KR101134587B1 - Polishing slurry for metal circuit - Google Patents
Polishing slurry for metal circuit Download PDFInfo
- Publication number
- KR101134587B1 KR101134587B1 KR1020050118678A KR20050118678A KR101134587B1 KR 101134587 B1 KR101134587 B1 KR 101134587B1 KR 1020050118678 A KR1020050118678 A KR 1020050118678A KR 20050118678 A KR20050118678 A KR 20050118678A KR 101134587 B1 KR101134587 B1 KR 101134587B1
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- polishing slurry
- metal wiring
- group
- weight
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 51
- 239000002002 slurry Substances 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000077 silane Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- -1 vinyl compound Chemical class 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000011664 nicotinic acid Substances 0.000 claims description 2
- 229960003512 nicotinic acid Drugs 0.000 claims description 2
- 235000001968 nicotinic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000012643 polycondensation polymerization Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000007517 polishing process Methods 0.000 abstract description 4
- 238000006748 scratching Methods 0.000 abstract 1
- 230000002393 scratching effect Effects 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- FPEANFVVZUKNFU-UHFFFAOYSA-N 2-sulfanylbenzotriazole Chemical compound C1=CC=CC2=NN(S)N=C21 FPEANFVVZUKNFU-UHFFFAOYSA-N 0.000 description 1
- OKEAMBAZBICIFP-UHFFFAOYSA-N 3-oxido-2,1,3-benzoxadiazol-3-ium Chemical compound C1=CC=CC2=[N+]([O-])ON=C21 OKEAMBAZBICIFP-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940114077 acrylic acid Drugs 0.000 description 1
- 125000005250 alkyl acrylate 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PXGPQCBSBQOPLZ-UHFFFAOYSA-N butanoic acid;propanoic acid Chemical compound CCC(O)=O.CCCC(O)=O PXGPQCBSBQOPLZ-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004756 silanes Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
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- 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
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- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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Abstract
본 발명은 금속 배선의 화학적 기계적 연마(chemical mechanical polishing: CMP)용 슬러리에 관한 것으로, 본 발명에 따른 연마 슬러리는 탄소수 1 내지 3개의 알킬기 및 알콕시기로 치환된 실란을 단독 또는 공중합하여 얻어진 오가노실리케이트(organosilicate)를 연마제로서 포함함으로써, 연마시 금속 배선에 대한 선택성이 높고, 스크래치, 디싱 및 에로젼을 최소화할 수 있어, 반도체 제조시 금속 배선의 평탄화를 위한 화학적 기계적 연마 공정에 유용하게 사용될 수 있다.The present invention relates to a slurry for chemical mechanical polishing (CMP) of metal wires, wherein the polishing slurry according to the present invention is an organosilicate obtained by singly or copolymerizing a silane substituted with an alkyl group having 1 to 3 carbon atoms and an alkoxy group. By including (organosilicate) as an abrasive, it has high selectivity for metal wiring during polishing, minimizes scratching, dishing and erosion, and thus can be usefully used in chemical mechanical polishing processes for planarization of metal wiring in semiconductor manufacturing. .
Description
본 발명은 금속 배선의 화학적 기계적 연마(chemical mechanical polishing: CMP)에 사용될 수 있는 연마 슬러리에 관한 것이다.The present invention relates to a polishing slurry that can be used for chemical mechanical polishing (CMP) of metal interconnects.
일반적으로, 반도체 제조시에는 텅스텐, 알루미늄 및 구리 등의 금속 배선막과 산화규소(SiO2) 및 질화규소(Si3N4) 등의 절연막의 평탄화를 구현하기 위해 연마 슬러리를 사용하여 웨이퍼를 연마하는 화학적 기계적 연마(CMP) 공정이 수행된다.Generally, in semiconductor manufacturing, wafers are polished using a polishing slurry to realize planarization of metal wiring films such as tungsten, aluminum and copper, and insulating films such as silicon oxide (SiO 2 ) and silicon nitride (Si 3 N 4 ). A chemical mechanical polishing (CMP) process is performed.
이러한 연마 공정에 사용되는 연마 슬러리는 연마제, 물, 분산제 및 첨가제를 포함하며, 이때 첨가제로는 산화제, 착화제, 부식방지제 및 pH 조절제 등이 사용되고, 연마제로는 퓸드(fumed) 알루미나, 퓸드 실리카, 세리아 및 지르코니아 등의 입자 경도가 큰 금속 산화물들이 주로 사용된다.The polishing slurry used in the polishing process includes an abrasive, water, a dispersant and an additive, wherein an additive includes an oxidizing agent, a complexing agent, a corrosion inhibitor and a pH adjusting agent, and the abrasive includes fumed alumina, fumed silica, Metal oxides with high particle hardness, such as ceria and zirconia, are mainly used.
그러나, 금속 배선은 절연막에 비해 막질이 부드럽고 무르며, 특히 반도체 제품의 고집적화 및 성능고속화를 위해 주목받고 있는 구리 배선은 다른 재질의 배선에 비해서도 훨씬 경도가 낮기 때문에, 경도가 큰 금속 산화물 연마제를 사용하 여 금속 배선의 CMP를 수행하는 경우에는 금속막에 스크래치(scratch), 디싱(dishing), 에로젼(erosion) 등의 손상을 입힐 수 있다.However, metal wiring is softer and softer than an insulating film. In particular, copper wiring, which is attracting attention for high integration and high performance of semiconductor products, is much lower in hardness than other materials, and therefore, a metal oxide abrasive having a high hardness is used. In the case of performing the CMP of the metal wiring, the metal film may be scratched, scratched, erosion, or the like.
이와 관련하여, 구리 배선을 형성하는 공정을 구체적으로 살펴보면, 절연막(예: 산화규소막, 질화규소막)에 트렌치(trench)를 형성한 다음, 구리의 확산을 방지하기 위한 배리어(barrier)막(확산 방지막, 예: 탄탈륨(Ta)막, 질화탄탈륨(TaN)막)을 증착시키고, 그 위에 구리 씨드 층(seed layer)을 증착시킨 후, 전기도금법(electroplating method)을 이용하여 절연막에 형성된 트렌치 패턴에 구리를 채우게 된다. 이때, 구리막이 모든 면에 대해서 같은 속도로 형성되기 때문에, 구리 배선의 형성을 완료한 후에는 항상 웨이퍼 표면에 단차가 존재하게 된다. 이런 웨이퍼 표면을 기존의 CMP용 슬러리를 이용하여 연마하게 되면, 단차가 높은 영역의 연마가 확산 방지막까지 진행되는 동안 상대적으로 단차가 낮은 영역의 구리 패턴이 깊게 파이는 디싱 등의 현상이 발생한다. 또한, 기존의 연마제 입자들은 배선막에 대한 선택비가 낮아 배선막 외에도 배리어막 또는 절연막에 대해서도 불필요한 연마를 일으켜 에로젼 등의 현상을 발생시킨다. In this regard, a process of forming a copper wiring is described in detail, and a trench is formed in an insulating film (for example, a silicon oxide film or a silicon nitride film), and then a barrier film (diffusion) is used to prevent diffusion of copper. A barrier film such as a tantalum (Ta) film and a tantalum nitride (TaN) film is deposited, and a copper seed layer is deposited thereon, and then the trench pattern formed in the insulating film by an electroplating method. It will fill copper. At this time, since the copper film is formed at the same speed for all the surfaces, there is always a step on the wafer surface after the formation of the copper wiring is completed. When the surface of the wafer is polished using a conventional slurry for CMP, a phenomenon such as dishing in which a copper pattern in a relatively low step area is deeply drilled while polishing of a high step area proceeds to the diffusion barrier layer. In addition, the conventional abrasive particles have a low selectivity to the wiring film, causing unnecessary polishing on the barrier film or the insulating film in addition to the wiring film, thereby causing phenomena such as erosion.
이러한 문제점을 해결하기 위해, 연마제를 포함하지 않는 슬러리에 대한 연구도 있었으나, 연마제 입자의 부재로 인해 충분한 연마가 이루어지기 힘들고, 웨이퍼나 연마대상에 구리 잔류물이 남아있는 등 여러 가지 문제점을 발생시켰다. In order to solve this problem, some studies have been conducted on slurries that do not contain abrasives, but due to the absence of abrasive particles, it is difficult to achieve sufficient polishing, and various problems such as copper residues remain on the wafer or the polishing target. .
이에, 본 발명의 목적은 금속 배선에 대한 선택성이 높고, 스크래치, 디싱 및 에로젼을 최소화할 수 있는 연마 슬러리를 제공하는 것이다. Accordingly, an object of the present invention is to provide a polishing slurry having high selectivity for metal wiring and minimizing scratch, dishing and erosion.
상기 목적을 달성하기 위하여 본 발명에서는, 탄소수 1 내지 3개의 알킬기 및 알콕시기로 치환된 실란을 단독 또는 공중합하여 얻어진 오가노실리케이트(organosilicate)를 연마제로서 포함하는, 금속 배선용 연마 슬러리를 제공한다. In order to achieve the above object, the present invention provides a polishing slurry for metal wiring, comprising an organosilicate obtained by singly or copolymerizing a silane substituted with an alkyl group having 1 to 3 carbon atoms and an alkoxy group as an abrasive.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 연마 슬러리는 탄소수 1 내지 3개의 알킬기 및 알콕시기를 갖는 실란으로부터 유도된 중합체인 오가노실리케이트를 연마제로서 함유하는 것을 특징으로 하며, 상기 오가노실리케이트 연마제 입자는 연마시 배리어막이나 절연막에 대한 연마속도를 크게 감소시키고, 입자 내의 알킬기 및 알콕시기가 금속막 표면에 대해서 쿠션(cushion) 역할을 함과 동시에 금속막 표면에 생성된 금속 이온과 결합하여 보호막을 형성함에 기인하여, 연마시 발생되는 스크래치, 디싱 및 에로젼 현상을 최소화시킬 수 있다. The polishing slurry of the present invention is characterized in that it contains an organosilicate, which is a polymer derived from a silane having an alkyl group and an alkoxy group having 1 to 3 carbon atoms, as an abrasive, wherein the organosilicate abrasive particles are used for the barrier film or the insulating film. Scratch generated at the time of polishing is greatly reduced, and the alkyl and alkoxy groups in the particles act as a cushion to the metal film surface and combine with metal ions formed on the metal film to form a protective film. Dicing and erosion can be minimized.
본 발명에 사용되는 오가노실리케이트는 탄소수 1 내지 3개의 알킬기 및 알콕시기로 치환된 실란을 단독 또는 공중합하여 얻어지는데, 이의 대표적인 예로는 메틸트라이메톡시실란 또는 다이메틸다이메톡시실란의 단독중합체; 및 메틸트라이메톡시실란 또는 다이메틸다이메톡시실란과, (R)4-n-Si-(OR)n, (R)4-n-Si-O-Si-(OR)n, (R')4-n-Si-(Cl)n 및 (R')4-n-Si-O-Si-(Cl)n 중에서 선택된 화합물(이때, R은 C2-3 알 킬기이고, R'는 C1-3 알킬기이고, n은 1, 2 또는 3이다)과의 공중합체를 들 수 있다. 본 발명에서는, 연마되는 금속막의 특성에 따라 알킬기 및 알콕시기를 적절히 선택하여 사용할 수 있다. 바람직하게는, 상기 오가노실리케이트는 1,000 내지 100,000의 중량평균 분자량을 가질 수 있으며, 분자량을 기준으로 5 내지 50%의 알킬기 및 알콕시기를 함유한다. 본 발명에 사용가능한 오가노실리케이트의 한 예를 화학식 1로서 나타내면 다음과 같다:The organosilicates used in the present invention are obtained by singly or copolymerizing silanes substituted with alkyl groups having 1 to 3 carbon atoms and alkoxy groups, and representative examples thereof include homopolymers of methyltrimethoxysilane or dimethyldimethoxysilane; And methyltrimethoxysilane or dimethyldimethoxysilane, (R) 4-n -Si- (OR) n , (R) 4-n -Si-O-Si- (OR) n , (R ' ) 4-n -Si- (Cl) n and (R ') 4-n -Si -O-Si- (Cl) compound selected from n (wherein, R is C 2-3 al kilgi, R' is C 1-3 is an alkyl group, and n is 1, 2, or 3). In the present invention, an alkyl group and an alkoxy group can be appropriately selected and used according to the characteristics of the metal film to be polished. Preferably, the organosilicate may have a weight average molecular weight of 1,000 to 100,000, and contains 5 to 50% of an alkyl group and an alkoxy group based on the molecular weight. An example of an organosilicate that can be used in the present invention is shown as Formula 1 below:
상기 식에서, m 및 n은 각각 독립적으로 1 이상의 정수이다.Wherein m and n are each independently an integer of 1 or more.
본 발명의 오가노실리케이트 연마제 입자는 0.05 내지 0.5㎛의 입자 크기를 가지며, 연마 슬러리 중량 대비 0.1 내지 30 중량%, 바람직하게는 0.5 내지 5 중량%의 양으로 사용할 수 있다.The organosilicate abrasive particles of the present invention have a particle size of 0.05 to 0.5 μm and may be used in an amount of 0.1 to 30% by weight, preferably 0.5 to 5% by weight, based on the weight of the polishing slurry.
본 발명에 따른 연마 슬러리는 통상의 방법에 따라 상기 오가노실리케이트를 물 및 분산제와 혼합한 후, 여기에 첨가제를 추가로 첨가함으로써 제조할 수 있다.The polishing slurry according to the present invention may be prepared by mixing the organosilicate with water and a dispersant according to a conventional method, and then further adding an additive thereto.
상기 분산제로는 시트르산 및 말산과 같은 유기산; 폴리아크릴산, 폴리메타크릴산 및 폴리에틸렌글리콜과 같은 중합체; 술폰산기, 술포네이트기, 포스폰산기, 포스포네이트기 및 포스페이트기 등의 강산 작용기를 갖는 화합물인, 예를 들면 스 티렌술폰산, 2-아크릴아미도-2-메틸프로판 술폰산(AMPS), 비닐술폰산 및 비닐포스폰산 중에서 둘 이상 선택된 단량체의 공중합체; 및 상기 강산 작용기를 갖는 화합물에 아크릴산, 메타아크릴산, 무수 말레인 및 알킬 아크릴레이트 등의 카복실기 함유 화합물, 에틸렌옥사이드 및 프로필렌옥사이드 등의 알킬렌 옥사이드, 스티렌, 비닐알콜, 비닐피롤리돈 및 비닐 아세테이트 등의 비닐계 화합물, 및 포름아미드, 디메틸포름아미드, 아세트아미드, 벤즈아미드 및 아크릴아미드 등의 아미드계 화합물 중에서 하나 이상 선택된 단량체를 축중합시킨 공중합체 등의 통상의 계면활성제가 있으며, 연마제 대비 0.05 내지 20 중량%의 양으로 사용할 수 있다. 이러한 분산제는 연마제 입자의 수화를 방지하여 입자 안정성을 향상시키므로, 연마 슬러리에 포함되었을 때 본 발명의 연마제가 장기간 안정된 분산성을 나타내게 한다. The dispersant includes organic acids such as citric acid and malic acid; Polymers such as polyacrylic acid, polymethacrylic acid and polyethylene glycol; Styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), which is a compound which has strong acid functional groups, such as a sulfonic acid group, a sulfonate group, a phosphonic acid group, a phosphonate group, and a phosphate group, for example Copolymers of two or more monomers selected from sulfonic acid and vinylphosphonic acid; And carboxyl group-containing compounds such as acrylic acid, methacrylic acid, maleic anhydride and alkyl acrylate, alkylene oxides such as ethylene oxide and propylene oxide, styrene, vinyl alcohol, vinylpyrrolidone and vinyl acetate Conventional surfactants such as vinyl-based compounds, and copolymers obtained by condensation polymerization of at least one monomer selected from amide compounds such as formamide, dimethylformamide, acetamide, benzamide, and acrylamide, and the like. To 20% by weight. This dispersant prevents hydration of the abrasive particles and thus improves particle stability, thereby making the abrasive of the present invention show stable dispersion for a long time when included in the polishing slurry.
연마 슬러리에 추가로 첨가되는 첨가제로는 산화제, 착화제(에칭제), 부식방지제 및 pH 조절제 등이 있다. Additives additionally added to the polishing slurry include oxidizing agents, complexing agents (etching agents), corrosion inhibitors and pH adjusting agents.
산화제는 연마 대상인 금속 배선막이 그에 상응하는 산화물, 수산화물 또는 이온으로 산화되도록 하여 연마를 돕는 역할을 한다. 본 발명의 연마 슬러리에 사용될 수 있는 산화제는 특별히 한정되지는 않으나, 예를 들면 CMP 공정에 통상적으로 사용되는 과산화수소(H2O2), 질산제2철(Fe(NO3)3) 또는 과옥소산칼륨(KIO3) 등을 사용할 수 있으며, 연마 슬러리 중량 대비 0.2 내지 30 중량%, 바람직하게는 1 내지 15 중량%의 양으로 사용할 수 있다.The oxidant serves to assist the polishing by causing the metal wiring film to be oxidized to be oxidized to a corresponding oxide, hydroxide or ion. The oxidizing agent that can be used in the polishing slurry of the present invention is not particularly limited, but for example, hydrogen peroxide (H 2 O 2 ), ferric nitrate (Fe (NO 3 ) 3 ) or peroxo commonly used in a CMP process. Potassium acid (KIO 3 ) and the like can be used, and may be used in an amount of 0.2 to 30% by weight, preferably 1 to 15% by weight based on the weight of the polishing slurry.
착화제는 산화제에 의해 금속 배선막 표면에 형성된 금속 산화물을 제거하는 역할과, 금속 산화물과 착물을 형성하여 더 이상의 산화를 막는 역할을 동시에 수행한다. 이러한 착화제로는 당업계에 공지된 것으로서 카복실산 및 아미노산과 같은 유기산을 사용할 수 있으며, 카복실산의 예로는 옥살산, 숙신산, 말레산, 말론산, 주석산, 프탈산, 말산, 글루타르산, 포름산, 아세트산, 프로피온산, 부티르산, 발레산, 아크릴산, 젖산, 니코틴산 및 이들의 혼합물을; 아미노산의 예로는 글라이신, 세린, 프롤린, 시스테인 및 이들의 혼합물을 들 수 있다. 착화제는 연마 슬러리 중량 대비 0.2 내지 5 중량%, 바람직하게는 0.3 내지 3 중량%의 양으로 사용할 수 있다.The complexing agent simultaneously serves to remove the metal oxide formed on the surface of the metal wiring film by the oxidant, and forms a complex with the metal oxide to prevent further oxidation. As such complexing agents, organic acids such as carboxylic acids and amino acids can be used as known in the art, and examples of carboxylic acids include oxalic acid, succinic acid, maleic acid, malonic acid, tartaric acid, phthalic acid, malic acid, glutaric acid, formic acid, acetic acid, propionic acid Butyric acid, valeric acid, acrylic acid, lactic acid, nicotinic acid and mixtures thereof; Examples of amino acids include glycine, serine, proline, cysteine and mixtures thereof. The complexing agent may be used in an amount of 0.2 to 5% by weight, preferably 0.3 to 3% by weight, based on the weight of the polishing slurry.
부식방지제는 금속 배선막 표면에 부동화층 또는 용해 억제층을 형성시켜 연마 속도를 조절하여 평탄화 향상에 도움을 주는 역할을 한다. 이러한 부식방지제의 대표적인 예로는 벤조트리아졸(BTA), 1,2,4-트리아졸, 벤조퓨록산(benzofuroxan), 2,1,3-벤조트리아졸, o-페닐렌디아민, m-페닐렌디아민, 카테콜(catechol), o-아미노페놀, 2-메캅토벤조트리아졸(2-mercaptobenzotriazole), 2-메캅토벤즈이미다졸(2-mercaptobanzimidazole), 2-메캅토벤조옥사졸, 멜라닌, 이들의 유도체 및 이들의 혼합물을 들 수 있다. 부식방지제는 연마 슬러리 중량 대비 0.001 내지 1 중량%, 바람직하게는 0.001 내지 0.3 중량%의 양으로 사용할 수 있으며, 부식 방지제의 사용량은 착화제의 양에 따라 변경될 수 있다.The corrosion inhibitor forms a passivation layer or a dissolution inhibiting layer on the surface of the metal wiring film, and serves to improve the planarization by controlling the polishing rate. Representative examples of such preservatives include benzotriazole (BTA), 1,2,4-triazole, benzofuroxan, 2,1,3-benzotriazole, o-phenylenediamine, m-phenylene Diamine, catechol, o-aminophenol, 2-mercaptobenzotriazole, 2-mercaptobenzimidazole, 2-mercaptobanzimidazole, 2-mercaptobenzooxazole, melanin, these Derivatives thereof and mixtures thereof. The corrosion inhibitor may be used in an amount of 0.001 to 1% by weight, preferably 0.001 to 0.3% by weight based on the weight of the polishing slurry, and the amount of the corrosion inhibitor may be changed depending on the amount of the complexing agent.
pH 조절제는 연마 조성물의 pH를 조절하는 역할을 한다. pH 조절제로는 통상적인 산, 염기 또는 아민 화합물을 사용할 수 있고, 예를 들면 수산화암모늄, 아민, 질산, 황산, 인산 및 유기산 등을 사용할 수 있으며, 본원 발명의 경우 연마제 를 보호하기 위해 연마 슬러리의 pH가 4 내지 9, 바람직하게는 6 내지 8이 되도록 첨가될 수 있다.The pH adjuster serves to adjust the pH of the polishing composition. As the pH adjusting agent, conventional acids, bases or amine compounds may be used. For example, ammonium hydroxide, amine, nitric acid, sulfuric acid, phosphoric acid and organic acids may be used. In the present invention, the polishing slurry may be used to protect the abrasive. pH can be added from 4 to 9, preferably from 6 to 8.
이렇게 얻어진 본 발명의 연마 슬러리는 쿠션 역할을 하는 알킬기 및 알콕시기를 갖는 오가노실리케이트 연마제 입자의 사용으로 인해 연마시 배리어막이나 절연막에 대한 연마속도를 크게 감소시키는 등 금속 배선에 대한 선택성이 높고, 스크래치, 디싱 및 에로젼 현상을 최소화시킬 수 있어, 반도체 제조시 금속 배선의 평탄화를 위한 화학적 기계적 연마 공정에 유용하게 사용될 수 있다.The polishing slurry of the present invention thus obtained has a high selectivity to metal wiring, such as greatly reducing the polishing rate for the barrier film or the insulating film during polishing due to the use of organosilicate abrasive particles having alkyl and alkoxy groups serving as cushions. Since dishing and erosion can be minimized, it can be usefully used in a chemical mechanical polishing process for planarization of metal wiring in semiconductor manufacturing.
이하, 본 발명을 하기 실시예에 의거하여 좀더 상세하게 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 한정하지는 않는다.Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.
제조예: 오가노실리케이트의 제조Preparation Example: Preparation of Organosilicate
다이메틸다이메톡시실란 1.5g 및 메틸트라이메톡시실란 0.6g을 50ml 용기에 넣은 후 여기에 99% 테트라하이드로퓨란 20ml를 첨가하였다. 이 혼합물을 수분이 제거된 둥근바닥 플라스크로 옮긴 후 여기에 테트라하이드로퓨란 5ml를 추가로 첨가하였다. 상기 플라스크를 얼음조(ice bath)에 위치시키고 혼합물에 물 3.4ml를 넣고, 감압한 다음 HCl 0.3ml를 첨가하였다. 얼음조를 제거한 다음 10분 후 플라스크를 오일조(oil bath)로 옮겨 혼합물을 70℃로 승온하고 16시간 동안 반응시켜, 목적하는 오가노실리케이트로서 중량평균 분자량 3000 및 입자 크기 200nm의 메틸실세퀴녹산(methylsilsequinoxane)을 제조하였다.1.5 g of dimethyldimethoxysilane and 0.6 g of methyltrimethoxysilane were placed in a 50 ml container, and 20 ml of 99% tetrahydrofuran was added thereto. The mixture was transferred to a round bottom flask with no moisture, and then 5 ml of tetrahydrofuran was added thereto. The flask was placed in an ice bath, 3.4 ml of water was added to the mixture, and the pressure was reduced and 0.3 ml of HCl was added. 10 minutes after the ice bath was removed, the flask was transferred to an oil bath, and the mixture was heated to 70 ° C. and reacted for 16 hours. As a desired organosilicate, methylsilsequinoxane having a weight average molecular weight of 3000 and a particle size of 200 nm was obtained. (methylsilsequinoxane) was prepared.
실시예: 연마 슬러리의 제조Example: Preparation of Abrasive Slurry
상기 제조예에서 제조된 메틸실세퀴녹산, 및 분산제로서 메틸실세퀴녹산 중량 대비 40 중량%의 시트르산과 200 중량%의 폴리아크릴산을 물과 함께 혼합한 후, 여기에 슬러리 총중량 대비 과산화수소수 3.0 중량%, 글라이신 1.4 중량% 및 벤조트리아졸(BTA) 0.01 중량%가 되도록 초순수와 함께 가하여 메틸실세퀴녹산을 5.0 중량%로 함유하는 연마 슬러리를 제조하였다.Methyl silsesquinoxane prepared in the above preparation, and 40 wt% citric acid and 200 wt% polyacrylic acid with water relative to the weight of methyl silsesquinoxane as a dispersant were mixed with water, and then 3.0 wt% hydrogen peroxide relative to the total weight of the slurry , 1.4% by weight of glycine and 0.01% by weight of benzotriazole (BTA) were added together with ultrapure water to prepare a polishing slurry containing 5.0% by weight of methylsilsequinoxane.
상기에서 살펴본 바와 같이, 본 발명에 따른 오가노실리케이트 연마제를 함유하는 연마 슬러리는 연마시 배리어막이나 절연막에 대한 연마속도를 크게 감소시키는 등 금속 배선에 대한 선택성이 높고, 스크래치, 디싱 및 에로젼 현상을 최소화시킬 수 있어, 반도체 제조시 금속 배선의 평탄화를 위한 화학적 기계적 연마 공정에 유용하게 사용될 수 있다.As described above, the polishing slurry containing the organosilicate abrasive according to the present invention has high selectivity to metal wiring, such as greatly reducing the polishing rate for the barrier film or the insulating layer during polishing, and scratch, dishing and erosion phenomenon. It can be minimized, it can be usefully used in the chemical mechanical polishing process for planarization of the metal wiring in the semiconductor manufacturing.
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EP0999254A1 (en) | 1998-11-05 | 2000-05-10 | JSR Corporation | Polymer particles and polishing material containing them |
KR20010070227A (en) * | 1999-11-22 | 2001-07-25 | 마쯔모또 에이찌 | Method of Production of Composited Particle, Composited Particle Produced by This Method and Aqueous Dispersion for Chemical Mechanical Polishing Containing This Composited Particle, and Method of Production of Aqueous Dispersion for Chemical Mechanical Polishing |
KR100445447B1 (en) | 2000-02-09 | 2004-08-21 | 제이에스알 가부시끼가이샤 | Aqueous dispersion for chemical mechanical polishing |
US20050261380A1 (en) | 2003-02-27 | 2005-11-24 | Ube Nitto Kasei Co., Ltd. | Method for producing polyorganosiloxane particles and for producing silica particles |
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EP0999254A1 (en) | 1998-11-05 | 2000-05-10 | JSR Corporation | Polymer particles and polishing material containing them |
KR20010070227A (en) * | 1999-11-22 | 2001-07-25 | 마쯔모또 에이찌 | Method of Production of Composited Particle, Composited Particle Produced by This Method and Aqueous Dispersion for Chemical Mechanical Polishing Containing This Composited Particle, and Method of Production of Aqueous Dispersion for Chemical Mechanical Polishing |
KR100445447B1 (en) | 2000-02-09 | 2004-08-21 | 제이에스알 가부시끼가이샤 | Aqueous dispersion for chemical mechanical polishing |
US20050261380A1 (en) | 2003-02-27 | 2005-11-24 | Ube Nitto Kasei Co., Ltd. | Method for producing polyorganosiloxane particles and for producing silica particles |
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