KR101101207B1 - CMP Composition for Polishing Metal - Google Patents
CMP Composition for Polishing Metal Download PDFInfo
- Publication number
- KR101101207B1 KR101101207B1 KR1020090046484A KR20090046484A KR101101207B1 KR 101101207 B1 KR101101207 B1 KR 101101207B1 KR 1020090046484 A KR1020090046484 A KR 1020090046484A KR 20090046484 A KR20090046484 A KR 20090046484A KR 101101207 B1 KR101101207 B1 KR 101101207B1
- Authority
- KR
- South Korea
- Prior art keywords
- polishing
- particles
- inorganic oxide
- metal film
- present
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title abstract description 30
- 239000002184 metal Substances 0.000 title abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 39
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 38
- 239000011146 organic particle Substances 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003139 buffering effect Effects 0.000 abstract 1
- -1 sulfate ester salts Chemical class 0.000 description 26
- 239000010954 inorganic particle Substances 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 150000003839 salts Chemical group 0.000 description 4
- 150000003871 sulfonates Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
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- 229920001477 hydrophilic polymer Polymers 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920006294 polydialkylsiloxane Polymers 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- VPGSXIKVUASQIY-UHFFFAOYSA-N 1,2-dibutylnaphthalene Chemical compound C1=CC=CC2=C(CCCC)C(CCCC)=CC=C21 VPGSXIKVUASQIY-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- JXBKZAYVMSNKHA-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-olate Chemical compound OC=1N=NNN=1 JXBKZAYVMSNKHA-UHFFFAOYSA-N 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical compound SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
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- 239000004472 Lysine Substances 0.000 description 1
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- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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- 150000003973 alkyl amines Chemical class 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
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- 239000012964 benzotriazole Substances 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical class [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000004310 lactic acid Substances 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
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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
- C09K3/1436—Composite particles, e.g. coated particles
- C09K3/1445—Composite particles, e.g. coated particles the coating consisting exclusively of metals
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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
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- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
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- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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Abstract
본 발명은 반도체 제조 공정에서 금속막을 화학 기계적 연마하기 위한 금속막 연마용 슬러리 조성물에 관한 것으로서, 본 발명에 따른 슬러리 조성물은 평균입경 10 ~ 1000nm인 구형의 유기입자로 된 코어와, 이의 표면에 1 ~ 100nm 두께의 무기산화물 막형태로 코팅된 코어-쉘 입자를 0.0001 ~ 20 중량% 포함하는 금속막 연마용 슬러리 조성물에 관한 것이다.The present invention relates to a slurry composition for polishing a metal film for chemical mechanical polishing in a semiconductor manufacturing process. The slurry composition according to the present invention comprises a core made of spherical organic particles having an average particle diameter of 10 to 1000 nm, and a surface of 1 It relates to a metal film polishing slurry composition comprising 0.0001 to 20% by weight of the core-shell particles coated in the form of an inorganic oxide film having a thickness of ~ 100nm.
본 발명에 따른 슬러리는 무기산화물이 막형태로 코팅된 유기 화합물을 사용하여 표면에 코팅된 무기산화물로 인해 낮은 압력에서도 높은 연마속도를 나타내며, 유기입자의 연성으로 인해 무기산화물로 발생하는 기계적인 충격을 완충시킴으로써 표면에 스크래치 발생이 적을 뿐만 아니라 디싱 감소 효과를 가지는 장점이 있다. 본 발명의 금속막 연마용 슬러리 조성물은 구리를 포함하는 금속막 연마용 슬러리로 유용하다. The slurry according to the present invention exhibits a high polishing rate even at low pressure due to the inorganic oxide coated on the surface using an organic compound coated with an inorganic oxide film, and mechanical impact caused by the inorganic oxide due to the softness of the organic particles. By buffering the scratches are less likely to occur on the surface as well as has the advantage of reducing the dishing effect. The metal film polishing slurry composition of the present invention is useful as a metal film polishing slurry containing copper.
화학 기계적 연마, 무기산화물, 유기화합물, 슬러리 Chemical mechanical polishing, inorganic oxides, organic compounds, slurries
Description
본 발명은 무기산화물이 코팅된 유기 화합물을 함유하는 것을 특징으로 하는 금속막 연마용 슬러리 조성물에 관한 것으로서, 구리를 포함하는 금속막 등의 반도체 웨이퍼의 연마에 사용될 수 있는 조성물에 관한 것이다.The present invention relates to a slurry composition for polishing a metal film comprising an organic compound coated with an inorganic oxide, and more particularly to a composition that can be used for polishing a semiconductor wafer such as a metal film containing copper.
반도체 제조 공정에서 금속막의 화학 기계 연마를 위해 이용되는 연마재로서 종래부터 실리카나 알루미나 등의 무기입자를 수계에 분산시킨 연마재가 많이 사용되고 있다. 그러나 이러한 무기입자가 분산된 슬러리는 무기입자가 가지는 높은 경도로 인해 연마 후 금속막 표면에 스크래치 및 크랙을 발생하여 수율 저하를 가져오게 되었다. 이러한 표면 스크래치를 방지하기 위해 여러 가지 첨가제가 혼합되어 연마가 진행되었으나 무기입자가 가지는 고유의 경도로 인해 야기되는 표면 스크래치 및 크랙을 방지할 수는 없었다.BACKGROUND ART [0002] Abrasives in which inorganic particles such as silica and alumina are dispersed in a water system are conventionally used as abrasives for chemical mechanical polishing of metal films in semiconductor manufacturing processes. However, due to the high hardness of the inorganic particles, the slurry in which the inorganic particles are dispersed may cause scratches and cracks on the surface of the metal film after polishing, resulting in a decrease in yield. In order to prevent such surface scratches, various additives were mixed and polished, but surface scratches and cracks caused by the inherent hardness of the inorganic particles could not be prevented.
또한 최근에는 무기입자가 아닌 고분자 유기입자를 연마제로 사용하여 금속막을 연마하는 방법이 개시되었다. 이러한 유기입자는 무기입자에 비해 연마 후 표면 스크래치 발생을 저하시키나 실리카나 알루미나 같은 무기입자와 비교하여 경도가 낮기 때문에 높은 연마속도를 구현할 수 없는 문제점을 가지고 있다.Recently, a method of polishing a metal film using polymer organic particles other than inorganic particles as an abrasive has been disclosed. These organic particles have a problem of lowering the surface scratch after polishing as compared to the inorganic particles, but have a problem in that a high polishing rate cannot be realized because the hardness is low compared to inorganic particles such as silica or alumina.
또한 무기입자로 인해 발생되는 스크래치를 감소하며, 유기 입자의 연마 속도를 개선하기 위해 유기 입자의 표면에 무기입자를 부착시켜 유기 복합체를 제조하여 연마제로 사용하는 방법이 개시되었다. 유기 입자의 표면에 무기입자를 부착시켜 예비 입자를 형성하고, 그 후, 상기 예비 입자 존재 하에 유기 규소 화합물 및 유기 금속 화합물을 중축합시켜 무기입자를 표면에 부착시키는 방법이 개시되었다. 그러나 이러한 방법은 표면에 무기입자를 부착시키기 위해 규소 예비 입자를 형성하는 것과 무기 및 금속 화합물에 유기 화합물을 결합시키는 과정이 복잡할 뿐만 아니라 유기 치환된 입자들끼리 미리 결합되어 응집되어 스크래치 증가의 문제점이 발생할 수 있다. In addition, to reduce the scratches caused by the inorganic particles, in order to improve the polishing rate of the organic particles, a method of preparing an organic composite using an inorganic particle by attaching the inorganic particles to the surface of the organic particles has been disclosed. Disclosed is a method of attaching inorganic particles to a surface by attaching inorganic particles to a surface of organic particles to form preliminary particles, and then polycondensing an organosilicon compound and an organometallic compound in the presence of the preliminary particles. However, this method is not only complicated to form silicon preliminary particles for attaching inorganic particles to the surface and to bond organic compounds to inorganic and metal compounds, but also to increase the scratches by pre-aggregation and aggregation of organic substituted particles. This can happen.
상기한 바와 같은 종래의 문제점을 해소하기 위한 것으로 본 발명은 유기입자로 된 코어(core)와 이의 표면에 무기산화물이 쉘(shell)형태의 막으로 코팅된 코어-쉘 입자를 사용함으로써, 무기입자로 인해 발생되는 스크래치를 감소시킬 수 있으며, 유기입자의 낮은 연마속도를 증가시킬 수 있다. 특히, 본 발명은 종래 유기입자의 표면에 무기입자가 흡착된 상태의 복합입자를 사용하는 것에 비하여 균일하게 연마되며, 연마 후 표면에 발생되는 스크래치를 감소시킬 수 있다.In order to solve the conventional problems as described above, the present invention provides an inorganic particle by using a core made of organic particles and core-shell particles coated with a shell-type film of inorganic oxide on the surface thereof. It is possible to reduce the scratches generated by, and to increase the low polishing rate of the organic particles. In particular, the present invention is uniformly polished as compared to the use of the composite particles of the inorganic particles adsorbed on the surface of the conventional organic particles, it is possible to reduce the scratches generated on the surface after polishing.
본 발명자들은 막형태의 무기산화물로 인해 낮은 압력 조건에서도 유기 입자가 가질 수 없는 높은 연마속도과 균일한 연마를 할 수 있으며, 유기입자의 연성으로 인해 무기산화물로 인해 발생되는 연마 후 표면 스크래치 및 디싱을 감소시킬 수 있는 가능성이 있어 본 발명을 완성하게 되었다. 만약 유기입자에 입자형태의 무기산화물이 부착된 경우에는 부분적인 유기 입자와 무기입자간의 분리가 일어날 수 있으며, 분리된 무기입자와 유기입자간의 응집이 일어날 수 있어 연마 특성의 불균일도가 나타나게 된다.The present inventors can achieve a high polishing rate and uniform polishing that organic particles cannot have even at low pressure due to the inorganic oxide in the form of a film, and perform surface scratching and dishing after polishing caused by the inorganic oxide due to the softness of the organic particles. There is a possibility of reducing the present invention. If the inorganic particles are attached to the organic particles in the form of particles, partial separation between the organic particles and the inorganic particles may occur, and agglomeration between the separated inorganic particles and the organic particles may occur, resulting in unevenness in polishing characteristics.
따라서 본 발명의 목적은 무기산화물이 코팅된 유기화합물을 포함하는 금속막 연마용 슬러리 조성물을 제공하는 데 있다.Accordingly, an object of the present invention is to provide a slurry composition for polishing a metal film including an organic compound coated with an inorganic oxide.
또한 본 발명의 또 다른 목적은 표면에 코팅되어 있는 무기산화물로 인해 낮은 압력 조건에서도 높은 연마속도를 가지며, 유기입자의 연성으로 인해 연마 후 표면에 스크래치 및 디싱을 감소시키는 데 있다.In addition, another object of the present invention is to have a high polishing rate even under low pressure conditions due to the inorganic oxide coated on the surface, and to reduce scratches and dishing on the surface after polishing due to the softness of the organic particles.
본 발명은 반도체 제조 공정에서 금속막을 화학 기계적 연마하기 위한 슬러리 조성물에 관한 것이다. 구체적으로 무기산화물의 높은 강도와 유기입자의 연성을 동시에 갖도록, 유지입자로 된 코어에 무기산화물이 쉘 형태로 코팅된 코어-쉘 입자를 포함하는 금속막 연마용 슬러리 조성물에 관한 것이다.The present invention relates to a slurry composition for chemical mechanical polishing of a metal film in a semiconductor manufacturing process. In particular, the present invention relates to a slurry composition for polishing a metal film including core-shell particles coated with an inorganic oxide in a shell form on a core of maintenance particles so as to have high strength of an inorganic oxide and ductility of organic particles at the same time.
구체적으로 본 발명은 평균입경 10 ~ 1000nm인 구형의 유기입자로 된 코어와, 이의 표면에 1 ~ 100nm 두께의 무기산화물이 막형태로 코팅된 코어-쉘 입자를 0.0001 ~ 20 중량% 포함하는 금속막 연마용 슬러리 조성물에 관한 것이다.Specifically, the present invention provides a metal film comprising 0.0001 to 20 wt% of a core made of spherical organic particles having an average particle diameter of 10 to 1000 nm and core-shell particles coated with an inorganic oxide having a thickness of 1 to 100 nm on the surface thereof. It relates to a polishing slurry composition.
본 발명의 금속막 연마용 슬러리는 연마 촉진제를 더 포함할 수 있으며, 상기 연마 촉진제와 함께 산화제를 더 포함할 수 있다.The slurry for polishing a metal film of the present invention may further include a polishing accelerator, and may further include an oxidizing agent together with the polishing accelerator.
또한, 본 발명의 금속막 연마용 슬러리는 pH가 3 내지 10인 것이 바람직하다.Moreover, it is preferable that pHs of the metal film polishing slurry of this invention are 3-10.
또한, 본 발명에 따른 연마 조성물은 부식억제제, 계면활성제를 추가로 더 함유할 수 있으며, pH를 3 내지 10으로 유지하기 위해 pH 조절제를 더 함유할 수 있다.In addition, the polishing composition according to the present invention may further contain a corrosion inhibitor, a surfactant, and may further contain a pH adjuster to maintain a pH of 3 to 10.
본 발명에 따른 연마용 슬러리는 반도체 기판의 금속막의 연마 공정에 적용할 경우 금속 막에 대한 연마속도가 높고 스크래치 발생을 억제할 뿐만 아니라 디싱을 감소시키는 장점을 가지고 있다. 특히, 구리를 포함하는 금속막에 사용하기에 적합하다.The polishing slurry according to the present invention has the advantage of high polishing rate for the metal film, suppression of scratches and reduction of dishing when applied to the polishing process of the metal film of the semiconductor substrate. In particular, it is suitable for use for the metal film containing copper.
이하는 본 발명에 대하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명자들은 상기 무기산화물이 코팅되어 있는 코어-쉘(core-shell) 형태의 유기화합물이 종래 유기입자의 표면에 무기입자가 부착되거나 결합된 형태에 비하여 균일하게 연마되며, 높은 연마속도 및 표면의 스크래치 감소 효과가 있음을 발견하여 본 발명을 완성하였다.The inventors of the present invention provide that the core-shell type organic compound coated with the inorganic oxide is uniformly polished as compared with a form in which inorganic particles are attached to or bonded to the surface of conventional organic particles. The present invention was completed by discovering the effect of scratch reduction.
특히, 유기입자의 평균입경 10 ~ 1000nm이고, 구형이며, 이러한 유기입자의 표면에 1 ~ 100nm 두께의 무기산화물이 쉘형태로 코팅된 경우 보다 우수한 연마속도 및 표면 스크래치 감소효과가 있다. In particular, when the average particle diameter of the organic particles is 10 ~ 1000nm, spherical, and the inorganic oxide having a thickness of 1 ~ 100nm coated on the surface of the organic particles in the form of a shell, there is an excellent polishing rate and surface scratch reduction effect.
본 발명의 금속막 연마용 슬러리 조성물은 이러한 코어-쉘 입자를 0.0001 ~ 20 중량%, 보다 바람직하게는 0.001 ~ 10 중량% 포함하는 것이 바람직하다. 0.0001 중량% 미만으로 포함하는 경우는 연마 속도가 매우 낮고, 20 중량%를 초과하는 경우 분산 안정성이 나빠져 스크래치 발생의 빈도가 높은 문제점이 발생할 수 있다. The slurry composition for polishing a metal film of the present invention preferably contains 0.0001 to 20% by weight, more preferably 0.001 to 10% by weight, of such core-shell particles. When the amount is less than 0.0001% by weight, the polishing rate is very low, and when the amount is more than 20% by weight, dispersion stability may deteriorate and a high frequency of scratches may occur.
본 발명에서 상기 유기입자는 평균입경이 10 ~ 1000nm인 것이 바람직한데, 더욱 바람직하게는 50 ~ 600nm인 범위인 것이 바람직하며, 상기 입경이 1000nm를 초과할 경우 거대 입자에 의한 스크래치가 발생할 수 있으며, 분산성이 나빠질 수 있어 불리하며, 상기 입경이 10nm 미만인 경우 제조하기 어려울 뿐만 아니라 연마속도가 현저히 저하되는 문제가 있어 바람직하지 못하다. 상기 유기 입자의 경우 폴리스티렌, 폴리메틸메타크릴레이트, 폴리비닐클로라이드, 폴리아세탈, 폴리에스테르, 폴리아미드, 폴리이미드 또는 이들의 공중합체인 것이 바람직하다.In the present invention, the organic particles preferably have an average particle diameter of 10 to 1000 nm, more preferably 50 to 600 nm, and when the particle diameter exceeds 1000 nm, scratches may occur due to large particles. Dispersibility may be deteriorated and disadvantageous, and when the particle diameter is less than 10 nm, not only is difficult to prepare, but also the polishing rate is significantly lowered, which is not preferable. In the case of the organic particles, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyacetal, polyester, polyamide, polyimide or copolymers thereof are preferable.
본 발명에서 유기입자의 표면에 코팅되는 무기산화물은 실리카, 알루미나, 제올라이트, 티타니아, 세리아, 지르코니아 등이 사용 가능하다. 바람직하게는 무기산화물의 두께가 1 ~ 100nm 범위인 것이 바람직하다. 더 바람직하게는 무기산화물의 두께가 1 ~ 50nm 범위인 것이 바람직하며, 상기 두께가 100nm를 초과할 경우 입자 사이즈가 커져 분산성이 나빠질 수 있어 불리하며, 상기 두께가 1nm 미만인 경우 무기산화물의 물성을 가질 수 없어 바람직하지 못하다. In the present invention, the inorganic oxide coated on the surface of the organic particles may be silica, alumina, zeolite, titania, ceria, zirconia, or the like. Preferably, the thickness of the inorganic oxide is preferably in the range of 1 to 100 nm. More preferably, the thickness of the inorganic oxide is preferably in the range of 1 to 50 nm, and if the thickness is greater than 100 nm, the particle size may be increased and the dispersibility may be deteriorated. If the thickness is less than 1 nm, the physical properties of the inorganic oxide are It is not desirable to have it.
상기 무기산화물을 막 형태로 코팅하기 위해서는 증류수 또는 용매에 유기입자를 균일하게 분산시킨 후, 여기에 무기산화물 전구체를 첨가하여 균일하게 혼합한다. 이때 반응시간을 단축하기 위하여 촉매를 사용할 수 있다. 무기산화물 전구체의 양에 따라 막형태로 코팅되며, 전구체는 상기 증류수 또는 용매의 함량에 대하여 5 ~ 15 중량%, 보다 바람직하게는 10 중량%를 사용하는 것이 막형태로 제조가 가능하다. 상기 무기산화물의 혼합 후에는 100℃ 이하의 온도에서 24시간 이내로 반응 후 상온으로 냉각시킨다. 냉각된 슬러리는 세척 및 필터하여 코어-쉘의 입자를 얻을 수 있다.In order to coat the inorganic oxide in the form of a film, organic particles are uniformly dispersed in distilled water or a solvent, and then, an inorganic oxide precursor is added thereto and mixed uniformly. In this case, a catalyst may be used to shorten the reaction time. According to the amount of the inorganic oxide precursor is coated in the form of a film, the precursor may be prepared in the form of a film using 5 to 15% by weight, more preferably 10% by weight based on the content of the distilled water or solvent. After mixing the inorganic oxide, the reaction is cooled to room temperature after the reaction within 24 hours at a temperature of 100 ℃ or less. The cooled slurry can be washed and filtered to obtain particles of the core-shell.
본 발명은 유기입자의 표면에 코팅된 무기산화물로 인해 낮은 압력에서도 높은 연마 속도를 가질 수 있다. 또한, 내부의 유기입자의 연성으로 인해 무기산화물에 의해 가해질 물리적인 힘을 감소시킬 수 있어 표면의 스크래치를 줄일 수 있는 장점을 가지고 있다. 또한 표면에 코팅되어 있는 무기산화물로 인해 유기입자 간의 응집 및 침전 현상을 방지할 수 있는 장점도 가지고 있다. The present invention can have a high polishing rate even at low pressure due to the inorganic oxide coated on the surface of the organic particles. In addition, due to the ductility of the organic particles therein can reduce the physical force to be applied by the inorganic oxide has the advantage of reducing the scratch of the surface. In addition, the inorganic oxide coated on the surface has the advantage of preventing aggregation and precipitation between organic particles.
본 발명에 따른 금속막 연마용 슬러리는 연마 촉진제를 더 포함할 수 있다. 상기 연마촉진제는 구리막의 연마속도를 증가시키는 역할을 하는 것으로 유기산, 아미노산, 킬레이트제, 및 고분자 유기산 등이 사용된다. 유기산으로는 시트르산, 아디프산, 숙신산, 옥살산, 글루콘산, 말산, 말론산, 프로피온산, 타르타르산, 머캅토숙신산, 벤젠테트라카르복시산, 글리콜산, 락트산, 말레산, 프탈산, 아스코르브산에서 선택되는 어느 하나 또는 둘 이상의 혼합물, 아미노산으로는 글루탐산, 알라닌, 글리신, 아르기닌, N-메틸글리신, 에틸글리신, 리신, 아스파트산에서 선택되는 어느 하나 또는 둘 이상의 혼합물, 킬레이트제로는 에틸렌디아민테트라아세트산(EDTA), 니트릴로트리아세트산(NTA), 이미노디아세트산(IDA), 퀴놀린산(QNA)에서 선택되는 어느 하나 또는 둘 이상의 혼합물, 고분자 유기산으로는 폴리아크릴산(PAA)을 사용할 수 있다. 이때 상기 연마 촉진제는 0.01 ~ 5 중량%, 보다 바람직하게는 0.1 ~ 4 중량% 범위로 포함되는 것이 바람직하다. 함량이 0.01중량% 미만일 경우 금속막의 연마속도가 낮아 사용할 수 없으며, 5중량% 초과하는 경우 과량의 촉진제로 인해 슬러리 안정성을 파괴하여 스크래치를 유도할 수 있으며, 금속막의 부식을 야기할 수 있다.The slurry for polishing a metal film according to the present invention may further include a polishing accelerator. The polishing accelerator serves to increase the polishing rate of the copper film, and organic acids, amino acids, chelating agents, and polymer organic acids are used. The organic acid is any one selected from citric acid, adipic acid, succinic acid, oxalic acid, gluconic acid, malic acid, malonic acid, propionic acid, tartaric acid, mercaptosuccinic acid, benzenetetracarboxylic acid, glycolic acid, lactic acid, maleic acid, phthalic acid, and ascorbic acid. Or mixtures of two or more, amino acids such as glutamic acid, alanine, glycine, arginine, N-methylglycine, ethylglycine, lysine, aspartic acid, or any mixture of two or more thereof, chelating agents include ethylenediaminetetraacetic acid (EDTA), Polyacrylic acid (PAA) may be used as the polymer organic acid, any one or two or more selected from nitrilotriacetic acid (NTA), imino diacetic acid (IDA), and quinoline acid (QNA). At this time, the polishing accelerator is preferably included in the range 0.01 to 5% by weight, more preferably 0.1 to 4% by weight. If the content is less than 0.01% by weight, the polishing rate of the metal film is low and cannot be used. If the content is more than 5% by weight, the excessive accelerator may destroy the stability of the slurry to induce scratches, and may cause corrosion of the metal film.
또한 본 발명의 금속막 연마용 슬러리는 산화제를 더 포함할 수 있다. 상기 산화제는 금속막의 표면을 산화시키는 역할을 하며, 본 발명에 따른 연마조성물에 함유되는 산화제로서는 하나 이상의 퍼옥시기를 가지는 화합물, 또는 이들의 혼합물이 사용될 수 있다. 하나 이상의 퍼옥시기를 함유하는 화합물의 구체적인 예로서는, 과산화수소, 우레아 과산화수소와 같은 과산화수소 첨가 생성물, 암모늄퍼설페이트, 모노퍼설페이트, 디퍼설페이트, 나트륨퍼옥사이드, KIO3, HI5O6 및 이들의 혼합물 등이 있다. 상기 산화제로서 바람직하게는 과산화수소, 암모늄퍼설페이트, KIO3, HI5O6가 바람직하며, 가장 바람직하게는 과산화수소가 사용된다. 이때 상기 산화제는 0.1 ~ 10 중량%, 보다 바람직하게는 0.1 ~ 5 중량% 범위로 포함되는 것이 바람직하다. 0.1중량% 이하일 경우 금속막의 연마속도가 낮으며, 10중량% 이상일 경우 금속막의 부식을 야기할 수 있다.In addition, the slurry for polishing a metal film of the present invention may further include an oxidizing agent. The oxidant serves to oxidize the surface of the metal film, and as the oxidant contained in the polishing composition according to the present invention, a compound having one or more peroxy groups, or a mixture thereof may be used. Specific examples of compounds containing one or more peroxy groups include hydrogen peroxide, hydrogen peroxide addition products such as urea hydrogen peroxide, ammonium persulfate, monopersulfate, dipersulfate, sodium peroxide, KIO3, HI5O6, and mixtures thereof. As the oxidizing agent, hydrogen peroxide, ammonium persulfate, KIO3, HI5O6 are preferable, and hydrogen peroxide is most preferably used. In this case, the oxidant is preferably included in the range 0.1 to 10% by weight, more preferably 0.1 to 5% by weight. If it is 0.1 wt% or less, the polishing rate of the metal film is low, and if it is 10 wt% or more, it may cause corrosion of the metal film.
본 발명의 금속막 연마용 슬러리 조성물의 적절한 pH 범위는 7 ~ 10이며, 더욱 바람직한 pH 범위는 7 ~ 9 이다. pH의 조절은 수산화칼륨, 암모니아, 테트라메틸암모늄하이드록사이드, 테트라에틸암모늄하이드록사이드, 테트라부틸암모늄하이드록사이드, 아민, 아미노알콜 또는 질산 등을 적절히 가함으로서 가능하다. pH가 10 보다 높으면 연마속도가 감소하여 적절하지 못하다. The suitable pH range of the slurry composition for polishing metal films of the present invention is 7 to 10, and more preferably 7 to 9 pH range. The pH can be adjusted by appropriately adding potassium hydroxide, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, amine, aminoalcohol or nitric acid and the like. If the pH is higher than 10, the polishing rate decreases, which is not appropriate.
또한 본 발명의 금속막 연마용 슬러리 조성물은 부식억제제, 계면활성제, 소포제로부터 선택되는 1종 또는 2종 이상을 더 포함할 수 있다.In addition, the slurry composition for polishing a metal film of the present invention may further include one or two or more selected from a corrosion inhibitor, a surfactant, and an antifoaming agent.
상기 부식억제제는 벤조트리아졸, 5-아미노테트라졸, 1-알킬-5-아미노테트라졸, 5-히드록시-테트라졸, 1-알킬-5-히드록시-테트라졸, 테트라졸-5치올, 이미다졸, 1-H-벤조트리아졸-5-카르복시산, 1,2,3-트리아졸, 1,2,4-트리아졸, 1,2,3-트리아졸-3-카로복시산, 테트라졸, 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것이 바람직하다. 이때 함량은 0.0001 ~ 1 중량%, 보다 바람직하게는 0.0005 ~ 0.6중량% 범위로 포함되는 것이 바람직하다.0.0001중량% 이하일 경우 금속막의 부식 조절능력이 저하되며, 1중량% 이상일 경우 금속막의 연마속도를 저하시킨다.The corrosion inhibitors include benzotriazole, 5-aminotetrazole, 1-alkyl-5-aminotetrazole, 5-hydroxy-tetrazole, 1-alkyl-5-hydroxy-tetrazole, tetrazol-5thiol, Imidazole, 1-H-benzotriazole-5-carboxylic acid, 1,2,3-triazole, 1,2,4-triazole, 1,2,3-triazole-3-carboxic acid, tetrazole , And mixtures thereof. In this case, the content is preferably included in the range of 0.0001 to 1% by weight, more preferably 0.0005 to 0.6% by weight. If the amount is 0.0001% by weight or less, the corrosion control ability of the metal film is lowered. Lowers.
계면활성제 및/또는 친수성 폴리머로서는 산형태의 구조가 바람직하고, 염 구조를 가질 경우에는 암모늄염, 칼륨염, 나트륨염 등을 들 수 있으며, 특히 암모늄염 및 칼륨염이 바람직하다. 계면활성제와 친수성 폴리머는 모두 피연마면으로의 접촉각을 저하시키는 작용을 갖고 있고, 균일한 연마를 촉진하는 작용을 갖는다. 사용되는 계면활성제 및/또는 친수성 폴리머로서는 이하의 군에서 선택된 것이 바람직하다.The surfactant and / or hydrophilic polymer is preferably an acidic structure, and in the case of having a salt structure, ammonium salts, potassium salts, sodium salts, and the like, and ammonium salts and potassium salts are particularly preferable. Both the surfactant and the hydrophilic polymer have a function of lowering the contact angle to the surface to be polished, and have a function of promoting uniform polishing. As surfactant and / or hydrophilic polymer used, what was chosen from the following groups is preferable.
음이온 계면활성제로서는 카르복실산염, 술폰산염, 황산에스테르염, 인산에스테르염 등을 들 수 있다. 그 중,카르복실산염으로서는 비누, N-아실아미노산염, 폴리옥시에틸렌 또는 폴리옥시프로필렌알킬에테르카르복실산염,아실화펩티드 등을 들 수 있다. 술폰산염으로서는 알킬술폰산염, 알킬벤젠 및 알킬나프탈렌술폰산염, 나프탈렌술폰산염, 술포숙신산염, α-올레핀술폰산염, N-아실술폰산염 등을 들 수 있다. 황산에스테르염으로서는 황산화유, 알킬황산염, 알킬에테르황산염, 폴리옥시에틸렌 또는 폴리옥시프로필렌알킬알릴에테르황산염, 알킬아미드황산염 등을 들 수 있다. 인산에스테르염으로서는 알킬인산염, 폴리옥시에틸렌 또는 폴리옥시프로필렌알킬알릴에테르인산염 등을 들 수 있다.Examples of the anionic surfactants include carboxylates, sulfonates, sulfate ester salts, and phosphate ester salts. Among them, soaps, N-acylamino acid salts, polyoxyethylene or polyoxypropylene alkyl ether carboxylates, acylated peptides and the like can be given. Examples of sulfonates include alkyl sulfonates, alkylbenzenes and alkylnaphthalene sulfonates, naphthalene sulfonates, sulfosuccinates, α-olefin sulfonates, N-acyl sulfonates, and the like. Examples of the sulfate ester salts include sulfated oils, alkyl sulfates, alkyl ether sulfates, polyoxyethylene or polyoxypropylene alkylallyl ether sulfates, and alkylamide sulfates. Examples of the phosphate ester salts include alkyl phosphates, polyoxyethylene or polyoxypropylene alkyl allyl ether phosphates.
양이온 계면활성제로서는 지방족 아민염, 지방족 4급 암모늄염, 염화벤잘코늄염, 염화벤제토늄, 피리디늄염,이미다졸리늄염 등을 들 수 있다. 양성 계면 활성제로서는 카르복시베타인형, 술포베타인형, 아미노카르복실산염, 이미다졸리늄베타인, 레시틴, 알킬아민옥사이드 등을 들 수 있다.Examples of the cationic surfactants include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium chlorides, benzetonium chlorides, pyridinium salts, and imidazolinium salts. Examples of the amphoteric surfactant include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine, lecithin, alkylamine oxide and the like.
비이온 계면활성제로서는 에테르형, 에테르에스테르형, 에스테르형, 질소함 유형 등을 들 수 있다. 에테르형으로서는 폴리옥시에틸렌알킬 및 알킬페닐에테르, 알킬알릴포름알데히드 축합 폴리옥시에틸렌에테르, 폴리옥시에틸렌 폴리옥시프로필렌 블록 폴리머, 폴리옥시에틸렌폴리옥시프로필렌알킬에테르 등을 들 수 있다. 에테르에스테르형으로서는 글리세린에스테르의 폴리옥시에틸렌에테르, 소르비탄에스테르의 폴리옥시에틸렌에테르, 소르비톨 에스테르의 폴리옥시에틸렌에테르 등을 들 수 있다. 에스테르형으로서는 폴리에틸렌글리콜 지방산 에스테르, 글리세린에스테르, 폴리글리세린에스테르, 소르비탄에스테르,프로필렌글리콜에스테르, 자당 에스테르 등을 들 수있다. 질소함유형으로서는 지방산 알칸올아미드, 폴리옥시에틸렌 지방산 아미드, 폴리옥시에틸렌알킬아미드 등을 들 수 있다.Examples of nonionic surfactants include ether type, ether ester type, ester type and nitrogen group type. Examples of the ether type include polyoxyethylene alkyl and alkylphenyl ether, alkyl allyl formaldehyde condensation polyoxyethylene ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether and the like. Examples of the ether ester type include polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester, and the like. Examples of the ester type include polyethylene glycol fatty acid esters, glycerin esters, polyglycerol esters, sorbitan esters, propylene glycol esters, and sucrose esters. Examples of the nitrogen-containing type include fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkylamides, and the like.
계면활성제 중 바람직하게는 음이온 계면활성제이며, 그중에 도데실벤젠 설폰산, 라우릴옥시설폰산, 리그닌설폰산, 나프탈렌설폰산, 디부틸나프탈렌설폰산, 라우릴에테르설폰산 또는 이들의 염으로부터 선택되는 1종 이상을 사용하는 것이 바람직하며 계면활성제의 함량은 연마용 조성물 총 중량에 대하여 0.001 내지 0.5 중량%인 것이 바람직하며, 0.05 내지 0.5중량%인 것이 보다 바람직하다. 도데실벤젠설폰산 또는 그의 염은 12개의 탄소 사슬과 말단에 설폰산(sulfonate, SO3-)기를 갖는 구조로서 부식방지 및 구리표면의 윤활작용을 함으로써 연마속도의 증가와 부식방지 기능이 모두 가능하여 보다 바람직하다. 계면활성제의 함량이 0.001중량% 미만으로 적을 경우 충분한 부식방지 작용을 할 수 없으며, 0.5 중량%을 초과하여 많을 경우 다량의 거품 발생으로 사용하기에 부적절하다.Among the surfactants are preferably anionic surfactants, among them selected from dodecylbenzene sulfonic acid, lauryl oxulonic acid, lignin sulfonic acid, naphthalene sulfonic acid, dibutylnaphthalene sulfonic acid, lauryl ether sulfonic acid or salts thereof. It is preferable to use at least one, and the content of the surfactant is preferably 0.001 to 0.5% by weight, more preferably 0.05 to 0.5% by weight based on the total weight of the polishing composition. Dodecylbenzenesulfonic acid or its salt has a structure of 12 carbon chains and sulfonic acid (sulfonate, SO 3- ) groups at the end, which can increase both the polishing rate and the corrosion prevention function by preventing corrosion and lubricating copper surface. It is more preferable. If the amount of the surfactant is less than 0.001% by weight, it may not be sufficient to prevent corrosion, and if it is more than 0.5% by weight, it is not suitable for use in generating a large amount of foam.
상기 소포제는 계면활성제의 사용에 따라 발생하는 거품 억제 기능을 하는 것으로서 그 종류에 제한을 둘 필요는 없고, 함량도 계면활성제의 사용에 따라 적절히 조절하여 사용할 수 있다. 소포제는 실리콘계와 비실리콘계 소포제로 분류할 수 있으며, 실리콘계 소포제로는 폴리디알킬실록산을 함유한 소포제를, 비실리콘계 소포제로는 폴리알킬렌글리콜을 함유한 소포제를 예로 들 수 있다. 상기 폴리디알킬실록산 및 폴리알킬렌글리콜의 알킬은 C1-C5의 직쇄 또는 분지쇄 알킬인 것이 바람직하다.The antifoaming agent has a foam suppression function generated by the use of the surfactant, and there is no need to limit the kind thereof, and the content may be appropriately adjusted according to the use of the surfactant. Defoamers can be classified into silicone-based and non-silicone-based antifoaming agents. Examples of the antifoaming agents include antifoaming agents containing polydialkylsiloxanes and antifoaming agents containing polyalkylene glycols. The alkyl of the polydialkylsiloxane and polyalkylene glycol is preferably C1-C5 straight or branched alkyl.
본 발명은 상술한 바와 같이 무기산화물의 강도와 유기입자의 연성을 동시에 가지며, 낮은 압력 조건에서도 높은 연마속도를 유지하면서 표면 스크래치 발생이 낮으며, 디싱을 감소시키는 장점이 있다.As described above, the inorganic oxide has the strength of the inorganic oxide and the ductility of the organic particles at the same time, while maintaining a high polishing rate even under low pressure conditions, the surface scratches are low, there is an advantage of reducing dishing.
이하 본 발명을 실시예를 들어 더욱 더 상세히 설명하나 하기의 실시예가 본 발명을 한정하는 것이 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the present invention.
[제조예][Manufacturing Example]
유기입자로는 평균입경이 150nm인 구형의 폴리스티렌 입자를 제조하여 사용하였다. 상기 폴리스티렌 입자의 표면에 쉘 형태로 실리카가 코팅된 SiO2/폴리스티렌 졸을 제조하였으며, 그 코팅 두께는 하기 표 1과 같다.As organic particles, spherical polystyrene particles having an average particle diameter of 150 nm were prepared and used. SiO 2 / polystyrene sol coated with silica in the form of a shell on the surface of the polystyrene particles was prepared, the coating thickness is shown in Table 1 below.
이때 코팅방법으로는 99.9% 에탄올 2000ml에 폴리스티렌 입자 50g을 넣어 분산시킨 후 29% 수산화암모늄 수용액 70ml와 98% 테트라에틸오르쏘실리케이트(TEOS) 70g, 80g, 90g을 각각 넣고 혼합하였다. 균일 혼합 후 50℃에서 1.5시간 반응 후 세척, 필터하여 실리카가 코팅된 폴리스티렌 입자를 제조하였다. 제조된 입자를 도 2에 도시하였다.In this case, 50 g of polystyrene particles were dispersed in 2000 ml of 99.9% ethanol, and 70 ml of aqueous 29% ammonium hydroxide solution and 70 g, 80 g, and 90 g of 98% tetraethylorthosilicate (TEOS) were mixed. After homogeneous mixing, the mixture was washed at 50 ° C. for 1.5 hours, washed, and filtered to prepare silica-coated polystyrene particles. The prepared particles are shown in FIG.
[실시예][Example]
연마에 사용된 웨이퍼는 실리콘 기판위에 Ta를 250Å 증착하고, CVD 법에 의해 Cu Seed를 1000Å 증착한 후에 EP법을 이용해 15000Å 증착한 구리 웨이퍼를 사용하였으며, 연마장비는 G&P Technology사의 Poli 400, 연마패드는 로델사의 IC 1000을 이용하여, 구리연마 테스트를 실시하였고, 연마조건은 Table/Head 속도를 93/87 rpm, 연마압력을 70 g/㎠, 슬러리 공급유량 100 ml로 하였다. 구리막 두께는 AIT사의 Four Point Probe로 측정하였다.The wafer used for polishing was 250Å of Ta on a silicon substrate, 1000Å of Cu Seed by CVD, and then 15000Å of copper using EP. The polishing equipment was Poli 400 and polishing pad of G & P Technology. The copper polishing test was carried out using a Rodel IC 1000, and the polishing conditions were Table / Head speed of 93/87 rpm, polishing pressure of 70 g / cm 2, and slurry supply flow rate of 100 ml. Copper film thickness was measured with AIT Four Point Probe.
본 실시예에서 pH 조절제로는 KOH와 HNO3를 사용하였다. 또한, 구리막 연마 후 투광기 또는 주사전자현미경(SEM)으로 연마 후 표면 상태를 관찰하여 스크래치나 부식이 발생하였는지 확인하였다. KOH and HNO 3 were used as pH adjusting agents in this example. In addition, after polishing the copper film, the surface state after polishing was observed with a light emitter or a scanning electron microscope (SEM) to check whether scratches or corrosion occurred.
[실시예 1 ~ 5][Examples 1 to 5]
상기 제조예에서 제조된 폴리스티렌/SiO2 입자와 연마 촉진제로 글리신을 사 용하여 표 1에 나타낸 바와 같은 조성으로 슬러리를 제조하였다.Slurry was prepared in the composition as shown in Table 1 using glycine as the polystyrene / SiO 2 particles prepared in the above preparation and the polishing accelerator.
무기산화물이 코팅된 두께에 따른 연마 평가를 진행하였으며, 폴리스티렌/SiO2입자의 함량 변화와 pH 변화에 의한 연마 평가를 진행하였다. Polishing evaluation was performed according to the thickness coated with the inorganic oxide, and polishing evaluation was performed by changing the content of polystyrene / SiO 2 particles and pH.
[비교예 1]Comparative Example 1
실리카가 코팅되지 않은 평균입경이 150nm인 폴리스티렌 입자를 사용한 것을 제외하고는 실시예와 동일한 방법으로 슬러리 제조 후 실시예와 동일한 조건으로 연마를 진행하였다. Except for using polystyrene particles having an average particle diameter of 150nm uncoated silica, polishing was carried out under the same conditions as in Example after slurry preparation in the same manner as in Example.
[비교예 2]Comparative Example 2
평균입경이 150nm인 폴리메틸메타크릴레이트 중합체 입자를 10 중량% 함유하는 수분산체(D2) 100 중량부에 대해, 콜로이달 실리카로 구성된 무기입자 10 중량%를 함유하는 수분산체(D1) 50 중량부를 2시간에 걸쳐 첨가하여 폴리메틸메타크릴레이트 중합체 입자의 외부 표면에 일차 평균입경이 12nm인 실리카 입자가 표면적의 80%로 부착된 복합입자를 사용한 것을 제외하고는 실시예와 동일한 방법으로 슬러리 제조 후 실시예와 동일한 조건으로 연마를 진행하였다. 50 parts by weight of an aqueous dispersion (D1) containing 10% by weight of inorganic particles composed of colloidal silica, relative to 100 parts by weight of an aqueous dispersion (D2) containing 10% by weight of polymethyl methacrylate polymer particles having an average particle diameter of 150 nm. After the slurry was prepared in the same manner as in Example except that the composite particles were added over 2 hours and silica particles having a primary average particle diameter of 12 nm were attached to the outer surface of the polymethyl methacrylate polymer particles at 80% of the surface area. Polishing was performed under the same conditions as in Example.
[표 1][Table 1]
상기 표 1에 나타난 바와 같이 실시예에 따른 슬러리는 낮은 압력에서도 높은 연마속도를 나타내었으며, 무기산화물의 코팅 형태가 입자 형태에 비해 막 형태로 코팅된 유기입자가 연마 속도가 높게 나타나는 것을 알 수 있었다. 또한 무기산화물 막 두께가 두꺼운 경우 연마속도가 더 높음을 확인할 수 있었다. 또한 무기산화물이 코팅되지 않은 유기입자와 비교한 경우 연마 속도도 높았으며, 표면 상태도 양호하고 매우 균일하게 막이 형성되는 것을 알 수 있다. 무기산화물이 코팅된 유기화합물의 함량이 감소하여도 연마 속도가 크게 감소하지 않았을 뿐만 아니라 유기화합물의 함량 증가에도 스크래치 발생이 증가하지 않고 표면이 양호함을 확인할 수 있다. 그리고 pH 범위가 9 영역에서 연마 속도가 더 높음을 확인 할 수 있다. 무기산화물의 경우 압력이 감소함에 따라 연마 속도가 크게 감소하는 경향이 있지만, 무기산화물이 코팅된 유기화합물의 경우 압력이 감소함에도 연마 속도가 크게 감소하지 않는 경향이 있다.As shown in Table 1, the slurry according to the embodiment showed a high polishing rate even at a low pressure, and it was found that the coating rate of the inorganic oxide showed a higher polishing rate of the organic particles coated in the form of a film than the particle form. . In addition, it was confirmed that the polishing rate was higher when the thickness of the inorganic oxide film was thick. In addition, when compared with the organic particles not coated with an inorganic oxide, the polishing rate was also high, and the surface state was also good and the film was formed very uniformly. Even if the content of the inorganic oxide-coated organic compound was reduced, the polishing rate did not decrease significantly, and even if the content of the organic compound was increased, scratches did not increase and the surface was good. And it can be seen that the polishing rate is higher in the nine pH range. In the case of the inorganic oxide, the polishing rate tends to decrease significantly as the pressure decreases, but in the case of the inorganic oxide-coated organic compound, the polishing rate does not tend to decrease significantly even when the pressure decreases.
도 1은 본 발명의 코어-쉘 입자를 나타낸 단면도이다.1 is a cross-sectional view showing core-shell particles of the present invention.
도 2는 본 발명의 실시예 1의 코어-쉘 입자의 TEM사진(×200000배)이다.Figure 2 is a TEM photograph (x 200000 times) of the core-shell particles of Example 1 of the present invention.
10 : 유기입자(코어)10: organic particle (core)
20 : 무기산화물(쉘)20: inorganic oxide (shell)
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