剤)
アニオン性界面活性剤としては、例えば、脂肪酸石鹸、アルキルエーテルカルボン酸塩等のカルボン酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩等のスルホン酸塩、高級アルコール硫酸エステル塩、アルキルエーテル硫酸塩等の硫酸エステル塩、アルキルリン酸エステル等のリン酸エステル塩などが挙げられる。
(Anionic surfactant)
Examples of the anionic surfactant include fatty acid soaps, carboxylates such as alkyl ether carboxylates, sulfonates such as alkylbenzene sulfonates and alkylnaphthalene sulfonates, higher alcohol sulfates, alkyl ether sulfates. And sulfate ester salts such as alkyl phosphate esters and the like.
(非イオン性界面活性剤)
非イオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル等のエーテル型、グリセリンエステルのポリオキシエチレンエーテル等のエーテルエステル型、ポリエチレングリコール脂肪酸エステル、グリセリンエステル、ソルビタンエステル等のエステル型などが挙げられる。
(Nonionic surfactant)
Nonionic surfactants include, for example, ether types such as polyoxyethylene alkyl ether, ether ester types such as glycerin ester polyoxyethylene ether, ester types such as polyethylene glycol fatty acid ester, glycerin ester, and sorbitan ester. Can be mentioned.
(酸化剤)
酸化剤としては、過マンガン酸、ペルオキソ酸等の過酸化物、クロム酸、または硝酸、並びにこれらの塩等が挙げられる。
(Oxidant)
Examples of the oxidizing agent include peroxides such as permanganic acid and peroxo acid, chromic acid, nitric acid, and salts thereof.
本実施形態の研磨液組成物の25℃におけるpHは、特に制限されないが、研磨速度をさらに向上できることから、8.0〜12.0が好ましく、より好ましくは9.0〜11.5、さらに好ましくは9.5〜11.0である。ここで、25℃におけるpHは、pHメータ(東亜電波工業株式会社、HM−30G)を用いて測定でき、電極の研磨液組成物への浸漬後1分後の数値である。 The pH at 25 ° C. of the polishing composition of the present embodiment is not particularly limited, but is preferably 8.0 to 12.0, more preferably 9.0 to 11.5, because the polishing rate can be further improved. Preferably it is 9.5 to 11.0. Here, the pH at 25 ° C. can be measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and is a value one minute after immersion of the electrode in the polishing composition.
本発明の研磨液組成物のフィルター通液量は、下記標準試験Aにおいて、2.0g/分・cm2以上であると好ましく、ナノスクラッチ等のLPDの低減の観点から、好ましくは3.7g/分・cm2以上、より好ましくは5g/分・cm2以上、更に好ましくは10g/分・cm2以上、更に好ましくは12g/分・cm2以上である。この通液量は、研磨液組成物の粘度を低減する、研磨液組成物中の研磨材の分散を高める、研磨液組成物中の研磨材の凝集物をろ過等で除く、等の方法により増大させることができる。 The amount of filter passing through the polishing composition of the present invention is preferably 2.0 g / min · cm 2 or more in the following standard test A, and preferably 3.7 g from the viewpoint of reducing LPD such as nano scratches. / Min · cm 2 or more, more preferably 5 g / min · cm 2 or more, still more preferably 10 g / min · cm 2 or more, still more preferably 12 g / min · cm 2 or more. This liquid passing amount is reduced by the method of reducing the viscosity of the polishing liquid composition, increasing the dispersion of the abrasive in the polishing liquid composition, removing aggregates of the abrasive in the polishing liquid composition by filtration, etc. Can be increased.
(標準試験A)
(1)試験室内温度:25℃
(2)吸引圧力:−100kPa
(3)ろ過フィルター:メンブランフィルター
材質:親水性PTFE(ポリテトラフルオロエチレン)
孔径:0.5μm
厚さ:35μm
ろ過面積:17.3cm2 (直径=47mm)
メンブランフィルターとして、例えば、アドバンテック東洋社製「H050A047A」使用できる。
(4)操作:上記フィルターが装着された吸引濾過器に上記吸引圧力下、250gの研磨液組成物を2秒間で流し込み、その直後から1分間にフィルターを通過した研磨液組成物の重量を測定する。この重量を標準試験で用いたフィルターのろ過面積で除したものを通液量とする。減圧の方法は特に限定はないが、例えば、水循環式のアスピレーターを用いることができる。
(Standard test A)
(1) Test room temperature: 25 ° C
(2) Suction pressure: -100 kPa
(3) Filtration filter: membrane filter Material: hydrophilic PTFE (polytetrafluoroethylene)
Pore diameter: 0.5 μm
Thickness: 35μm
Filtration area: 17.3 cm 2 (diameter = 47 mm)
As the membrane filter, for example, “H050A047A” manufactured by Advantech Toyo Co., Ltd. can be used.
(4) Operation: 250 g of the polishing composition was poured into the suction filter equipped with the filter under the suction pressure for 2 seconds, and the weight of the polishing composition that passed through the filter was measured immediately after that for 1 minute. To do. The amount obtained by dividing this weight by the filtration area of the filter used in the standard test is defined as the flow rate. The method for reducing the pressure is not particularly limited. For example, a water circulation aspirator can be used.
なお、上記において説明した各成分の含有量は、使用時における含有量であるが、本実施形態の研磨液組成物は、その安定性が損なわれない範囲で濃縮された状態で保存および供給されてもよい。この場合、製造および輸送コストをさらに低くできる点で好ましい。濃縮液は、必要に応じて前述の水系媒体で適宜希釈して使用すればよい。 The content of each component described above is the content at the time of use, but the polishing liquid composition of the present embodiment is stored and supplied in a concentrated state as long as the stability is not impaired. May be. In this case, it is preferable in that the manufacturing and transportation costs can be further reduced. The concentrate may be used after appropriately diluted with the above-mentioned aqueous medium as necessary.
本実施形態の研磨液組成物が上記濃縮液である場合、上記一般式(1)で表される構成単位を有する重合体の含有量は、製造および輸送コストを低くする観点から、5重量%以上が好ましく、より好ましくは7重量%以上、さらに好ましくは8重量%以上である。また、濃縮液中における重合体の含有量は、分散安定性を向上させる観点から、40重量%以下が好ましく、より好ましくは35重量%以下、さらに好ましくは30重量%以下である。 When the polishing liquid composition of the present embodiment is the concentrated liquid, the content of the polymer having the structural unit represented by the general formula (1) is 5% by weight from the viewpoint of reducing the production and transportation costs. The above is preferable, more preferably 7% by weight or more, and still more preferably 8% by weight or more. Further, the content of the polymer in the concentrated liquid is preferably 40% by weight or less, more preferably 35% by weight or less, and still more preferably 30% by weight or less from the viewpoint of improving dispersion stability.
本実施形態の研磨液組成物が上記濃縮液である場合、研磨材の含有量は、製造および輸送コストを低くする観点から、5重量%以上が好ましく、より好ましくは7重量%以上、さらに好ましくは8重量%以上である。また、濃縮液中における研磨材の含有量は、分散安定性を向上させる観点から、40重量%以下が好ましく、より好ましくは35重量%以下、さらに好ましくは30重量%以下である。 When the polishing liquid composition of the present embodiment is the concentrated liquid, the content of the abrasive is preferably 5% by weight or more, more preferably 7% by weight or more, and still more preferably from the viewpoint of reducing manufacturing and transportation costs. Is 8% by weight or more. Further, the content of the abrasive in the concentrate is preferably 40% by weight or less, more preferably 35% by weight or less, and further preferably 30% by weight or less from the viewpoint of improving dispersion stability.
本実施形態の研磨液組成物が上記濃縮液である場合、水溶性高分子の含有量は、製造および輸送コストを低くする観点から、0.04重量%以上が好ましく、より好ましくは0.06重量%以上、さらに好ましくは0.1重量%以上である。また、濃縮液中における水溶性高分子の含有量は、分散安定性を向上させる観点から、5重量%以下が好ましく、より好ましくは2重量%以下、さらに好ましくは1重量%以下である。 When the polishing liquid composition of the present embodiment is the concentrated liquid, the content of the water-soluble polymer is preferably 0.04% by weight or more, more preferably 0.06, from the viewpoint of reducing manufacturing and transportation costs. % By weight or more, more preferably 0.1% by weight or more. The content of the water-soluble polymer in the concentrate is preferably 5% by weight or less, more preferably 2% by weight or less, and further preferably 1% by weight or less from the viewpoint of improving dispersion stability.
次に、本実施形態の研磨液組成物の製造方法の一例について説明する。 Next, an example of the manufacturing method of the polishing liquid composition of this embodiment is demonstrated.
本実施形態の研磨液組成物の製造方法の一例は、何ら制限されず、例えば、研磨材と、水系媒体と、上記一般式(1)で表される構成単位を有する重合体と、必要に応じて任意成分とを混合することによって調製できる。 An example of the manufacturing method of the polishing composition of the present embodiment is not limited at all, and for example, an abrasive, an aqueous medium, a polymer having a structural unit represented by the general formula (1), and necessary Accordingly, it can be prepared by mixing arbitrary components.
これらの各成分の混合順序については特に制限はなく、全ての成分を同時に混合してもよいし、任意成分として水溶性高分子を含む場合は、予め、水溶性高分子を溶解した水系媒体に研磨材を混合してもよい。研磨材の凝集等を十分に防止する観点からは、後者が好ましい。 The order of mixing these components is not particularly limited, and all the components may be mixed at the same time. In the case where a water-soluble polymer is included as an optional component, an aqueous medium in which the water-soluble polymer is dissolved in advance is used. An abrasive may be mixed. The latter is preferable from the viewpoint of sufficiently preventing the agglomeration and the like of the abrasive.
研磨材の水系媒体への分散は、例えば、ホモミキサー、ホモジナイザー、超音波分散機、湿式ボールミル、またはビーズミル等の撹拌機等を用いて行うことができる。研磨材が凝集等してできた粗大粒子が水系媒体中に含まれる場合、遠心分離やフィルターを用いたろ過等により、当該粗大粒子を除去すると好ましい。研磨材の水系媒体への分散は、水溶性高分子の存在下で行うと好ましい。 The dispersion of the abrasive in the aqueous medium can be performed using a stirrer such as a homomixer, a homogenizer, an ultrasonic disperser, a wet ball mill, or a bead mill, for example. When coarse particles produced by agglomeration of the abrasive are contained in the aqueous medium, it is preferable to remove the coarse particles by centrifugation or filtration using a filter. It is preferable to disperse the abrasive in the aqueous medium in the presence of a water-soluble polymer.
本発明の研磨液組成物は、例えば、半導体基板の製造過程における、シリコンウエハの研磨工程に用いられる。 The polishing composition of the present invention is used, for example, in a silicon wafer polishing step in the process of manufacturing a semiconductor substrate.
シリコンウエハの研磨工程には、シリコン単結晶インゴットを薄円板状にスライスすることにより得られたウエハを平面化するラッピング(粗研磨)工程と、ラッピングされたウエハをエッチングした後、ウエハ表面を鏡面化する仕上げ研磨工程とがある。本発明の研磨液組成物は、上記仕上げ研磨工程で用いられるとより好ましい。 The silicon wafer polishing process includes a lapping (rough polishing) process for flattening a wafer obtained by slicing a silicon single crystal ingot into a thin disk shape, and etching the lapped wafer. There is a finish polishing process to make a mirror surface. The polishing composition of the present invention is more preferably used in the above-described finish polishing step.
本発明の研磨液組成物は、上記シリコンウエハの研磨のみならず、アニール・ウエハ(Annealed Wafer)、エピタキシャル・ウエハ(EW:Epitaxial Wafer)、埋め込み層付エピタキシャル・ウエハ(JIW:Junction Isolated Wafer)、SOIウエハ(Silicon-on-Insulator Wafer)、誘電体分離ウエハ等の形成のための仕上げ研磨にも好適に使用できる。 The polishing composition of the present invention is not only for polishing the silicon wafer, but also annealed wafer (Annealed Wafer), epitaxial wafer (EW), epitaxial wafer with buried layer (JIW: Junction Isolated Wafer), It can also be suitably used for finish polishing for forming an SOI wafer (Silicon-on-Insulator Wafer), a dielectric separation wafer, and the like.
アニール・ウエハは、シリコンウエハを還元雰囲気中(水素、アルゴン)で熱処理してウエハ表面の結晶完全性を高めたウエハである。エピタキシャル・ウエハとは、ウエハの表面に単結晶シリコン層を気相成長させたウエハである。埋め込み層付エピタキシャル・ウエハは、露光、イオン注入、および熱拡散技術等を利用してIC用埋め込み層を形成させたウエハである。SOIウエハは、デバイスの高集積化、低消費電力化、高速化、高信頼性の実現を目指して電気絶縁性の高い酸化膜層を内部に形成させたウエハである。SOIウエハの一種である貼り合わせウエハ(DBW:Direct Bonded Wafer)は、2枚のシリコンウエハが酸化膜が介在するように貼り合わされたウエハである。SOIウエハの一種であるSIMOX(Separation by implanted oxygen)は、シリコンウエハに酸素イオンを注入して内部に酸化膜層が形成されたウエハである。 An annealed wafer is a wafer in which a silicon wafer is heat-treated in a reducing atmosphere (hydrogen, argon) to improve crystal integrity on the wafer surface. An epitaxial wafer is a wafer obtained by vapor-depositing a single crystal silicon layer on the surface of the wafer. An epitaxial wafer with a buried layer is a wafer in which a buried layer for IC is formed using exposure, ion implantation, thermal diffusion technology, and the like. The SOI wafer is a wafer in which an oxide film layer having high electrical insulation is formed inside for the purpose of realizing high integration of devices, low power consumption, high speed, and high reliability. A bonded wafer (DBW: Direct Bonded Wafer) which is a kind of SOI wafer is a wafer in which two silicon wafers are bonded so that an oxide film is interposed therebetween. SIMOX (Separation by implanted oxygen), which is a kind of SOI wafer, is a wafer in which oxygen ions are implanted into a silicon wafer and an oxide film layer is formed inside.
誘電体分離ウエハは、下記のようにして形成されたウエハである。活性基板(Active Wafer)となるウエハに、分離のための溝を作成し、溝が形成された表面を酸化する。次いで、その表面上にCVD法にて多結晶シリコン膜を形成する。次に、多結晶シリコン膜が形成された活性基板に、全表面が酸化処理された支持基板(Handle Wafer)を張り合わせた後、これらを熱処理し、2枚の基板を結合させる。その後、活性基板を、上記支持基板と向かい合う面の反対面から所定の厚さとなるまで研削、研磨する。 The dielectric separation wafer is a wafer formed as follows. A groove for separation is created on a wafer to be an active wafer, and the surface on which the groove is formed is oxidized. Next, a polycrystalline silicon film is formed on the surface by CVD. Next, a support substrate (Handle Wafer) whose entire surface is oxidized is bonded to the active substrate on which the polycrystalline silicon film is formed, and then these are heat-treated to bond the two substrates. Thereafter, the active substrate is ground and polished from the surface opposite to the surface facing the support substrate to a predetermined thickness.
<平均一次粒子径>
研磨材(コロイダルシリカ)の平均一次粒子径(nm)は、BET(窒素吸着)法によって算出される比表面積S(m2/g)を用いて下記式で算出した。
平均一次粒子径(nm)=2727/S
<Average primary particle size>
The average primary particle diameter (nm) of the abrasive (colloidal silica) was calculated by the following formula using the specific surface area S (m 2 / g) calculated by the BET (nitrogen adsorption) method.
Average primary particle diameter (nm) = 2727 / S
研磨材の比表面積は、下記の[前処理]をした後、測定サンプル約0.1gを測定セルに小数点以下4桁(0.1mgの桁)まで精量し、比表面積の測定直前に110℃の雰囲気下で30分間乾燥した後、比表面積測定装置(マイクロメリティック自動比表面積測定装置 フローソーブIII2305、島津製作所製)を用いて窒素吸着法(BET法)により測定した。 The specific surface area of the abrasive was subjected to the following [pre-treatment], and then approximately 0.1 g of a measurement sample was accurately weighed to 4 digits after the decimal point (0.1 mg digit) in the measurement cell, and 110 immediately before the measurement of the specific surface area. After drying for 30 minutes in an atmosphere at 0 ° C., measurement was carried out by a nitrogen adsorption method (BET method) using a specific surface area measuring device (Micromeritic automatic specific surface area measuring device Flowsorb III 2305, manufactured by Shimadzu Corporation).
[前処理]
(a)スラリー状の研磨材を硝酸水溶液でpH2.5±0.1に調整する。
(b)スラリー状の研磨材をシャーレにとり150℃の熱風乾燥機内で1時間乾燥させる。
(c)乾燥後、得られた試料をメノウ乳鉢で細かく粉砕する。
(d)粉砕された試料を40℃のイオン交換水に懸濁させ、1μmのメンブランフィルターで濾過する。
(e)フィルター上の濾過物を20gのイオン交換水(40℃)で5回洗浄する。
(f)濾過物が付着したフィルターをシャーレにとり、110℃の雰囲気下で4時間乾燥させる。
(g)乾燥した濾過物(砥粒)をフィルター屑が混入しないようにとり、乳鉢で細かく粉砕して測定サンプルを得た。
[Preprocessing]
(A) The slurry-like abrasive is adjusted to pH 2.5 ± 0.1 with an aqueous nitric acid solution.
(B) The slurry-like abrasive is placed in a petri dish and dried in a hot air dryer at 150 ° C. for 1 hour.
(C) After drying, the obtained sample is finely ground in an agate mortar.
(D) The pulverized sample is suspended in ion exchange water at 40 ° C. and filtered through a 1 μm membrane filter.
(E) The filtrate on the filter is washed 5 times with 20 g of ion exchange water (40 ° C.).
(F) The filter with the filtrate attached is taken in a petri dish and dried in an atmosphere of 110 ° C. for 4 hours.
(G) The dried filtrate (abrasive grains) was taken so as not to be mixed with filter waste, and finely pulverized with a mortar to obtain a measurement sample.
<平均二次粒子径>
研磨材の平均二次粒子径(nm)は、研磨材の濃度が0.5%となるように研磨材をイオン交換水に添加した後、得られた水溶液をDisposable Sizing Cuvette(ポリスチレン製 10mmセル)に下底からの高さ10mmまで入れ、動的光散乱法(装置名:ゼータサイザーNano ZS、シスメックス(株)製)を用いて測定した。
<Average secondary particle size>
The average secondary particle size (nm) of the abrasive was added to the ion-exchanged water so that the abrasive concentration was 0.5%, and the resulting aqueous solution was then treated with Disposable Sizing Cuvette (polystyrene 10 mm cell). ) To a height of 10 mm from the bottom, and measured using a dynamic light scattering method (device name: Zetasizer Nano ZS, manufactured by Sysmex Corporation).
<ポリ(N-アシルアルキレンイミン)の合成>
硫酸ジエチルと2−オキサゾリン系化合物とを脱水した酢酸エチルに溶解し、窒素雰囲気下で加熱還流し、表1の実施例1〜19に示した重合体を合成した。
<Synthesis of poly (N-acylalkylenimine)>
Diethyl sulfate and 2-oxazoline-based compound were dissolved in dehydrated ethyl acetate and heated to reflux in a nitrogen atmosphere to synthesize the polymers shown in Examples 1 to 19 in Table 1.
(1)研磨液組成物の調整
研磨材(コロイダルシリカ)、重合体、28%アンモニア水(キシダ化学(株)試薬特級)、およびイオン交換水を攪拌混合して得た研磨液組成物の濃縮液(pH10.0〜11.0)を、イオン交換水で20倍希釈して、pH10.0〜11.0の研磨液組成物を得た。上記研磨液組成物中のシリカ粒子の含有量および重合体の含有量は表1に示すとおりとした。また、各濃縮液中のアンモニアの含有量は0.4重量%とした。濃縮液の残部は、アンモニア水中の水とイオン交換水である。
(1) Preparation of polishing liquid composition Concentration of polishing liquid composition obtained by stirring and mixing polishing material (colloidal silica), polymer, 28% ammonia water (special grade of Kishida Chemical Co., Ltd.), and ion-exchanged water The liquid (pH 10.0 to 11.0) was diluted 20 times with ion-exchanged water to obtain a polishing liquid composition having a pH of 10.0 to 11.0. The content of silica particles and the content of polymer in the polishing liquid composition were as shown in Table 1. The content of ammonia in each concentrated solution was 0.4% by weight. The balance of the concentrate is water in ammonia water and ion exchange water.
(2)研磨方法
得られた研磨液組成物を用いて、下記の研磨条件で下記研磨対象を20分間研磨した。
<研磨対象>2インチシリコン片面鏡面ウエハ(二段研磨終了後のもの、厚さ0.7mm)を4cm×4cmに切断して使用
<研磨条件>
研磨機:片面研磨機MA-300(武蔵野電子(株)製、プラテン直径300mm)
研磨パッド:SUPREME RN-H(Nitta Haas製)
回転盤回転数:90r/min(線速度45m/min)
プラテン回転数:16r/min
研磨液組成物供給量:15ml/min(回転盤中心に供給)
研磨荷重:100g/cm2
研磨時間:15min
(2) Polishing method The following polishing object was polished for 20 minutes under the following polishing conditions using the obtained polishing composition.
<Polishing target> A 2-inch silicon single-sided mirror wafer (after two-stage polishing, thickness 0.7 mm) is cut into 4 cm × 4 cm and used <Polishing conditions>
Polishing machine: Single-side polishing machine MA-300 (Musashino Electronics Co., Ltd. platen diameter 300mm)
Polishing pad: SUPREME RN-H (Nita Haas)
Turntable rotation speed: 90 r / min (linear velocity 45 m / min)
Platen rotation speed: 16r / min
Polishing liquid composition supply amount: 15 ml / min (supplied to the center of the rotating disk)
Polishing load: 100 g / cm 2
Polishing time: 15 min
上記研磨条件で研磨されたウエハを、ウエハジェット洗浄機WJS−150B(エムテック(株)製)を用いて洗浄した後、乾燥させた。具体的には、イオン交換水を用いたスピンリンス(回転速度1500rpm、30秒間)、イオン交換水を用いたスクラブリンス(回転速度100rpm、60秒間)、イオン交換水を用いたスピンリンス(回転速度1500rpm、30秒間)をこの順で行った後、スピン乾燥(回転速度3000rpm、30秒間)を行った。 The wafer polished under the above polishing conditions was cleaned using a wafer jet cleaning machine WJS-150B (manufactured by MTEC Co., Ltd.) and then dried. Specifically, spin rinse using ion-exchanged water (rotation speed 1500 rpm, 30 seconds), scrub rinse using ion-exchanged water (rotation speed 100 rpm, 60 seconds), spin rinse using ion-exchanged water (rotation speed) After performing 1500 rpm for 30 seconds in this order, spin drying (rotation speed 3000 rpm, 30 seconds) was performed.
(3)評価方法
<研磨速度の評価>
実施例1〜19及び比較例1〜4の研磨液組成物を用いたときの研磨速度は、以下の方法で評価した。まず、研磨前後の各シリコンウエハの重さを計り(Sartorius社製「BP−210S」)を用いて測定し、得られた重量差をシリコンウエハの密度、面積および研磨時間で除して、単位時間当たりの片面研磨速度を求めた。なお、表1には、比較例1の研磨液組成物を用いた場合の片面研磨速度を「1.00」として、他の研磨液組成物を用いた場合の研磨速度を相対値で示した。
(3) Evaluation method <Evaluation of polishing rate>
The polishing rate when the polishing liquid compositions of Examples 1 to 19 and Comparative Examples 1 to 4 were used was evaluated by the following method. First, the weight of each silicon wafer before and after polishing was measured using “BP-210S” manufactured by Sartorius, and the obtained weight difference was divided by the density, area and polishing time of the silicon wafer to obtain a unit. The single-side polishing rate per hour was determined. In Table 1, the single-side polishing rate when the polishing liquid composition of Comparative Example 1 was used was “1.00”, and the polishing rates when other polishing liquid compositions were used were shown as relative values. .
<通液量の評価>
1.通液量の測定条件
(1)吸引圧力設定手段:水循環式アスピレーター(「CIRCULATING ASPIRATOR WJ−15」、柴田科学器械工業社製)を用い、アスピレーターと吸引濾過器との間(吸引濾過器から20cm離れた位置)に圧力計を接続して、濾過中の圧力を−100kPaに調整した。
(2)吸引濾過器:減圧濾過用フィルターホルダー(型番:KGS−47、アドバンテック東洋株式会社製)付の1L吸引瓶
(3)フィルター:メンブランフィルター(「H050A047A」、アドバンテック東洋株式会社製)材質:親水性PTFE、孔径:0.5μm、厚さ:35μm、ろ過面積:17.3cm2 (直径=47mm)
(4)通液時間:1分(300gの研磨液組成物を2秒間で上記フィルター上のファンネルに投入し終わった時点から1分)
(5)通液量:通液1分後の吸引瓶中の研磨液組成物の重量(g)をフィルターのろ過面積で除して求めた。
<Evaluation of flow rate>
1. Conditions for measuring liquid flow rate (1) Suction pressure setting means: Water circulation type aspirator ("CIRCULATING ASPIRETOR WJ-15", manufactured by Shibata Kagaku Kogyo Co., Ltd.), between the aspirator and the suction filter (20 cm from the suction filter) A pressure gauge was connected to the remote position to adjust the pressure during filtration to -100 kPa.
(2) Suction filter: 1L suction bottle with filter holder for vacuum filtration (model number: KGS-47, manufactured by Advantech Toyo Co., Ltd.) (3) Filter: membrane filter (“H050A047A”, manufactured by Advantech Toyo Co., Ltd.) Material: Hydrophilic PTFE, pore size: 0.5 μm, thickness: 35 μm, filtration area: 17.3 cm 2 (diameter = 47 mm)
(4) Liquid passing time: 1 minute (1 minute from the time when 300 g of the polishing liquid composition has been put into the funnel on the filter in 2 seconds)
(5) Amount of liquid flow: It was determined by dividing the weight (g) of the polishing liquid composition in the suction bottle 1 minute after the liquid flow by the filtration area of the filter.
表1に示すように、実施例1〜19では、比較例1〜4よりも研磨速度が高くなっており、さらに、実施例1〜19では、比較例1よりも通液量が多い。この結果から、実施例1〜19では、比較例1〜4よりも、研磨速度の確保と通液量の確保とが良好に両立されていることがわかる。 As shown in Table 1, in Examples 1 to 19, the polishing rate is higher than in Comparative Examples 1 to 4, and in Examples 1 to 19, the amount of liquid flow is larger than that in Comparative Example 1. From this result, in Examples 1-19, it turns out that ensuring of a grinding | polishing rate and ensuring of the amount of liquid flow are made compatible better than Comparative Examples 1-4.
本発明の研磨液組成物を用いれば、シリコンウエハを高速研磨でき、しかも、フィルターの目詰まりも低減できる。よって、本発明の研磨液組成物は、様々な半導体基板の製造過程で用いられる研磨液組成物として有用であり、なかでも、シリコンウエハの仕上げ研磨用の研磨液組成物として有用である。 By using the polishing composition of the present invention, a silicon wafer can be polished at a high speed, and filter clogging can be reduced. Therefore, the polishing liquid composition of the present invention is useful as a polishing liquid composition used in various semiconductor substrate manufacturing processes, and is particularly useful as a polishing liquid composition for finish polishing of silicon wafers.
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