JP4501694B2 - Additive for CMP abrasives - Google Patents
Additive for CMP abrasives Download PDFInfo
- Publication number
- JP4501694B2 JP4501694B2 JP2005007242A JP2005007242A JP4501694B2 JP 4501694 B2 JP4501694 B2 JP 4501694B2 JP 2005007242 A JP2005007242 A JP 2005007242A JP 2005007242 A JP2005007242 A JP 2005007242A JP 4501694 B2 JP4501694 B2 JP 4501694B2
- Authority
- JP
- Japan
- Prior art keywords
- cerium oxide
- dispersant
- weight
- polishing
- slurry
- 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 - Lifetime
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- 239000000654 additive Substances 0.000 title claims description 108
- 230000000996 additive effect Effects 0.000 title claims description 107
- 239000003082 abrasive agent Substances 0.000 title claims description 23
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 202
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 202
- 238000005498 polishing Methods 0.000 claims description 168
- 239000002270 dispersing agent Substances 0.000 claims description 136
- 239000002002 slurry Substances 0.000 claims description 133
- 239000002245 particle Substances 0.000 claims description 98
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 47
- -1 amine salt Chemical class 0.000 claims description 45
- 229920000642 polymer Polymers 0.000 claims description 44
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 41
- 229920002125 Sokalan® Polymers 0.000 claims description 32
- 239000004584 polyacrylic acid Substances 0.000 claims description 32
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 150000003863 ammonium salts Chemical class 0.000 claims description 22
- 229920000058 polyacrylate Polymers 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 13
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 24
- 239000004065 semiconductor Substances 0.000 description 24
- 238000002955 isolation Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000006748 scratching Methods 0.000 description 6
- 230000002393 scratching effect Effects 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- KHSBAWXKALEJFR-UHFFFAOYSA-H cerium(3+);tricarbonate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O KHSBAWXKALEJFR-UHFFFAOYSA-H 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- RZRILSWMGXWSJY-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;sulfuric acid Chemical compound OS(O)(=O)=O.OCCN(CCO)CCO RZRILSWMGXWSJY-UHFFFAOYSA-N 0.000 description 1
- HVYJSOSGTDINLW-UHFFFAOYSA-N 2-[dimethyl(octadecyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O HVYJSOSGTDINLW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- JZKFHQMONDVVNF-UHFFFAOYSA-N dodecyl sulfate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCCCCCCOS(O)(=O)=O JZKFHQMONDVVNF-UHFFFAOYSA-N 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 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 1
- 229940100608 glycol distearate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 1
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 239000001816 polyoxyethylene sorbitan tristearate Substances 0.000 description 1
- 235000010988 polyoxyethylene sorbitan tristearate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical group Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Description
本発明は、半導体素子製造技術に使用されるＣＭＰ研磨剤用添加液に関し、より詳しくは、基板表面の平坦化工程、特に、層間絶縁膜の平坦化工程、シャロー・トレンチ分離の形成工程等において使用されるＣＭＰ研磨剤用添加液に関する。 The present invention relates to an additive solution for a CMP abrasive used in semiconductor element manufacturing technology, and more specifically, in a substrate surface planarization process, particularly in an interlayer insulating film planarization process, shallow trench isolation formation process, and the like. The present invention relates to an additive solution for CMP abrasive used.
現在の超々大規模集積回路では、実装密度を高める傾向にあり、種々の微細加工技術が研究、開発されている。既に、デザインルールは、サブハーフミクロンのオーダーになっている。このような厳しい微細化の要求を満足するために開発されている技術の一つにＣＭＰ（ケミカルメカニカルポリッシング）技術がある。この技術は、半導体装置の製造工程において、露光を施す層を完全に平坦化し、露光技術の負担を軽減し、歩留まりを安定させることができるため、例えば、層間絶縁膜の平坦化、シャロー・トレンチ分離等を行う際に必須となる技術である。 In the present ultra-large scale integrated circuit, there is a tendency to increase the mounting density, and various fine processing techniques are being researched and developed. Already, the design rules are on the order of sub-half microns. One of the techniques that have been developed in order to satisfy such demands for strict miniaturization is a CMP (chemical mechanical polishing) technique. Since this technology can completely planarize the layer to be exposed in the manufacturing process of the semiconductor device, reduce the burden of the exposure technology, and stabilize the yield, for example, planarization of the interlayer insulating film, shallow trench This technique is essential when performing separation or the like.
従来、半導体装置の製造工程において、プラズマ−ＣＶＤ（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ、化学的蒸着法）、低圧−ＣＶＤ等の方法で形成される酸化珪素絶縁膜等無機絶縁膜層を平坦化するためのＣＭＰ研磨剤として、コロイダルシリカ系の研磨剤が一般的に検討されていた。コロイダルシリカ系の研磨剤は、シリカ粒子を四塩化珪酸を熱分解する等の方法で粒成長させ、ｐＨ調整を行って製造している。しかしながら、この様な研磨剤は無機絶縁膜の研磨速度が十分な速度をもたず、実用化には低研磨速度を改善する必要があるという技術課題があった。 Conventionally, CMP polishing for planarizing an inorganic insulating film layer such as a silicon oxide insulating film formed by a method such as plasma-CVD (Chemical Vapor Deposition) or low-pressure CVD in a manufacturing process of a semiconductor device. Colloidal silica-based abrasives have been generally studied as agents. Colloidal silica-based abrasives are produced by growing silica particles by a method such as thermal decomposition of tetrachlorosilicic acid and adjusting pH. However, such a polishing agent has a technical problem that the polishing rate of the inorganic insulating film does not have a sufficient speed, and it is necessary to improve the low polishing rate for practical use.
デザインルール０．５μｍ以上の世代では、集積回路内の素子分離にＬＯＣＯＳ（シリコン局所酸化）が用いられていた。その後さらに加工寸法が微細化すると素子分離幅の狭い技術が要求され、シャロー・トレンチ分離が用いられつつある。シャロー・トレンチ分離では、基板上に成膜した余分の酸化珪素膜を除くためにＣＭＰが使用され、研磨を停止させるために、酸化珪素膜の下に研磨速度の遅いストッパ膜が形成される。ストッパ膜には窒化珪素などが使用され、酸化珪素膜とストッパ膜との研磨速度比が大きいことが望ましい。従来のコロイダルシリカ系の研磨剤は、上記の酸化珪素膜とストッパ膜の研磨速度比が３程度と小さく、シャロー・トレンチ分離用としては実用に耐える特性を有していなかった。
一方、フォトマスクやレンズ等のガラス表面研磨剤として、酸化セリウム研磨剤が用いられている。酸化セリウム粒子はシリカ粒子やアルミナ粒子に比べ硬度が低く、したがって、研磨表面に傷が入りにくいことから、仕上げ鏡面研磨に有用である。しかしながら、ガラス表面研磨用酸化セリウム研磨剤にはナトリウム塩を含む分散剤を使用しているため、そのまま半導体用研磨剤として適用することはできない。
In generations with a design rule of 0.5 μm or more, LOCOS (silicon local oxidation) was used for element isolation in an integrated circuit. Thereafter, when the processing dimension is further reduced, a technology with a narrow element isolation width is required, and shallow trench isolation is being used. In shallow trench isolation, CMP is used to remove an excess silicon oxide film formed on the substrate, and a stopper film having a low polishing rate is formed under the silicon oxide film in order to stop polishing. Silicon nitride or the like is used for the stopper film, and it is desirable that the polishing rate ratio between the silicon oxide film and the stopper film is large. Conventional colloidal silica-based abrasives have a polishing rate ratio of the above-described silicon oxide film and stopper film as small as about 3, and have no practical characteristics for shallow trench isolation.
On the other hand, a cerium oxide abrasive is used as a glass surface abrasive for photomasks and lenses. Cerium oxide particles have a lower hardness than silica particles and alumina particles, and therefore are less likely to scratch the polished surface, and are useful for finish mirror polishing. However, since a cerium oxide abrasive for polishing glass surfaces uses a dispersant containing a sodium salt, it cannot be directly applied as an abrasive for semiconductors.
本発明の目的は、酸化珪素絶縁膜等の被研磨面を、傷なく、高速に研磨することが可能なＣＭＰ研磨剤を提供することにある。
本発明の他の目的は、上記の発明に加えて、酸化珪素絶縁膜等の被研磨面を、被研磨面にナトリウムイオン等のアルカリ金属汚染をせずに、傷なく、高速に研磨することが可能なＣＭＰ研磨剤を提供することにある。
本発明の他の目的は、上記の発明に加えて、酸化珪素絶縁膜研磨速度と窒化珪素絶縁膜研磨速度の比を大きくすることができるＣＭＰ研磨剤を提供することにある。
本発明の他の目的は、酸化珪素絶縁膜等の被研磨面を、被研磨面にナトリウムイオン等のアルカリ金属汚染をせずに、傷なく、高速に研磨することが可能で、酸化セリウムスラリーの保存安定性を改良したＣＭＰ研磨剤を提供することにある。
本発明の他の目的は、上記の発明に加えて、酸化珪素絶縁膜等の被研磨面を、被研磨面にナトリウムイオン等のアルカリ金属汚染をせずに、傷なく、高速に研磨することが可能で、酸化珪素絶縁膜研磨速度と窒化珪素絶縁膜研磨速度の比を５０以上にするＣＭＰ研磨剤を提供することにある。
本発明の他の目的は、上記のＣＭＰ研磨剤において保存安定性を改良するために用いられるＣＭＰ研磨剤用添加液を提供することにある。
本発明の他の目的は、基板の被研磨面の平坦性を改良するために用いられるＣＭＰ研磨剤用添加液を提供することにある。
本発明の他の目的は、基板の被研磨面を、傷なく、研磨することが可能な基板の研磨方法を提供することにある。
本発明の他の目的は、酸化珪素絶縁膜等の被研磨面を、傷なく、高速に研磨することが可能で、酸化珪素膜研磨速度と窒化珪素膜研磨速度の比率を５０以上にできる基板の研磨方法を提供することにある。
An object of the present invention is to provide a CMP polishing agent capable of polishing a surface to be polished such as a silicon oxide insulating film at a high speed without scratching.
In addition to the above-described invention, another object of the present invention is to polish a surface to be polished such as a silicon oxide insulating film at high speed without scratching the surface to be polished without causing alkali metal contamination such as sodium ions. It is an object of the present invention to provide a CMP abrasive capable of performing
Another object of the present invention is to provide a CMP polishing agent capable of increasing the ratio of the silicon oxide insulating film polishing rate to the silicon nitride insulating film polishing rate in addition to the above invention.
Another object of the present invention is to polish a surface to be polished such as a silicon oxide insulating film at a high speed without scratching the surface to be polished without causing alkali metal contamination such as sodium ions. An object of the present invention is to provide a CMP abrasive having improved storage stability.
In addition to the above-described invention, another object of the present invention is to polish a surface to be polished such as a silicon oxide insulating film at high speed without scratching the surface to be polished without causing alkali metal contamination such as sodium ions. An object of the present invention is to provide a CMP polishing agent capable of providing a ratio of a silicon oxide insulating film polishing rate to a silicon nitride insulating film polishing rate of 50 or more.
Another object of the present invention is to provide an additive solution for a CMP abrasive used for improving storage stability in the above-described CMP abrasive.
Another object of the present invention is to provide an additive solution for CMP abrasive used for improving the flatness of the surface to be polished of a substrate.
Another object of the present invention is to provide a substrate polishing method capable of polishing a surface to be polished of a substrate without scratching.
Another object of the present invention is to provide a substrate capable of polishing a surface to be polished such as a silicon oxide insulating film at a high speed without scratching and capable of increasing the ratio of the silicon oxide film polishing rate to the silicon nitride film polishing rate to 50 or more. A polishing method is provided.
本発明は、次のものに関する。
（１）酸化セリウム粒子、分散剤及び水を含む酸化セリウムスラリー並びに分散剤と水を含む添加液からなるＣＭＰ研磨剤。
（２）酸化セリウムスラリー及び添加液のそれぞれに含まれる分散剤が、高分子分散剤であり、アクリル酸アンモニウム塩を共重合成分とした重合体である（１）のＣＭＰ研磨剤。
（３）酸化セリウムスラリー及び添加液のそれぞれに含まれる分散剤が、高分子分散剤であり、ポリアクリル酸アンモニウム塩又はポリアクリル酸アミン塩である（１）のＣＭＰ研磨剤。
（４）高分子分散剤の重量平均分子量が１００〜５０，０００である（２）又は（３）のＣＭＰ研磨剤。
（５）酸化セリウムスラリー中の分散剤の含有量が酸化セリウム粒子１００重量部に対して０．０１〜２．０重量部で、酸化セリウム粒子の含有量が酸化セリウムスラリーに対して０．３〜４０重量％である（１）のＣＭＰ研磨剤。
（６）酸化セリウムスラリーのｐＨが６〜１０である（１）〜（５）のいずれかのＣＭＰ研磨剤。
（７）酸化珪素膜研磨速度と窒化珪素膜研磨速度の比が５０以上である（１）〜（６）いずれかのＣＭＰ研磨剤。
（８）分散剤と水を含むＣＭＰ研磨剤用添加液。
（９）分散剤の含有量が１〜１０重量％である（８）のＣＭＰ研磨剤用添加液。
（１０）分散剤がポリアクリル酸アンモニウム塩又はポリアクリル酸アミン塩である（９）のＣＭＰ研磨剤用添加液。
（１１）ポリアクリル酸アンモニウム塩又はポリアクリル酸アミン塩が重量平均分子量が１，０００〜１００，０００である（９）のＣＭＰ研磨剤用添加液。
（１２）ポリアクリル酸アンモニウム塩又はポリアクリル酸アミン塩の分子量分布が（重量平均分子量／数平均分子量）が１．００５〜１．３００である（１１）のＣＭＰ研磨剤用添加液。
（１３）ポリアクリル酸アンモニウム塩又はポリアクリル酸アミン塩の塩を構成していないフリーのアンモニア又はアミンの割合が１０モル％以下である（１０）のＣＭＰ研磨剤用添加液。
（１４）添加液のｐＨが４〜８である（１０）のＣＭＰ研磨剤用添加液。
（１５）添加液の粘度が１．２０〜２．５０ｍＰａ・ｓである（１０）のＣＭＰ研磨剤用添加液。
（１６）被研磨膜を形成した基板を研磨定盤の研磨布に押しあて加圧し、（１）〜（７）のいずれかのＣＭＰ研磨剤を被研磨膜と研磨布との間に供給しながら、基板と研磨定盤を動かして被研磨膜を研磨することを特徴とする基板の研磨方法。
（１７）少なくとも酸化珪素膜又は窒化珪素膜が形成された基板を研磨する（１６）の基板の研磨方法。
The present invention relates to the following.
(1) A CMP abrasive comprising a cerium oxide slurry containing cerium oxide particles, a dispersant and water, and an additive liquid containing a dispersant and water.
(2) The CMP polishing slurry according to (1), wherein the dispersant contained in each of the cerium oxide slurry and the additive liquid is a polymer dispersant and a polymer having an ammonium acrylate salt as a copolymerization component.
(3) The CMP polishing slurry according to (1), wherein the dispersant contained in each of the cerium oxide slurry and the additive solution is a polymer dispersant and is a polyacrylic acid ammonium salt or a polyacrylic acid amine salt.
(4) The CMP polishing slurry according to (2) or (3), wherein the polymer dispersant has a weight average molecular weight of 100 to 50,000.
(5) The content of the dispersant in the cerium oxide slurry is 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the cerium oxide particles, and the content of the cerium oxide particles is 0.3 with respect to the cerium oxide slurry. (1) CMP abrasive | polishing agent which is -40weight%.
(6) The CMP abrasive | polishing agent in any one of (1)-(5) whose pH of a cerium oxide slurry is 6-10.
(7) The CMP abrasive | polishing agent in any one of (1)-(6) whose ratio of a silicon oxide film polishing rate and a silicon nitride film polishing rate is 50 or more.
(8) An additive solution for CMP abrasives containing a dispersant and water.
(9) The additive solution for CMP polishing slurry according to (8), wherein the content of the dispersant is 1 to 10% by weight.
(10) The additive for CMP polishing slurry according to (9), wherein the dispersant is polyacrylic acid ammonium salt or polyacrylic acid amine salt.
(11) The additive liquid for CMP polishing slurry according to (9), wherein the polyacrylic acid ammonium salt or the polyacrylic acid amine salt has a weight average molecular weight of 1,000 to 100,000.
(12) The additive solution for CMP polishing slurry according to (11), wherein the polyacrylic acid ammonium salt or the polyacrylic acid amine salt has a molecular weight distribution (weight average molecular weight / number average molecular weight) of from 1.005 to 1.300.
(13) The additive solution for CMP polishing slurry according to (10), wherein the proportion of free ammonia or amine that does not constitute a polyacrylic acid ammonium salt or a polyacrylic acid amine salt is 10 mol% or less.
(14) The additive solution for CMP polishing slurry according to (10), wherein the pH of the additive solution is 4 to 8.
(15) The additive liquid for CMP polishing slurry according to (10), wherein the viscosity of the additive liquid is 1.20 to 2.50 mPa · s.
(16) The substrate on which the film to be polished is formed is pressed against the polishing cloth of the polishing platen and pressed, and the CMP abrasive of any one of (1) to (7) is supplied between the film to be polished and the polishing cloth. A method for polishing a substrate, comprising moving the substrate and a polishing surface plate to polish a film to be polished.
(17) The substrate polishing method according to (16), wherein the substrate on which at least the silicon oxide film or the silicon nitride film is formed is polished.
本発明のＣＭＰ研磨剤は、酸化珪素膜等の被研磨面を、傷なく、高速に研磨することに優れ、半導体素子製造技術に使用される研磨方法、特にシャロー・トレンチ分離用の基板の研磨方法に好適である。
本発明のＣＭＰ研磨剤は、また、被研磨面にナトリウムイオン等のアルカリ金属汚染をしない点、酸化珪素膜研磨速度／窒化珪素膜研磨速度の比を大きくすることができる点に優れる。
本発明のＣＭＰ研磨剤は、酸化セリウムスラリーの保存安定性を改善することができ、半導体素子製造技術に使用される研磨方法に好適である。
本発明の基板の研磨方法は、酸化珪素膜等の被研磨面を、傷なく、高速に研磨することに優れ、半導体素子製造技術に使用される研磨方法に好適である。
The CMP abrasive | polishing agent of this invention is excellent in grinding | polishing to-be-polished surfaces, such as a silicon oxide film, without a flaw, and is excellent in the grinding | polishing method used for a semiconductor element manufacturing technique, especially the board | substrate for shallow trench isolation | separation Suitable for the method.
The CMP polishing agent of the present invention is also excellent in that the surface to be polished is not contaminated with alkali metal such as sodium ions, and the ratio of the silicon oxide film polishing rate / silicon nitride film polishing rate can be increased.
The CMP abrasive | polishing agent of this invention can improve the storage stability of a cerium oxide slurry, and is suitable for the grinding | polishing method used for a semiconductor element manufacturing technique.
The substrate polishing method of the present invention is excellent in polishing a surface to be polished such as a silicon oxide film at high speed without scratches, and is suitable for a polishing method used in a semiconductor element manufacturing technique.
一般に酸化セリウムは、炭酸塩、硝酸塩、硫酸塩、しゅう酸塩のセリウム化合物を酸化することによって得られる。ＴＥＯＳ−ＣＶＤ法等で形成される酸化珪素膜の研磨に使用する酸化セリウム研磨剤は、一次粒子径が大きく、単結晶の酸化セリウム粒子が用いられているが、研磨傷が入りやすい傾向がある。そこで、本発明で用いる酸化セリウム粒子は、その製造方法を限定するものではないが、５ｎｍ以上３００ｎｍ以下の単結晶の粒子が集合した多結晶であることが好ましい。また、半導体チップ研磨に使用することから、アルカリ金属及びハロゲン類の含有率は酸化セリウム粒子中１０ｐｐｍ以下に抑えることが好ましい。 In general, cerium oxide is obtained by oxidizing a cerium compound of carbonate, nitrate, sulfate, or oxalate. The cerium oxide abrasive used for polishing a silicon oxide film formed by TEOS-CVD or the like has a large primary particle size and single crystal cerium oxide particles are used, but there is a tendency that polishing scratches are likely to occur. . Therefore, although the production method of the cerium oxide particles used in the present invention is not limited, it is preferable that the cerium oxide particles are polycrystalline in which single crystal particles of 5 nm to 300 nm are aggregated. Moreover, since it uses for semiconductor chip grinding | polishing, it is preferable to suppress the content rate of an alkali metal and halogens to 10 ppm or less in a cerium oxide particle.
本発明において、酸化セリウム粉末を作製する方法として焼成または過酸化水素等による酸化法が使用できる。焼成温度は３５０℃以上９００℃以下が好ましい。このときの原料としては、炭酸セリウムが好ましい。 In the present invention, as a method for producing the cerium oxide powder, firing or oxidation using hydrogen peroxide or the like can be used. The firing temperature is preferably 350 ° C. or higher and 900 ° C. or lower. As a raw material at this time, cerium carbonate is preferable.
上記の方法により製造された酸化セリウム粒子は凝集しているため、機械的に粉砕することが好ましい。粉砕方法として、ジェットミル等による乾式粉砕や遊星ビーズミル等による湿式粉砕方法が好ましい。 Since the cerium oxide particles produced by the above method are agglomerated, it is preferably mechanically pulverized. As the pulverization method, a dry pulverization method such as a jet mill or a wet pulverization method such as a planetary bead mill is preferable.
本発明における酸化セリウムスラリーは、例えば、上記の特徴を有する酸化セリウム粒子と酸化セリウム粒子の水への分散剤と水からなる組成物を分散させることによって得られる。ここで、酸化セリウム粒子の含有量に制限はないが、分散液の取り扱いやすさから０．３〜４０重量％が好ましく、０．５〜２０重量％の範囲がより好ましい。また、酸化セリウムスラリーと添加液を混合したときのＣＭＰ研磨剤中の酸化セリウム粒子の含有量は、０．０１〜１０重量％が好ましく、０．１〜５重量％がより好ましい。 The cerium oxide slurry in the present invention can be obtained, for example, by dispersing a composition comprising cerium oxide particles having the above characteristics, a dispersant for cerium oxide particles in water, and water. Here, although there is no restriction | limiting in content of a cerium oxide particle, 0.3 to 40 weight% is preferable from the ease of handling of a dispersion liquid, and the range of 0.5 to 20 weight% is more preferable. Moreover, 0.01-10 weight% is preferable and, as for content of the cerium oxide particle in CMP abrasive | polishing agent when mixing a cerium oxide slurry and an addition liquid, 0.1-5 weight% is more preferable.
分散剤としては、高分子分散剤、水溶性陰イオン性界面活性剤、水溶性非イオン性界面活性剤、水溶性陽イオン性界面活性剤及び水溶性両性界面活性剤から選ばれる１種又は２種以上の化合物が使用される。半導体チップ研磨に使用することから、分散剤中のナトリウムイオン、カリウムイオン等のアルカリ金属及びハロゲン、イオウの含有率は１０ｐｐｍ以下に抑えることが好ましい。 As the dispersant, one or two selected from a polymer dispersant, a water-soluble anionic surfactant, a water-soluble nonionic surfactant, a water-soluble cationic surfactant and a water-soluble amphoteric surfactant. More than one compound is used. Since it is used for semiconductor chip polishing, the content of alkali metals such as sodium ions and potassium ions, halogens and sulfur in the dispersant is preferably suppressed to 10 ppm or less.
高分子分散剤としては、アクリル酸、メタクリル酸、マレイン酸等の不飽和カルボン酸の重合体又はそのアンモニウム塩、アミン塩；アクリル酸、メタクリル酸、マレイン酸等の不飽和カルボン酸と、アクリル酸メチル、アクリル酸エチル等のアクリル酸アルキル、アクリル酸ヒドロキシエチル等のアクリル酸ヒドロキシアルキル、メタクリル酸メチル、メタクリル酸エチル等のメタクリル酸アルキル、メタクリル酸ヒドロキシエチル等のメタクリル酸ヒドロキシアルキル、酢酸ビニル、ビニルアルコール等の共重合性単量体との共重合体、そのアンモニウム塩又はアミン塩等がある。これらの重合体又は共重合体において不飽和カルボン酸は重合前にアンモニウム塩とされていてもよい。また、これらの重合体又は共重合体において不飽和カルボン酸の割合は、１〜１００モル％であることが好ましく、特に、１０〜１００モル％であることが好ましい。 Polymer dispersing agents include polymers of unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid, or ammonium salts and amine salts thereof; unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid; and acrylic acid. Alkyl acrylates such as methyl and ethyl acrylate, hydroxyalkyl acrylates such as hydroxyethyl acrylate, alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, hydroxyalkyl methacrylates such as hydroxyethyl methacrylate, vinyl acetate, vinyl Examples thereof include a copolymer with a copolymerizable monomer such as alcohol, an ammonium salt or an amine salt thereof. In these polymers or copolymers, the unsaturated carboxylic acid may be converted to an ammonium salt before polymerization. Moreover, it is preferable that the ratio of unsaturated carboxylic acid in these polymers or copolymers is 1-100 mol%, and it is especially preferable that it is 10-100 mol%.
分散剤としては、アクリル酸アンモニウム塩を共重合成分とした重合体、ポリアクリル酸アンモニウム、ポリアクリル酸アミン塩が好ましい。ポリアクリル酸アンモニウム又はポリアクリル酸アミン塩の重量平均分子量は、好ましくは１，０００〜１００，０００、より好ましくは３，０００〜６０，０００、さらに好ましくは１０，０００〜４０，０００である。重量平均分子量が１，０００未満であると酸化セリウム粒子が凝集する傾向があり、１００，０００を超えると研磨速度比が低下する傾向がある。また、ポリアクリル酸アンモニウム又はポリアクリル酸アミン塩の分子量分布（重量平均分子量／数平均分子量）は、好ましくは１．００５〜１．３００、より好ましくは１．１００〜１．２５０、さらに好ましくは１．１５０〜１．２００である。分子量分布が１．００５未満であると、酸化セリウム粒子が凝集する傾向があり、１．３００を超えると研磨速度比が低下する傾向がある。なお、重量平均分子量及び数平均分子量は標準ポリスチレンの検量線を用いてゲルパーミエーションクロマトグラフィーにより測定したものを用いる。 As the dispersant, a polymer containing ammonium acrylate as a copolymerization component, ammonium polyacrylate, and amine polyacrylate are preferable. The weight average molecular weight of the polyacrylic acid ammonium or the polyacrylic acid amine salt is preferably 1,000 to 100,000, more preferably 3,000 to 60,000, and still more preferably 10,000 to 40,000. When the weight average molecular weight is less than 1,000, the cerium oxide particles tend to aggregate, and when it exceeds 100,000, the polishing rate ratio tends to decrease. Further, the molecular weight distribution (weight average molecular weight / number average molecular weight) of poly (ammonium acrylate) or poly (amine acrylate) is preferably 1.005 to 1.300, more preferably 1.100 to 1.250, and still more preferably. 1.150 to 1.200. When the molecular weight distribution is less than 1.005, the cerium oxide particles tend to aggregate, and when it exceeds 1.300, the polishing rate ratio tends to decrease. The weight average molecular weight and the number average molecular weight are those measured by gel permeation chromatography using a standard polystyrene calibration curve.
ポリアクリル酸アンモニウム又はポリアクリル酸アミン塩は、ポリアクリル酸と、そのカルボキシル基と等モルのアンモニア又はアミンと混合し、中和反応させて得られるが、塩を形成していないフリーのアンモニア又はアミンの割合が１０モル％以下のもの（換言すればポリアクリル酸のカルボキシル基の９０モル％以上が中和されている）が、高平坦性の点で特に好ましい。なお、塩を形成していないフリーのアンモニア又はアミンの量は、有機溶媒を加えてポリマーを沈殿ろ過した液中のアンモニア又はアミンを定量することによって行える。 Ammonium polyacrylate or amine salt of polyacrylate is obtained by mixing polyacrylic acid and its carboxyl group with an equimolar amount of ammonia or amine and carrying out a neutralization reaction. An amine ratio of 10 mol% or less (in other words, 90 mol% or more of the carboxyl group of polyacrylic acid is neutralized) is particularly preferable from the viewpoint of high flatness. The amount of free ammonia or amine that does not form a salt can be determined by quantifying ammonia or amine in the liquid obtained by adding an organic solvent and precipitating and filtering the polymer.
水溶性陰イオン性界面活性剤としては、例えば、ラウリル硫酸トリエタノールアミン、ラウリル硫酸アンモニウム、ポリオキシエチレンアルキルエーテル硫酸トリエタノールアミン等が挙げられる。 Examples of the water-soluble anionic surfactant include lauryl sulfate triethanolamine, lauryl ammonium sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, and the like.
水溶性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ラウリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレン高級アルコールエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレン誘導体、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリステアレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタントリオレエート、テトラオレイン酸ポリオキシエチレンソルビット、ポリエチレングリコールモノラウレート、ポリエチレングリコールモノステアレート、ポリエチレングリコールジステアレート、ポリエチレングリコールモノオレエート、ポリオキシエチレンアルキルアミン、ポリオキシエチレン硬化ヒマシ油、アルキルアルカノールアミド等が挙げられ、水溶性陽イオン性界面活性剤としては、例えば、ココナットアミンアセテート、ステアリルアミンアセテート等が挙げられる。 Examples of the water-soluble nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether. , Polyoxyethylene nonylphenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene derivatives, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate , Polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, tetraoleic acid Reoxyethylene sorbit, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, alkyl alkanolamide, etc. Examples of the water-soluble cationic surfactant include coconut amine acetate and stearyl amine acetate.
水溶性両性界面活性剤としては、例えば、ラウリルベタイン、ステアリルベタイン、ラウリルジメチルアミンオキサイド、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン等が挙げられる。 Examples of the water-soluble amphoteric surfactant include lauryl betaine, stearyl betaine, lauryl dimethylamine oxide, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine and the like.
酸化セリウムスラリー中のこれらの分散剤添加量は、スラリー中の粒子の分散性及び沈降防止、さらに研磨傷と分散剤添加量との関係から酸化セリウム粒子１００重量部に対して、０．０１重量部以上２．０重量部以下の範囲が好ましい。 上記の分散剤のうち、高分子分散剤の分子量は、標準ポリスチレンの検量線を用いてゲルパーミエーションクロマトグラフィーにより測定した重量平均分子量で、１００〜１００，０００が好ましく、１００〜５０，０００がより好ましく、１，０００〜１０，０００がさらに好ましい。分散剤の分子量が小さすぎると、酸化珪素膜あるいは窒化珪素膜を研磨するときに、十分な研磨速度が得られず、分散剤の分子量が大きすぎると、粘度が高くなり、酸化セリウムスラリーの保存安定性が低下するからである。 The amount of these dispersants added in the cerium oxide slurry is 0.01 weight with respect to 100 parts by weight of the cerium oxide particles from the relationship between the dispersibility of the particles in the slurry and the settling prevention, and the relationship between polishing scratches and the amount of dispersant added. The range of not less than 2.0 parts and not more than 2.0 parts by weight is preferred. Among the above dispersants, the molecular weight of the polymer dispersant is a weight average molecular weight measured by gel permeation chromatography using a standard polystyrene calibration curve, and is preferably 100 to 100,000, preferably 100 to 50,000. More preferred is 1,000 to 10,000. If the molecular weight of the dispersant is too small, a sufficient polishing rate cannot be obtained when polishing a silicon oxide film or a silicon nitride film. If the molecular weight of the dispersant is too large, the viscosity increases and the cerium oxide slurry is stored. This is because the stability is lowered.
また、酸化セリウムスラリーのｐＨは、６〜１０が好ましい。ｐＨが小さすぎると、酸化セリウムスラリーと添加液の混合液の保存安定性が低下し、酸化珪素膜あるいは窒化珪素膜を研磨した場合に、研磨傷が発生し、ｐＨが大きすぎると、酸化セリウムスラリーと添加液の混合液の保存安定性が低下し、酸化珪素膜あるいは窒化珪素膜を研磨した場合に、研磨傷が発生するからである。このｐＨの調整には、アンモニア水を混合撹拌する方法が用いられる。 The pH of the cerium oxide slurry is preferably 6-10. If the pH is too low, the storage stability of the mixed solution of the cerium oxide slurry and the additive solution is reduced, and when a silicon oxide film or a silicon nitride film is polished, polishing flaws occur. If the pH is too high, the cerium oxide This is because the storage stability of the mixed liquid of the slurry and the additive liquid is lowered, and polishing flaws occur when the silicon oxide film or the silicon nitride film is polished. For adjusting the pH, a method of mixing and stirring ammonia water is used.
これらの酸化セリウム粒子を水中に分散させる方法としては、通常の撹拌機による分散処理の他にホモジナイザー、超音波分散機、湿式ボールミルなどを用いることができる。 As a method for dispersing these cerium oxide particles in water, a homogenizer, an ultrasonic disperser, a wet ball mill or the like can be used in addition to a dispersion treatment using a normal stirrer.
こうして作製されたスラリー中の酸化セリウム粒子の平均粒径は、０．０１μｍ〜１．０μｍであることが好ましい。研磨液の平均粒径が小さすぎると研磨速度が低くなりすぎ、平均粒径が大きすぎると研磨する膜に傷がつきやすくなるからである。 The average particle size of the cerium oxide particles in the slurry thus prepared is preferably 0.01 μm to 1.0 μm. This is because if the average particle size of the polishing liquid is too small, the polishing rate becomes too low, and if the average particle size is too large, the film to be polished is easily damaged.
一方、本発明におけるＣＭＰ研磨剤用添加液は、分散剤と水を含有する。分散剤としては、前記した酸化セリウムスラリーに用いた酸化セリウム粒子の水への分散剤が用いられ、研磨面の研磨速度比、高平坦性の点から、酸化セリウムスラリーに好ましく用いられたものが添加液においても好ましく用いられる。酸化セリウムスラリーと添加液の分散剤の種類は同一であっても異なっていてもよい。分散剤の濃度は添加液中１〜１０重量％であることが好ましい。１重量％未満であると研磨面の平坦性が低下する傾向があり、１０重量％を超えると酸化セリウム粒子が凝集する傾向がある。 On the other hand, the additive solution for CMP abrasive in the present invention contains a dispersant and water. As the dispersant, a dispersant for water of the cerium oxide particles used in the cerium oxide slurry described above is used, and those preferably used for the cerium oxide slurry from the viewpoint of the polishing rate ratio of the polished surface and high flatness. It is also preferably used in the additive solution. The kind of dispersant for the cerium oxide slurry and the additive solution may be the same or different. The concentration of the dispersant is preferably 1 to 10% by weight in the additive solution. If the amount is less than 1% by weight, the flatness of the polished surface tends to decrease, and if it exceeds 10% by weight, the cerium oxide particles tend to aggregate.
本発明のＣＭＰ研磨剤は、酸化セリウムスラリーと添加液を別々に用意し、研磨時に両者を混合して使用するもので、酸化セリウムスラリーと上記添加液とを混合した状態で保存すると酸化セリウム粒子が凝集して研磨傷の発生、研磨速度の変動をもたらす。このため、この添加液は、酸化セリウムスラリーと別々に研磨定盤上に供給し、研磨定盤上で混合するか、研磨直前に酸化セリウムスラリーと混合し研磨定盤上に供給する方法がとられる。このとき、酸化セリウムスラリーと添加液の混合比率は、最終的に目的の濃度になれば、特に制限はない。 The CMP polishing slurry of the present invention is prepared by separately preparing a cerium oxide slurry and an additive liquid, and mixing and using both at the time of polishing. When the cerium oxide slurry and the additive liquid are stored in a mixed state, cerium oxide particles Agglomerates, resulting in generation of polishing flaws and fluctuations in the polishing rate. For this reason, the additive solution is supplied separately from the cerium oxide slurry on the polishing platen and mixed on the polishing platen, or mixed with the cerium oxide slurry and supplied onto the polishing platen immediately before polishing. It is done. At this time, the mixing ratio of the cerium oxide slurry and the additive solution is not particularly limited as long as it finally reaches a target concentration.
また、添加液中の分散剤の酸化セリウムに対する使用量は、スラリー中の粒子の分散性及び沈降防止、さらに研磨傷と分散剤の添加量との関係から、酸化セリウムスラリー中の酸化セリウム粒子１００重量部に対して、添加液中の分散剤が０．００１〜２０００重量部の範囲が好ましく、０．０１〜１０００重量部の範囲がより好ましく、０．０１〜５００重量部の範囲がより好ましい。 Further, the amount of the dispersant in the additive liquid used with respect to cerium oxide is determined based on the dispersibility of the particles in the slurry and the prevention of sedimentation, and the relationship between the polishing scratches and the amount of the dispersant added, and the cerium oxide particles 100 in the cerium oxide slurry. The range of 0.001-2000 weight part of the dispersing agent in an additive liquid is preferable with respect to a weight part, The range of 0.01-1000 weight part is more preferable, The range of 0.01-500 weight part is more preferable. .
添加液は比重が１．００５〜１．０５０であることが好ましい。比重はより好ましくは１．００７〜１．０４０、さらに好ましくは１．０１０〜１．０３０である。比重が１．００５未満であると研磨面の平坦性が低下する傾向があり、比重が１．０５０を超えると酸化セリウム粒子が凝集する傾向がある。また、添加液はｐＨが４〜８であることが好ましい。ｐＨはより好ましくは５〜７、さらに好ましくは６〜７である。ｐＨが４未満であると研磨速度が低下する傾向があり、ｐＨが８を超えると研磨面の平坦性が低下する傾向がある。ｐＨの調整は添加液に、例えば、酢酸、アンモニア水などの酸又はアルカリを添加することにより行われる。また、添加液は２５℃における粘度が１．２０〜２．５０ｍＰａ・ｓであることが好ましい。粘度はより好ましくは１．３０〜２．３０ｍＰａ・ｓ、さらに好ましくは１．４０〜２．２０ｍＰａ・ｓである。粘度が１．２０ｍＰａ・ｓ未満だと酸化セリウム粒子が凝集する傾向があり、２．５０Ｐａ・ｓを超えると研磨面の平坦性が低下する傾向がある。 The additive liquid preferably has a specific gravity of 1.005 to 1.050. The specific gravity is more preferably 1.007 to 1.040, and still more preferably 1.010 to 1.030. When the specific gravity is less than 1.005, the flatness of the polished surface tends to decrease, and when the specific gravity exceeds 1.050, the cerium oxide particles tend to aggregate. Moreover, it is preferable that pH of the additive liquid is 4-8. The pH is more preferably 5-7, still more preferably 6-7. When the pH is less than 4, the polishing rate tends to decrease, and when the pH exceeds 8, the flatness of the polished surface tends to decrease. The pH is adjusted by adding an acid or alkali such as acetic acid or aqueous ammonia to the additive solution. The additive solution preferably has a viscosity at 25 ° C. of 1.20 to 2.50 mPa · s. The viscosity is more preferably 1.30 to 2.30 mPa · s, and still more preferably 1.40 to 2.20 mPa · s. If the viscosity is less than 1.20 mPa · s, the cerium oxide particles tend to aggregate, and if it exceeds 2.50 Pa · s, the flatness of the polished surface tends to decrease.
本発明のＣＭＰ研磨剤は、上記酸化セリウムスラリー及び添加液をそのまま使用してもよいが、Ｎ，Ｎ−ジエチルエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、アミノエチルエタノールアミン等の非高分子添加剤を酸化セリウムスラリー又はＣＭＰ用添加液に添加してＣＭＰ研磨剤とすることができる。これらの添加剤は、最終的なＣＭＰ研磨剤における濃度が、０．００１〜２０重量％になるように使用されることが好ましく、さらに、０．０１〜１０重量％になるように使用されることが好ましい。 The CMP polishing slurry of the present invention may use the cerium oxide slurry and additive solution as they are, but non-polymer addition such as N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethylethanolamine, etc. An agent can be added to the cerium oxide slurry or the CMP additive to form a CMP abrasive. These additives are preferably used so that the final CMP abrasive has a concentration of 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight. It is preferable.
本発明のＣＭＰ研磨剤が使用される無機絶縁膜の作製方法として、低圧ＣＶＤ法、プラズマＣＶＤ法等が挙げられる。低圧ＣＶＤ法による酸化珪素膜形成は、Ｓｉ源としてモノシラン：ＳｉＨ4、酸素源として酸素：Ｏ2を用いる。このＳｉＨ4−Ｏ2系酸化反応を４００℃以下の低温で行わせることにより得られる。場合によっては、ＣＶＤ後１０００℃またはそれ以下の温度で熱処理される。高温リフローによる表面平坦化を図るためにリン：Ｐをドープするときには、ＳｉＨ4−Ｏ2−ＰＨ3系反応ガスを用いることが好ましい。プラズマＣＶＤ法は、通常の熱平衡下では高温を必要とする化学反応が低温でできる利点を有する。プラズマ発生法には、容量結合型と誘導結合型の２つが挙げられる。反応ガスとしては、Ｓｉ源としてＳｉＨ4、酸素源としてＮ2Ｏを用いたＳｉＨ4−Ｎ2Ｏ系ガスとテトラエトキシシラン（ＴＥＯＳ）をＳｉ源に用いたＴＥＯＳ−Ｏ2系ガス（ＴＥＯＳ−プラズマＣＶＤ法）が挙げられる。基板温度は２５０℃〜４００℃、反応圧力は６７〜４００Ｐａの範囲が好ましい。このように、本発明の酸化珪素膜にはリン、ホウ素等の元素がドープされていても良い。 Examples of a method for producing an inorganic insulating film using the CMP abrasive of the present invention include a low pressure CVD method and a plasma CVD method. Silicon oxide film formation by low-pressure CVD uses monosilane: SiH 4 as the Si source and oxygen: O 2 as the oxygen source. It can be obtained by performing this SiH 4 —O 2 oxidation reaction at a low temperature of 400 ° C. or lower. In some cases, heat treatment is performed at a temperature of 1000 ° C. or lower after CVD. When doping phosphorus: P in order to achieve surface flattening by high-temperature reflow, it is preferable to use a SiH 4 —O 2 —PH 3 reaction gas. The plasma CVD method has an advantage that a chemical reaction requiring a high temperature can be performed at a low temperature under normal thermal equilibrium. There are two plasma generation methods, capacitive coupling type and inductive coupling type. As the reaction gas, a SiH 4 —N 2 O gas using SiH 4 as a Si source and N 2 O as an oxygen source and a TEOS-O 2 gas (TEOS—) using tetraethoxysilane (TEOS) as a Si source are used. Plasma CVD method). The substrate temperature is preferably 250 to 400 ° C., and the reaction pressure is preferably 67 to 400 Pa. Thus, the silicon oxide film of the present invention may be doped with elements such as phosphorus and boron.
同様に、低圧ＣＶＤ法による窒化珪素膜形成は、Ｓｉ源としてジクロルシラン：ＳｉＨ2Ｃｌ2、窒素源としてアンモニア：ＮＨ3を用いる。このＳｉＨ2Ｃｌ2−ＮＨ3系酸化反応を９００℃の高温で行わせることにより得られる。プラズマＣＶＤ法は、反応ガスとしては、Ｓｉ源としてＳｉＨ4、窒素源としてＮＨ3を用いたＳｉＨ4−ＮＨ3系ガスが挙げられる。基板温度は３００℃〜４００℃が好ましい。 Similarly, a silicon nitride film formed by low pressure CVD, dichlorosilane as Si source: SiH 2 Cl 2, ammonia as a nitrogen source: the NH 3 is used. The SiH 2 Cl 2 —NH 3 oxidation reaction is performed at a high temperature of 900 ° C. In the plasma CVD method, examples of the reactive gas include SiH 4 —NH 3 -based gas using SiH 4 as the Si source and NH 3 as the nitrogen source. The substrate temperature is preferably 300 ° C to 400 ° C.
基板として、半導体基板すなわち回路素子と配線パターンが形成された段階の半導体基板、回路素子が形成された段階の半導体基板等の半導体基板上に酸化珪素膜層あるいは窒化珪素膜層が形成された基板が使用できる。このような半導体基板上に形成された酸化珪素膜層あるいは窒化珪素膜層を上記ＣＭＰ研磨剤で研磨することによって、酸化珪素膜層表面の凹凸を解消し、半導体基板全面にわたって平滑な面とすることができる。また、シャロー・トレンチ分離にも使用できる。シャロー・トレンチ分離に使用するためには、酸化珪素膜研磨速度と窒化珪素膜研磨速度の比、酸化珪素膜研磨速度／窒化珪素膜研磨速度が１０以上であることが必要である。この比が小さすぎると、酸化珪素膜研磨速度と窒化珪素膜研磨速度の差が小さくなり、シャロー・トレンチ分離をする際、所定の位置で研磨を停止することができなくなる。また、この比が５０以上の場合は、特に、窒化珪素膜の研磨速度がさらに小さくなって研磨の停止が容易になり、シャロー・トレンチ分離により好適である。 As a substrate, a semiconductor substrate, that is, a semiconductor substrate on which a circuit element and a wiring pattern are formed, a substrate on which a silicon oxide film layer or a silicon nitride film layer is formed on a semiconductor substrate such as a semiconductor substrate on which a circuit element is formed Can be used. By polishing the silicon oxide film layer or silicon nitride film layer formed on such a semiconductor substrate with the above-described CMP abrasive, the unevenness on the surface of the silicon oxide film layer is eliminated and the entire surface of the semiconductor substrate is made smooth. be able to. It can also be used for shallow trench isolation. In order to use for shallow trench isolation, the ratio of the silicon oxide film polishing rate to the silicon nitride film polishing rate, and the silicon oxide film polishing rate / silicon nitride film polishing rate must be 10 or more. If this ratio is too small, the difference between the polishing rate of the silicon oxide film and the polishing rate of the silicon nitride film becomes small, and polishing cannot be stopped at a predetermined position when performing shallow trench isolation. In addition, when this ratio is 50 or more, the polishing rate of the silicon nitride film is further reduced and polishing can be easily stopped, which is preferable for shallow trench isolation.
研磨する装置としては、半導体基板を保持するホルダーと研磨布（パッド）を貼り付けた（回転数が変更可能なモータ等を取り付けてある）定盤を有する一般的な研磨装置が使用できる。研磨布としては、一般的な不織布、発泡ポリウレタン、多孔質フッ素樹脂などが使用でき、特に制限がない。また、研磨布にはＣＭＰ研磨剤がたまるような溝加工を施すことが好ましい。研磨条件には制限はないが、定盤の回転速度は半導体基板が飛び出さないように２００ｒｐｍ以下の低回転が好ましく、半導体基板にかける圧力は研磨後に傷が発生しないように１ｋｇ／ｃｍ2以下が好ましい。シャロー・トレンチ分離に使用するためには、研磨時に傷の発生が少ないことが必要である。研磨している間、研磨布にはスラリーをポンプ等で連続的に供給する。この供給量には制限はないが、研磨布の表面が常にスラリーで覆われていることが好ましい。 As a polishing apparatus, a general polishing apparatus having a holder for holding a semiconductor substrate and a surface plate to which a polishing cloth (pad) is attached (a motor or the like whose rotation speed can be changed) is attached. As an abrasive cloth, a general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used, and there is no restriction | limiting in particular. Further, it is preferable that the polishing cloth is grooved so that the CMP abrasive is accumulated. The polishing conditions are not limited, but the rotation speed of the surface plate is preferably low rotation of 200 rpm or less so that the semiconductor substrate does not jump out, and the pressure applied to the semiconductor substrate is 1 kg / cm 2 or less so that no scratches are generated after polishing. Is preferred. In order to be used for shallow trench isolation, it is necessary that scratches are less likely to occur during polishing. During polishing, slurry is continuously supplied to the polishing cloth with a pump or the like. Although there is no restriction | limiting in this supply amount, it is preferable that the surface of polishing cloth is always covered with the slurry.
研磨終了後の半導体基板は、流水中で良く洗浄後、スピンドライヤ等を用いて半導体基板上に付着した水滴を払い落としてから乾燥させることが好ましい。このようにして平坦化されたシャロー・トレンチを形成したあと、酸化珪素絶縁膜層の上に、アルミニウム配線を形成し、その配線間及び配線上に再度上記方法により酸化珪素絶縁膜を形成後、上記ＣＭＰ研磨剤を用いて研磨することによって、絶縁膜表面の凹凸を解消し、半導体基板全面にわたって平滑な面とする。この工程を所定数繰り返すことにより、所望の層数の半導体を製造する。 The semiconductor substrate after the polishing is preferably washed in running water, and then dried after removing water droplets adhering to the semiconductor substrate using a spin dryer or the like. After forming the planarized shallow trench in this way, an aluminum wiring is formed on the silicon oxide insulating film layer, and after forming the silicon oxide insulating film again between the wirings and on the wiring by the above method, By polishing using the above-described CMP abrasive, unevenness on the surface of the insulating film is eliminated, and a smooth surface is obtained over the entire surface of the semiconductor substrate. By repeating this process a predetermined number of times, a desired number of semiconductor layers are manufactured.
本発明のＣＭＰ研磨剤は、半導体基板に形成された酸化珪素膜だけでなく、所定の配線を有する配線板に形成された酸化珪素膜、ガラス、窒化珪素等の無機絶縁膜、フォトマスク・レンズ・プリズムなどの光学ガラス、ＩＴＯ等の無機導電膜、ガラス及び結晶質材料で構成される光集積回路・光スイッチング素子・光導波路、光ファイバーの端面、シンチレータ等の光学用単結晶、固体レーザ単結晶、青色レーザＬＥＤ用サファイヤ基板、ＳｉＣ、ＧａＰ、ＧａＡＳ等の半導体単結晶、磁気ディスク用ガラス基板、磁気ヘッド等を研磨することができる。 The CMP polishing agent of the present invention includes not only a silicon oxide film formed on a semiconductor substrate, but also a silicon oxide film formed on a wiring board having a predetermined wiring, an inorganic insulating film such as glass and silicon nitride, a photomask lens・ Optical integrated circuits composed of optical glass such as prisms, inorganic conductive films such as ITO, glass and crystalline materials ・ Optical switching elements / optical waveguides, optical fiber end faces, optical single crystals such as scintillators, solid state laser single crystals A sapphire substrate for blue laser LED, a semiconductor single crystal such as SiC, GaP, and GaAS, a glass substrate for magnetic disk, a magnetic head, and the like can be polished.
以下に、本発明の実施例及びその比較例を示し、本発明をさらに具体的に説明するが本発明は、これらの実施例に限定されるものではない。 Examples of the present invention and comparative examples thereof will be shown below, and the present invention will be described more specifically. However, the present invention is not limited to these examples.
作製例１（酸化セリウム粒子の作製）
炭酸セリウム水和物２ｋｇを白金製容器に入れ、７００℃で２時間空気中で焼成することにより黄白色の粉末を約１ｋｇ得た。この粉末をＸ線回折法で相同定を行ったところ酸化セリウムであることを確認した。酸化セリウム粉末１０重量％になるように脱イオン水と混合し、横型湿式超微粒分散粉砕機を用いて１４００ｒｐｍで１２０分間粉砕処理をした。得られた研磨液を１１０℃で３時間乾燥することにより酸化セリウム粒子を得た。この酸化セリウム粒子は、透過型電子顕微鏡による観察から多結晶体を構成する１次粒子径が１０ｎｍ〜６０ｎｍであること、さらにＢＥＴ法による比表面積測定の結果が３９．５ｍ2／ｇであることがわかった。
Production Example 1 (Production of cerium oxide particles)
About 1 kg of yellowish white powder was obtained by putting 2 kg of cerium carbonate hydrate in a platinum container and firing in air at 700 ° C. for 2 hours. When this powder was phase-identified by X-ray diffraction, it was confirmed to be cerium oxide. It mixed with deionized water so that it might become 10 weight% of cerium oxide powder, and it grind | pulverized for 120 minutes at 1400 rpm using the horizontal type wet ultrafine particle dispersion grinder. The obtained polishing liquid was dried at 110 ° C. for 3 hours to obtain cerium oxide particles. The cerium oxide particles have a primary particle diameter of 10 nm to 60 nm constituting a polycrystal as observed from a transmission electron microscope, and a specific surface area measurement result by the BET method is 39.5 m 2 / g. I understood.
作製例２（酸化セリウム粒子の作製）
炭酸セリウム水和物２ｋｇを白金製容器に入れ、７００℃で２時間空気中で焼成することにより黄白色の粉末を約１ｋｇ得た。この粉末をＸ線回折法で相同定を行ったところ酸化セリウムであることを確認した。酸化セリウム粉末１ｋｇをジェットミルを用いて乾式粉砕を行った。この酸化セリウム粒子は、透過型電子顕微鏡による観察から多結晶体を構成する１次粒子径が１０ｎｍ〜６０ｎｍであること、さらにＢＥＴ法による比表面積測定の結果、４１．２ｍ2／ｇであることがわかった。
Production Example 2 (Production of cerium oxide particles)
About 1 kg of yellowish white powder was obtained by putting 2 kg of cerium carbonate hydrate in a platinum container and firing in air at 700 ° C. for 2 hours. When this powder was phase-identified by X-ray diffraction, it was confirmed to be cerium oxide. 1 kg of cerium oxide powder was dry pulverized using a jet mill. The cerium oxide particles have a primary particle size of 10 nm to 60 nm constituting a polycrystal as observed from a transmission electron microscope, and are 41.2 m 2 / g as a result of measuring a specific surface area by the BET method. I understood.
作製例３（酸化セリウムスラリーの作製）
上記酸化セリウム粒子の作製例１で作製した酸化セリウム粒子１２５ｇとアクリル酸とアクリル酸メチルを３：１で共重合した重量平均分子量１０，０００のポリアクリル酸共重合体のアンモニウム塩水溶液（４０重量％）３ｇと脱イオン水２３７２ｇを混合し、撹拌をしながら超音波分散を行った。超音波周波数は４０ｋＨｚで、分散時間１０分で分散を行った。得られたスラリーを０．８ミクロンフィルターでろ過し、さらに脱イオン水を加えることにより２重量％の酸化セリウムスラリー（Ａ−１）を得た。酸化セリウムスラリー（Ａ−１）のｐＨは８．５であった。酸化セリウムスラリー（Ａ−１）の粒度分布をレーザー回折式粒度分布計で調べたところ、平均粒子径が０．２０μｍと小さいことがわかった。また、１．０μｍ以下の粒子が９５．０％であった。
Production Example 3 (Production of cerium oxide slurry)
Ammonium salt aqueous solution of polyacrylic acid copolymer having a weight average molecular weight of 10,000 obtained by copolymerizing 125 g of cerium oxide particles prepared in Preparation Example 1 of the above cerium oxide particles and acrylic acid and methyl acrylate 3: 1 (40 wt. %) 3 g and 2372 g of deionized water were mixed and subjected to ultrasonic dispersion while stirring. The ultrasonic frequency was 40 kHz, and dispersion was performed with a dispersion time of 10 minutes. The obtained slurry was filtered with a 0.8 micron filter, and further deionized water was added to obtain a 2 wt% cerium oxide slurry (A-1). The pH of the cerium oxide slurry (A-1) was 8.5. When the particle size distribution of the cerium oxide slurry (A-1) was examined with a laser diffraction particle size distribution meter, it was found that the average particle size was as small as 0.20 μm. Moreover, the particle | grains of 1.0 micrometer or less were 95.0%.
作製例４（酸化セリウムスラリーの作製）
酸化セリウム粒子の作製例１で作製した酸化セリウム粒子の代わりに酸化セリウム粒子の作製例２で作製した酸化セリウムスラリーを使用した以外は酸化セリウムスラリーの作製例３と同様の方法で酸化セリウムスラリー（Ａ−２）を作製した。この酸化セリウムスラリー（Ａ−２）のｐＨは８．７であった。酸化セリウムスラリー（Ａ−２）の粒度分布を調べたところ、平均粒子径が０．２１μｍと小さいことがわかった。また、１．０μｍ以下の粒子が９５．０％であった。
Production Example 4 (Production of cerium oxide slurry)
The cerium oxide slurry was prepared in the same manner as the cerium oxide slurry preparation example 3 except that the cerium oxide slurry prepared in preparation example 2 of the cerium oxide particles was used instead of the cerium oxide particles prepared in preparation example 1 of the cerium oxide particles. A-2) was produced. The pH of this cerium oxide slurry (A-2) was 8.7. When the particle size distribution of the cerium oxide slurry (A-2) was examined, it was found that the average particle size was as small as 0.21 μm. Moreover, the particle | grains of 1.0 micrometer or less were 95.0%.
作製例５（酸化セリウム粒子の作製）
炭酸セリウム水和物２ｋｇを白金製容器に入れ、９００℃で２時間空気中で焼成することにより黄白色の粉末を約１ｋｇ得た。この粉末をＸ線回折法で相同定を行ったところ、酸化セリウムであることを確認した。酸化セリウム粉末１ｋｇをジェットミルを用いて乾式粉砕を行った。この酸化セリウム粒子は、透過型電子顕微鏡による観察から粒子径が８０ｎｍ〜１５０ｎｍの単結晶体であること、さらにＢＥＴ法による比表面積測定の結果、１８．５ｍ2／ｇであることがわかった。
Production Example 5 (Production of cerium oxide particles)
About 1 kg of yellowish white powder was obtained by putting 2 kg of cerium carbonate hydrate into a platinum container and firing in air at 900 ° C. for 2 hours. When this powder was phase-identified by X-ray diffraction, it was confirmed to be cerium oxide. 1 kg of cerium oxide powder was dry pulverized using a jet mill. This cerium oxide particle was found to be a single crystal having a particle diameter of 80 nm to 150 nm from observation with a transmission electron microscope, and as a result of measuring the specific surface area by the BET method, it was found to be 18.5 m 2 / g.
作製例６（酸化セリウムスラリーの作製）
酸化セリウム粒子の作製例１で作製した酸化セリウム粒子の代わりに比較作製例１で作製した酸化セリウム粒子を使用した以外は酸化セリウムスラリーの作製例１と同様の方法で酸化セリウムスラリー（Ｂ−１）を作製した。この酸化セリウムスラリー（Ｂ−１）のｐＨは８．４であった。酸化セリウムスラリー（Ｂ−１）の粒度分布を調べたところ、平均粒子径が０．３５μｍと小さいことがわかった。また、１．０μｍ以下の粒子が８５．５％であった。
Production Example 6 (Production of cerium oxide slurry)
The cerium oxide slurry (B-1) was prepared in the same manner as the cerium oxide slurry production example 1 except that the cerium oxide particles produced in comparative production example 1 were used instead of the cerium oxide particles produced in production example 1 of the cerium oxide particles. ) Was produced. The pH of this cerium oxide slurry (B-1) was 8.4. When the particle size distribution of the cerium oxide slurry (B-1) was examined, it was found that the average particle size was as small as 0.35 μm. Moreover, the particle | grains of 1.0 micrometer or less were 85.5%.
実施例１〜１０及び比較例１、２
表１に示すように、酸化セリウムスラリーと添加液を調製してＣＭＰ研磨剤を作製し、酸化セリウムスラリーと添加液の混合液を用いて下記に示す方法で絶縁膜を研磨した。その結果を表１に示す。
Examples 1 to 10 and Comparative Examples 1 and 2
As shown in Table 1, a cerium oxide slurry and an additive solution were prepared to produce a CMP abrasive, and the insulating film was polished by the following method using a mixed solution of the cerium oxide slurry and the additive solution. The results are shown in Table 1.
実施例１〜５及び実施例７、９においては添加液中の分散剤は実施例１の酸化セリウムスラリーに用いたものと同じものを用い、脱イオン水に所定量溶解して用いた。 In Examples 1 to 5 and Examples 7 and 9, the same dispersant as that used in the cerium oxide slurry of Example 1 was used, and a predetermined amount dissolved in deionized water was used.
実施例６、８、１０で分散剤として用いたポリアクリル酸アンモニウムは重量平均分子量１０，０００、数平均分子量８，３３３、分子量分布１．２、フリーアンモニア４．３モル％のものを用いた。また実施例６で用いた添加液の粘度は１．４６ｍＰａ・ｓ、比重は１．０１０であった。 The ammonium polyacrylate used as a dispersant in Examples 6, 8, and 10 was a weight average molecular weight of 10,000, a number average molecular weight of 8,333, a molecular weight distribution of 1.2, and free ammonia of 4.3 mol%. . The additive solution used in Example 6 had a viscosity of 1.46 mPa · s and a specific gravity of 1.010.
比較例２は実施例１における酸化セリウムスラリーと添加液を予め混合しておき１日経過後、この混合物を使用して絶縁膜を研磨した。 In Comparative Example 2, the cerium oxide slurry and the additive solution in Example 1 were mixed in advance, and after 1 day, the insulating film was polished using this mixture.
（絶縁膜の研磨）
多孔質ウレタン樹脂製の研磨パッドを貼りつけた定盤上に、基板取り付け用の吸着パッドを貼り付けたホルダーにＴＥＯＳ−プラズマＣＶＤ法で作製した酸化珪素膜を形成した直径１２５ｍｍのシリコンウエハを絶縁膜面を下にしてセットし、研磨荷重が３００ｇ／ｃｍ2になるように重りをのせた。定盤上に上記の酸化セリウムスラリー（固形分：２重量％）と添加液を各々２５ｍｌ／ｍｉｎの速度で送り、定盤の直前で１液になるようにノズルを調節して滴下しながら、定盤を４０ｒｐｍで２分間回転させ、絶縁膜を研磨した。研磨後ウエハをホルダーから取り外して、流水で良く洗浄後、超音波洗浄機によりさらに２０分間洗浄した。洗浄後、スピンドライヤーで水滴を除去し、１２０℃の乾燥機で１０分間乾燥させた。光干渉式膜厚測定装置を用いて、研磨前後の膜厚変化を測定し、研磨速度を計算した。
(Insulating film polishing)
A silicon wafer with a diameter of 125 mm is formed by forming a silicon oxide film made by TEOS-plasma CVD method on a holder with a suction pad for attaching a substrate on a surface plate with a porous urethane resin polishing pad. The film surface was set downward and a weight was applied so that the polishing load was 300 g / cm 2 . While feeding the above cerium oxide slurry (solid content: 2% by weight) and the additive liquid on the surface plate at a rate of 25 ml / min, while adjusting the nozzle so that it becomes one liquid immediately before the surface plate, The surface plate was rotated at 40 rpm for 2 minutes to polish the insulating film. After polishing, the wafer was removed from the holder, washed thoroughly with running water, and further washed with an ultrasonic cleaner for 20 minutes. After washing, water droplets were removed with a spin dryer and dried for 10 minutes with a 120 ° C. dryer. The change in film thickness before and after polishing was measured using an optical interference type film thickness measuring device, and the polishing rate was calculated.
同様にして、ＴＥＯＳ−プラズマＣＶＤ法で作製した酸化珪素膜の代わりに低圧ＣＶＤ法で作製した窒化珪素膜を同じ条件で研磨し、研磨前後の膜厚変化を測定し、研磨速度を計算した。また、膜厚測定の結果から、ＴＥＯＳ−プラズマＣＶＤ法で作製した酸化珪素膜及び低圧ＣＶＤ法で作製した窒化珪素膜は、ウエハ全面にわたって均一の厚みになっていることがわかった。また、水銀灯の光源下での目視観察では絶縁膜表面に傷はみられなかったが、さらにウエハの外観検査装置（オリンパスＡＬ−２０００、オリンパス光学工業（株）商品名）で詳細に観察した。 Similarly, a silicon nitride film produced by a low pressure CVD method instead of a silicon oxide film produced by TEOS-plasma CVD method was polished under the same conditions, a change in film thickness before and after polishing was measured, and a polishing rate was calculated. From the results of film thickness measurement, it was found that the silicon oxide film produced by the TEOS-plasma CVD method and the silicon nitride film produced by the low pressure CVD method had a uniform thickness over the entire surface of the wafer. Further, the surface of the insulating film was not scratched by visual observation under a mercury lamp light source, but was further observed in detail with a wafer appearance inspection device (Olympus AL-2000, Olympus Optical Co., Ltd., trade name).
同様にして、２０μｍ角で高さが５，０００Åの凸部を１００μｍ間隔で形成した酸化珪素膜を研磨し、凸部が研磨されたときの凸部と凸部の中間点のへこみ（ディッシング）量を求め、平坦性を評価した。 In the same manner, a silicon oxide film in which convex portions having a diameter of 20 μm and a height of 5,000 mm are formed at intervals of 100 μm is polished, and a dent (dishing) between the convex portion and the convex portion when the convex portion is polished. The amount was determined and the flatness was evaluated.
表１から明らかなように、本発明のＣＭＰ研磨剤及び基板の研磨方法を用いることによって、酸化珪素膜あるいは窒化珪素膜等の被研磨面を、被研磨面にナトリウムイオン等のアルカリ金属汚染をせずに、傷なく、研磨することが可能で、かつ、酸化珪素膜研磨速度／窒化珪素膜研磨速度の比を５０以上にするＣＭＰ研磨剤、及びこれらＣＭＰ研磨剤を使用した基板の研磨方法が得られることが分かる。 As is apparent from Table 1, by using the CMP polishing agent and the substrate polishing method of the present invention, the surface to be polished such as a silicon oxide film or a silicon nitride film is contaminated with alkali metal such as sodium ions on the surface to be polished. Polishing agent capable of polishing without scratches and having a ratio of silicon oxide film polishing rate / silicon nitride film polishing rate of 50 or more, and substrate polishing method using these CMP abrasives It can be seen that
Claims (32)
ＣＭＰ研磨剤が、酸化セリウム粒子、分散剤及び水を含む酸化セリウムスラリー、並びに、分散剤と水を含む添加液からなるＣＭＰ研磨剤であって、
酸化セリウムスラリー及び添加液のそれぞれに含まれる分散剤が高分子分散剤であり、
高分子分散剤が、アクリル酸アンモニウム塩を共重合成分とする重合体、ポリアクリル酸アンモニウム塩又はポリアクリル酸アミン塩であり、
酸化セリウムスラリー中の分散剤の含有量が酸化セリウム粒子１００重量部に対して０．０１〜２．０重量部であり、酸化セリウム粒子の含有量が酸化セリウムスラリーに対して０．３〜４０重量％であり、添加液中の分散剤の含有量が１〜１０重量％であり、
研磨定盤上で酸化セリウムスラリーと添加液とを別々に同時に供給することにより混合し、ＣＭＰ研磨剤を被研磨膜と研磨布との間に供給する研磨方法。 The substrate on which the film to be polished is formed is pressed against the polishing cloth of the polishing surface plate and pressurized, and the substrate and the polishing surface plate are moved while the CMP abrasive is being supplied between the film to be polished and the polishing cloth. A method for polishing a substrate to be polished, comprising:
The CMP abrasive is a CMP abrasive comprising a cerium oxide slurry containing cerium oxide particles, a dispersant and water, and an additive liquid containing a dispersant and water,
The dispersant contained in each of the cerium oxide slurry and the additive solution is a polymer dispersant,
The polymer dispersant is a polymer having an acrylic acid ammonium salt as a copolymerization component, a polyacrylic acid ammonium salt or a polyacrylic acid amine salt,
The content of the dispersant in the cerium oxide slurry is 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the cerium oxide particles, and the content of the cerium oxide particles is 0.3 to 40 with respect to the cerium oxide slurry. weight%, and the content of the dispersant additive solution is Ri 1 to 10 wt% der,
A polishing method in which a cerium oxide slurry and an additive solution are mixed and supplied separately on a polishing platen, and a CMP abrasive is supplied between a film to be polished and a polishing cloth .
ＣＭＰ研磨剤が、酸化セリウム粒子、分散剤及び水を含む酸化セリウムスラリー、並びに、分散剤と水を含む添加液からなるＣＭＰ研磨剤であって、
酸化セリウムスラリー及び添加液のそれぞれに含まれる分散剤が高分子分散剤であり、
高分子分散剤が、アクリル酸アンモニウム塩を共重合成分とする重合体、ポリアクリル酸アンモニウム塩又はポリアクリル酸アミン塩であり、
酸化セリウムスラリー中の分散剤の含有量が酸化セリウム粒子１００重量部に対して０．０１〜２．０重量部であり、酸化セリウム粒子の含有量が酸化セリウムスラリーに対して０．３〜４０重量％であり、添加液中の分散剤の含有量が１〜１０重量％であり、
別々に分けて保存された酸化セリウムスラリーと添加液とを研磨直前に混合してＣＭＰ研磨剤を被研磨膜と研磨布との間に供給する研磨方法。 The substrate on which the film to be polished is formed is pressed against the polishing cloth of the polishing surface plate and pressurized, and the substrate and the polishing surface plate are moved while the CMP abrasive is being supplied between the film to be polished and the polishing cloth. A method for polishing a substrate to be polished, comprising:
The CMP abrasive is a CMP abrasive comprising a cerium oxide slurry containing cerium oxide particles, a dispersant and water, and an additive liquid containing a dispersant and water,
The dispersant contained in each of the cerium oxide slurry and the additive solution is a polymer dispersant,
The polymer dispersant is a polymer having an acrylic acid ammonium salt as a copolymerization component, a polyacrylic acid ammonium salt or a polyacrylic acid amine salt,
The content of the dispersant in the cerium oxide slurry is 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the cerium oxide particles, and the content of the cerium oxide particles is 0.3 to 40 with respect to the cerium oxide slurry. And the content of the dispersant in the additive liquid is 1 to 10% by weight,
A polishing method in which cerium oxide slurry and separately stored separately are mixed immediately before polishing and a CMP abrasive is supplied between a film to be polished and a polishing cloth .
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| WO1997029510A1 (en) * | 1996-02-07 | 1997-08-14 | Hitachi Chemical Company, Ltd. | Cerium oxide abrasive, semiconductor chip, semiconductor device, process for the production of them, and method for the polishing of substrates |
| JPH10154672A (en) * | 1996-09-30 | 1998-06-09 | Hitachi Chem Co Ltd | Cerium oxide abrasive material and polishing method of substrate |
| JPH10172937A (en) * | 1996-12-05 | 1998-06-26 | Fujimi Inkooporeetetsudo:Kk | Composition for polishing |
| JPH10286756A (en) * | 1997-04-10 | 1998-10-27 | Toshiba Corp | Dressing method of polishing pad, polishing device, and manufacture of semiconductor device |
| JP3649279B2 (en) * | 1998-12-25 | 2005-05-18 | 日立化成工業株式会社 | Substrate polishing method |
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| WO1997029510A1 (en) * | 1996-02-07 | 1997-08-14 | Hitachi Chemical Company, Ltd. | Cerium oxide abrasive, semiconductor chip, semiconductor device, process for the production of them, and method for the polishing of substrates |
| JPH10154672A (en) * | 1996-09-30 | 1998-06-09 | Hitachi Chem Co Ltd | Cerium oxide abrasive material and polishing method of substrate |
| JPH10172937A (en) * | 1996-12-05 | 1998-06-26 | Fujimi Inkooporeetetsudo:Kk | Composition for polishing |
| JPH10286756A (en) * | 1997-04-10 | 1998-10-27 | Toshiba Corp | Dressing method of polishing pad, polishing device, and manufacture of semiconductor device |
| JP3649279B2 (en) * | 1998-12-25 | 2005-05-18 | 日立化成工業株式会社 | Substrate polishing method |
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