JP5859055B2 - シリコンウェーハ研磨用組成物 - Google Patents
シリコンウェーハ研磨用組成物 Download PDFInfo
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- JP5859055B2 JP5859055B2 JP2014082951A JP2014082951A JP5859055B2 JP 5859055 B2 JP5859055 B2 JP 5859055B2 JP 2014082951 A JP2014082951 A JP 2014082951A JP 2014082951 A JP2014082951 A JP 2014082951A JP 5859055 B2 JP5859055 B2 JP 5859055B2
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- silicon wafer
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- 238000005498 polishing Methods 0.000 title claims description 287
- 239000000203 mixture Substances 0.000 title claims description 145
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 66
- 229910052710 silicon Inorganic materials 0.000 title claims description 66
- 239000010703 silicon Substances 0.000 title claims description 66
- 229920000642 polymer Polymers 0.000 claims description 79
- 239000006061 abrasive grain Substances 0.000 claims description 74
- 125000003368 amide group Chemical group 0.000 claims description 62
- 150000002894 organic compounds Chemical class 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 18
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 64
- -1 alkylol group Chemical group 0.000 description 59
- 235000012431 wafers Nutrition 0.000 description 54
- 230000009467 reduction Effects 0.000 description 29
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- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 230000000694 effects Effects 0.000 description 20
- 238000004140 cleaning Methods 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- 239000011164 primary particle Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000007517 polishing process Methods 0.000 description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 11
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 11
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 11
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000007514 bases Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000011163 secondary particle Substances 0.000 description 9
- 239000002738 chelating agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 229920003169 water-soluble polymer Polymers 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000007518 final polishing process Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 125000005702 oxyalkylene group Chemical group 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 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
- 235000017060 Arachis glabrata Nutrition 0.000 description 3
- 241001553178 Arachis glabrata Species 0.000 description 3
- 235000010777 Arachis hypogaea Nutrition 0.000 description 3
- 235000018262 Arachis monticola Nutrition 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 125000002091 cationic group Chemical group 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
- 235000008504 concentrate Nutrition 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002738 metalloids Chemical class 0.000 description 3
- 235000020232 peanut Nutrition 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 description 2
- AAYSXEMBWUMDIZ-UHFFFAOYSA-N 2-methyl-n,n-dipropylprop-2-enamide Chemical compound CCCN(CCC)C(=O)C(C)=C AAYSXEMBWUMDIZ-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 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
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical group CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products 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 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- JMCVCHBBHPFWBF-UHFFFAOYSA-N n,n-diethyl-2-methylprop-2-enamide Chemical compound CCN(CC)C(=O)C(C)=C JMCVCHBBHPFWBF-UHFFFAOYSA-N 0.000 description 2
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 2
- WHJNQEHPYYGWGL-UHFFFAOYSA-N n-(1-hydroxy-2-methylpropan-2-yl)prop-2-enamide Chemical compound OCC(C)(C)NC(=O)C=C WHJNQEHPYYGWGL-UHFFFAOYSA-N 0.000 description 2
- GVKDCYNVGQYGCX-UHFFFAOYSA-N n-(1-hydroxybutan-2-yl)-2-methylprop-2-enamide Chemical compound CCC(CO)NC(=O)C(C)=C GVKDCYNVGQYGCX-UHFFFAOYSA-N 0.000 description 2
- CJDWAHPSQSGIRR-UHFFFAOYSA-N n-(1-hydroxybutan-2-yl)prop-2-enamide Chemical compound CCC(CO)NC(=O)C=C CJDWAHPSQSGIRR-UHFFFAOYSA-N 0.000 description 2
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
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- 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
- 125000004169 (C1-C6) alkyl group Chemical group 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
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- SFRLSTJPMFGBDP-UHFFFAOYSA-N 1,2-diphosphonoethylphosphonic acid Chemical compound OP(O)(=O)CC(P(O)(O)=O)P(O)(O)=O SFRLSTJPMFGBDP-UHFFFAOYSA-N 0.000 description 1
- OTIXUSNHAKOJBX-UHFFFAOYSA-N 1-(aziridin-1-yl)ethanone Chemical compound CC(=O)N1CC1 OTIXUSNHAKOJBX-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
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- H01L21/02041—Cleaning
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
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Description
ここに開示される研磨用組成物は、下記一般式(1)で表わされる単量体aに由来する構成単位Aを主鎖に有するアミド基含有ポリマーXを含んでいる。
ここに開示される研磨用組成物は、上述したアミド基含有ポリマーXのほか、アミド基を含有しない有機化合物Yを含有する。かかる有機化合物Yは、典型的には分子量(My)が200以上であることが好ましい。また、炭素原子数が5以上(好ましくは6以上、より好ましくは10以上)である有機化合物を用いることが好ましい。このような条件を満たす有機化合物Yを特に限定することなく用いることができる。かかる有機化合物Yの一例としては、アミド基を含有しない界面活性剤もしくは水溶性ポリマーが挙げられる。
EOとPOとのブロック共重合体またはランダム共重合体において、該共重合体を構成するEOとPOとのモル比(EO/PO)は、水への溶解性や洗浄性等の観点から、1より大きいことが好ましく、2以上であることがより好ましく、3以上(例えば5以上)であることがさらに好ましい。
ここに開示される研磨用組成物は、典型的には、上記アミド基含有ポリマーのほかに水を含む。水としては、イオン交換水(脱イオン水)、純水、超純水、蒸留水等を好ましく用いることができる。使用する水は、研磨用組成物に含有される他の成分の働きが阻害されることを極力回避するため、例えば遷移金属イオンの合計含有量が100ppb以下であることが好ましい。例えば、イオン交換樹脂による不純物イオンの除去、フィルタによる異物の除去、蒸留等の操作によって水の純度を高めることができる。
ここに開示される研磨用組成物は、必要に応じて、水と均一に混合し得る有機溶剤(低級アルコール、低級ケトン等)をさらに含有してもよい。通常は、研磨用組成物に含まれる溶媒の90体積%以上が水であることが好ましく、95体積%以上(典型的には99〜100体積%)が水であることがより好ましい。
ここに開示される研磨用組成物は砥粒の存在下で用いられる。砥粒はシリコンウェーハの表面を機械的に研磨する機能を有する。砥粒はまた、ここに開示される研磨用組成物中で、該砥粒表面に吸着した上記アミド基含有ポリマーをシリコンウェーハにこすり付ける機能、あるいはシリコンウェーハに吸着した上記アミド基含有ポリマーをはがす機能を有する。これによって、シリコンウェーハ研磨促進剤による化学的研磨を調整する。なお、本明細書において「研磨用組成物は砥粒の存在下で用いられる」には、研磨用組成物に砥粒が含まれる態様が包含され得るものとする。かかる態様は、ここに開示される研磨用組成物の好適な一態様として把握される。したがって、「研磨用組成物は砥粒の存在下で用いられる」は「研磨用組成物は砥粒を含む」と換言することができる。あるいは、砥粒は、例えば研磨パッドに内包された固定砥粒の形態で用いられてもよい。
砥粒の平均二次粒子径DP2は、対象とする砥粒の水分散液を測定サンプルとして、例えば、日機装株式会社製の型式「UPA−UT151」を用いた動的光散乱法により測定することができる。測定サンプルの水分散液中の砥粒の濃度は特に限定されないが、測定精度の観点からは、砥粒の濃度は0.5重量%以下にすることが好ましく、0.2重量%以下にすることがより好ましい。
ここに開示される研磨用組成物は、典型的には、アミド基含有ポリマーX、有機化合物Yおよび水の他に、シリコンウェーハ研磨促進剤を含有する。シリコンウェーハ研磨促進剤は、研磨用組成物に添加されることによって研磨対象となる面を化学的に研磨する働きをし、研磨速度の向上に寄与する成分である。シリコンウェーハ研磨促進剤は、シリコンを化学的にエッチングする作用を有し、典型的には塩基性化合物である。研磨用組成物に含まれる塩基性化合物は、研磨用組成物のpHを増大させ、砥粒やアミド基含有ポリマーの分散状態を向上させるため、研磨用組成物の分散安定性の向上や砥粒による機械的な研磨作用の向上に役立ち得る。
ここに開示される研磨用組成物は、本発明の効果が著しく妨げられない範囲で、キレート剤、有機酸、有機酸塩、無機酸、無機酸塩、防腐剤、防カビ剤等の、研磨用組成物(典型的には、シリコンウェーハのファイナルポリシングに用いられる研磨用組成物)に用いられ得る公知の添加剤を、必要に応じてさらに含有してもよい。
防腐剤および防カビ剤の例としては、イソチアゾリン系化合物、パラオキシ安息香酸エステル類、フェノキシエタノール等が挙げられる。
ここに開示される研磨用組成物は、単結晶シリコンからなる研磨対象物(シリコンウェーハ)の研磨に用いられ得る。研磨対象物の形状は特に制限されない。ここに開示される研磨用組成物は、例えば、板状や多面体状等の、平面を有する研磨対象物の研磨、もしくは研磨対象物の端部の研磨(例えばウェーハエッジの研磨)に好ましく適用され得る。
ここに開示される研磨用組成物は、典型的には該研磨用組成物を含む研磨液の形態で研磨対象物に供給されて、その研磨対象物の研磨に用いられる。上記研磨液は、例えば、ここに開示されるいずれかの研磨用組成物を希釈(典型的には、水により希釈)して調製されたものであり得る。あるいは、該研磨用組成物をそのまま研磨液として使用してもよい。すなわち、ここに開示される技術における研磨用組成物の概念には、研磨対象物に供給されて該研磨対象物の研磨に用いられる研磨液(ワーキングスラリー)と、希釈して研磨液として用いられる濃縮液(研磨液の原液)との双方が包含される。ここに開示される研磨用組成物を含む研磨液の他の例として、該組成物のpHを調整してなる研磨液が挙げられる。
ここに開示される研磨用組成物は、研磨対象物に供給される前には濃縮された形態(すなわち、研磨液の濃縮液の形態)であってもよい。このように濃縮された形態の研磨用組成物は、製造、流通、保存等の際における利便性やコスト低減等の観点から有利である。濃縮倍率は、例えば、体積換算で2倍〜100倍程度とすることができ、通常は5倍〜50倍程度が適当である。好ましい一態様に係る研磨用組成物の濃縮倍率は10倍〜40倍であり、例えば15倍〜25倍である。
ここに開示される研磨用組成物の製造方法は特に限定されない。例えば、翼式攪拌機、超音波分散機、ホモミキサー等の周知の混合装置を用いて、研磨用組成物に含まれる各成分を混合するとよい。これらの成分を混合する態様は特に限定されず、例えば全成分を一度に混合してもよく、適宜設定した順序で混合してもよい。
ここに開示される研磨用組成物は、例えば以下の操作を含む態様で、研磨対象物の研磨に使用することができる。以下、ここに開示される研磨用組成物を用いて研磨対象物を研磨する方法の好適な一態様につき説明する。
すなわち、ここに開示されるいずれかの研磨用組成物を含む研磨液(典型的にはスラリー状の研磨液であり、研磨スラリーと称されることもある。)を用意する。上記研磨液を用意することには、研磨用組成物に濃度調整(例えば希釈)、pH調整等の操作を加えて研磨液を調製することが含まれ得る。あるいは、上記研磨用組成物をそのまま研磨液として使用してもよい。また、多剤型の研磨用組成物の場合、上記研磨液を用意することには、それらの剤を混合すること、該混合の前に1または複数の剤を希釈すること、該混合の後にその混合物を希釈すること、等が含まれ得る。
なお、上記研磨工程で使用される研磨パッドは特に限定されない。例えば、不織布タイプ、スウェードタイプ、砥粒を含むもの、砥粒を含まないもの等のいずれを用いてもよい。
ここに開示される研磨用組成物であって砥粒を含む研磨用組成物を用いて研磨された研磨物は、砥粒を含まない他は上記研磨用組成物と同じ成分を含むリンス液を用いてリンスされ得る。換言すると、砥粒を含まない他は上記研磨用組成物と同じ成分を含むリンス液を用いて上記研磨物をリンスする工程(リンス工程)を有してもよい。リンス工程により、研磨物の表面の欠陥やヘイズの原因となる砥粒等の残留物を低減させることができる。リンス工程は、ポリシング工程とポリシング工程との間に行われてもよいし、ファイナルポリシング工程の後であって後述の洗浄工程の前に行われてもよい。砥粒を含まない他は上記研磨用組成物と同じ成分を含むリンス液を用いてリンスすることにより、シリコンウェーハ表面に吸着した上記アミド基含有ポリマーの作用を阻害せず、欠陥やヘイズをさらに低減することができる。かかるリンス液は、典型的にはシリコンウェーハ研磨促進剤とアミド基含有ポリマーと水とを含むシリコンウェーハ研磨用組成物(具体的には、シリコンウェーハ研磨のリンスに用いられる組成物。リンス用組成物ともいう。)であり得る。このシリコンウェーハのリンス用組成物の組成等については、砥粒を含まない他は上述のシリコンウェーハ研磨用組成物と基本的に同じなので、ここでは説明は繰り返さない。
また、ここに開示される研磨用組成物を用いて研磨された研磨物は、典型的には、研磨後に(必要であればリンス後に)洗浄される。この洗浄は、適当な洗浄液を用いて行うことができる。使用する洗浄液は特に限定されず、例えば、半導体等の分野において一般的なSC−1洗浄液(水酸化アンモニウム(NH4OH)と過酸化水素(H2O2)と水(H2O)との混合液。以下、SC−1洗浄液を用いて洗浄することを「SC−1洗浄」という。)、SC−2洗浄液(HClとH2O2とH2Oとの混合液。)等を用いることができる。洗浄液の温度は、例えば常温〜90℃程度とすることができる。洗浄効果を向上させる観点から、50℃〜85℃程度の洗浄液を好ましく使用し得る。
(実施例1)
砥粒、水溶性ポリマー、有機化合物、アンモニア水(濃度29%)および脱イオン水を混合して、研磨用組成物の濃縮液を得た。この濃縮液を脱イオン水で20倍に希釈して、実施例1に係る研磨用組成物を調製した。
砥粒としては、平均一次粒子径35nmのコロイダルシリカを使用した。上記平均一次粒子径は、マイクロメリテックス社製の表面積測定装置、商品名「Flow Sorb II 2300」を用いて測定されたものである。
水溶性ポリマーとしては、Mwが2.5×104のN−(2−ヒドロキシエチル)アクリルアミド(以下「HEAA」と表記する。)を使用した。
有機化合物としては、Mwが9×103のPEO−PPO−PEO型のトリブロック共重合体(中心部がPPO、両端がPEO、以下「PEO−PPO−PEO」と表記する。)を使用した。
砥粒、水溶性ポリマー、有機化合物およびアンモニア水の使用量は、研磨用組成物中における砥粒の含有量が0.46%となり、水溶性ポリマーの含有量が0.015%となり、有機化合物の含有量が0.0025%となり、アンモニア(NH3)の含有量が0.010%となる量とした。
組成物中に含まれるHEAAの含有量を0.008%とした他は実施例1と同様にして、本例に係る研磨用組成物を調製した。
分子量が378のポリオキシエチレン(エチレンオキサイド付加モル数5)デシルエーテル(以下、「C10PEO5」)を使用し、組成物中に含まれるC10PEO5の含有量を0.0001%とした他は実施例1と同様にして、本例に係る研磨用組成物を調製した。
Mwが1.2×104のポリビニルアルコール(ビニルアルコール単位80モル%、ヘキサン酸ビニル単位20モル%;以下、「PVA」)を使用し、組成物中に含まれるPVAの含有量を0.005%、HEAAの含有量を0.005%とした他は実施例1と同様にして、本例に係る研磨用組成物を調製した。
PEO−PPO−PEOを用いなかったこと以外は実施例1と同様にして、本例に係る研磨用組成物を調製した。
PEO−PPO−PEOに代えて、ポリビニルピロリドン(PVP、Mw4.5×104)を使用した他は実施例1と同様にして、本例に係る研磨用組成物を調製した。
HEAAに代えてヒドロキシエチルセルロース(HEC、Mw2.5×105)を使用した他は実施例1と同様にして、本例に係る研磨用組成物を調製した。
各例に係る研磨用組成物をそのまま研磨液として使用して、シリコンウェーハの表面を下記の条件で研磨した。シリコンウェーハとしては、粗研磨を行い直径が300mm、伝導型がP型、結晶方位が<100>、抵抗率が0.1Ω・cm以上100Ω・cm未満であるものを、研磨スラリー(株式会社フジミインコーポレーテッド製、商品名「GLANZOX 2100」)を用いて予備研磨を行うことにより表面粗さ0.1nm〜10nmに調整して使用した。
研磨機:株式会社岡本工作機械製作所製の枚葉研磨機、型式「PNX−332B」
研磨テーブル:上記研磨機の有する3テーブルのうち後段の2テーブルを用いて、予備研磨後のファイナル研磨1段目および2段目を実施した。
(以下の条件は各テーブル同一である。)
研磨荷重:15kPa
定盤回転数:30rpm
ヘッド回転数:30rpm
研磨時間:2分
研磨液の温度:20℃
研磨液の供給速度:2.0リットル/分(掛け流し使用)
研磨後のシリコンウェーハを、NH4OH(29%):H2O2(31%):脱イオン水(DIW)=1:3:30(体積比)の洗浄液を用いて洗浄した(SC−1洗浄)。より具体的には、周波数950kHzの超音波発振器を取り付けた洗浄槽を2つ用意し、それら第1および第2の洗浄槽の各々に上記洗浄液を収容して60℃に保持し、研磨後のシリコンウェーハを第1の洗浄槽に6分、その後超純水と超音波によるリンス槽を経て、第2の洗浄槽に6分、それぞれ上記超音波発振器を作動させた状態で浸漬した。
洗浄後のシリコンウェーハ表面につき、ケーエルエー・テンコール社製のウェーハ検査装置、商品名「Surfscan SP2」を用いて、DWOモードでヘイズ(ppm)を測定した。得られた結果を、比較例1のヘイズ値を100%とする相対値に換算して表1に示した。
研磨用組成物の濾過性を次のように評価した。すなわち、各例に係る研磨用組成物(すなわち、研磨用組成物の濃縮液を20倍に希釈した研磨用組成物)を、温度25℃、濾過差圧50kPaの条件で吸引濾過した。フィルタとしては、日本ポール社製のディスクフィルタ、商品名「ウルチポア(登録商標)N66」(直径47mm、定格濾過精度0.2μm)を使用した。上記フィルタを通過する研磨用組成物の流れが止まるまでに該フィルタを通過した研磨用組成物の体積から、以下の2水準で濾過性を評価した。得られた結果を表1の「濾過性」の欄に示した。
A:フィルタを通過した研磨用組成物の体積が200mL以上。
C:フィルタを通過した研磨用組成物の体積が200mL未満。
Claims (8)
- 砥粒の存在下で用いられ、単結晶シリコンからなるシリコンウェーハの研磨に用いられるシリコンウェーハ研磨用組成物であって、
シリコンウェーハ研磨促進剤と、
アミド基含有ポリマーXと、
アミド基を含有しない有機化合物Yと、
水と
を含み、
前記アミド基含有ポリマーXは、下記一般式(1):
前記アミド基含有ポリマーXの分子量Mxと前記有機化合物Yの分子量Myとの関係が次式:
200≦My<Mx;
を満たす、シリコンウェーハ研磨用組成物。 - 前記アミド基含有ポリマーXの分子量Mxに対する前記有機化合物Yの分子量Myの比(My/Mx)が0.5より小さい、請求項1に記載のシリコンウェーハ研磨用組成物。
- 前記アミド基含有ポリマーXの分子量Mxは、5×104未満である、請求項1または2に記載のシリコンウェーハ研磨用組成物。
- 前記アミド基含有ポリマーXはノニオン性である、請求項1から3のいずれか一項に記載のシリコンウェーハ研磨用組成物。
- 前記一般式(1)中のR1は水素原子またはメチル基である、請求項1から4のいずれか一項に記載のシリコンウェーハ研磨用組成物。
- 前記一般式(1)中のR2,R3は、同じかまたは異なり、いずれも水素原子、炭素原子数1〜3のアルキル基、アルキロール基、アルコキシアルキル基またはアセチル基である(ただし、R2,R3の両方が水素原子であるものは除く。)、請求項1から5のいずれか一項に記載のシリコンウェーハ研磨用組成物。
- 前記砥粒はシリカ粒子である、請求項1から6のいずれか一項に記載のシリコンウェーハ研磨用組成物。
- pHが9.5〜12.0である、請求項1から7のいずれか一項に記載のシリコンウェーハ研磨用組成物。
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