WO1998029515A1 - Composition for oxide cmp - Google Patents
Composition for oxide cmp Download PDFInfo
- Publication number
- WO1998029515A1 WO1998029515A1 PCT/US1997/023627 US9723627W WO9829515A1 WO 1998029515 A1 WO1998029515 A1 WO 1998029515A1 US 9723627 W US9723627 W US 9723627W WO 9829515 A1 WO9829515 A1 WO 9829515A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chemical mechanical
- mechanical polishing
- cerium
- weight percent
- acid
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 119
- 238000005498 polishing Methods 0.000 claims abstract description 111
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000000126 substance Substances 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 50
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 27
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001785 cerium compounds Chemical class 0.000 claims abstract description 20
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims description 132
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- 229910044991 metal oxide Inorganic materials 0.000 claims description 40
- 150000004706 metal oxides Chemical class 0.000 claims description 40
- 239000000377 silicon dioxide Substances 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 38
- 150000003839 salts Chemical class 0.000 claims description 34
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 30
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 30
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052684 Cerium Inorganic materials 0.000 claims description 21
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical group [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 21
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000002738 chelating agent Substances 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 14
- 150000002823 nitrates Chemical class 0.000 claims description 14
- -1 H Inorganic materials 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021485 fumed silica Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000006172 buffering agent Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 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
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 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
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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
- 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 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229960001759 cerium oxalate Drugs 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 3
- XHKOOTFZHJHDTI-UHFFFAOYSA-K cerium(3+);tribromate Chemical compound [Ce+3].[O-]Br(=O)=O.[O-]Br(=O)=O.[O-]Br(=O)=O XHKOOTFZHJHDTI-UHFFFAOYSA-K 0.000 claims description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 3
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 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
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 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
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 235000011087 fumaric acid Nutrition 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 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
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 229940107700 pyruvic acid Drugs 0.000 claims description 2
- 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 description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 7
- KKVSNHQGJGJMHA-UHFFFAOYSA-H cerium(3+);trisulfate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KKVSNHQGJGJMHA-UHFFFAOYSA-H 0.000 claims 2
- 239000006069 physical mixture Substances 0.000 claims 2
- CLLLODNOQBVIMS-UHFFFAOYSA-N 2-(2-methoxyethoxy)acetic acid Chemical compound COCCOCC(O)=O CLLLODNOQBVIMS-UHFFFAOYSA-N 0.000 claims 1
- YHBWXWLDOKIVCJ-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]acetic acid Chemical compound COCCOCCOCC(O)=O YHBWXWLDOKIVCJ-UHFFFAOYSA-N 0.000 claims 1
- DSLZVSRJTYRBFB-LLEIAEIESA-N D-glucaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O DSLZVSRJTYRBFB-LLEIAEIESA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 description 27
- 239000003082 abrasive agent Substances 0.000 description 14
- 150000004767 nitrides Chemical group 0.000 description 14
- 229910000420 cerium oxide Inorganic materials 0.000 description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 12
- 235000012431 wafers Nutrition 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 238000007517 polishing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940058180 edetate dipotassium anhydrous Drugs 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910004755 Cerium(III) bromide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000010296 bead milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 description 1
- DPUCLPLBKVSJIB-UHFFFAOYSA-N cerium;tetrahydrate Chemical compound O.O.O.O.[Ce] DPUCLPLBKVSJIB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006400 oxidative hydrolysis reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000916 rhodite Inorganic materials 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-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
- 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
-
- 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
-
- 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
- H01L21/31—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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Definitions
- the present invention relates to chemical mechanical polishing slurries for semiconductor integrated circuit substrates Specifically, this invention is a CMP slurry having a unique chemistry that is especially suitable for chemical mechanical planarization where a high silicon dioxide removal rate, and a low silicon nitride removal rate are required on the same substrate
- Integrated circuits are made up of millions of active devices formed in or on a silicon substrate The active devices form functional circuits and components These devices are then connected by the use of multilevel metallized interconnects and vias Interconnection structures normally have a first layer metallization, an interconnect plug, a second layer of metallization, and sometimes a third or more layers of metallization with their respective interconnects Inter level dielectrics (ILDs), such as doped and undoped SiO2 are used to electrically isolate the different levels of interconnections.
- ILDs Inter level dielectrics
- Shallow trench isolation is a technology for device isolation in a give layer in the IC manufacturing process.
- silicon nitride is deposited on thermally grown oxide After deposition of the nitride, a shallow trench is etched into the substrate using a mask A layer of oxide is then deposited into the trench so that the trench forms an area of insulated dielectric which acts to isolate the devices in a chip, and thus reduces the cross-talk between active devices The excess deposited oxide must be polished of and the trench planarized to prepare for the next level of metallization The silicon nitride is applied to the silicon to prevent polishing of the masked silicon oxide of the device
- the substrate is placed in direct contact with a rotating polishing pad
- a carrier applies pressure against the backside of the substrate
- the pad and table are rotated while a downward force is maintained against the substrate back
- An abrasive and chemically reactive solution commonly referred to as “a CMP slurry”
- the chemicals and abrasive particles in the slurry initiate the polishing process by interacting with the wafer being polished
- the polishing process is facilitated by the rotational movement of the pad relative to the substrate as slurry is provided to the wafer/pad interface Polishing is continued in this manner until the final desired film thickness is achieved by removal of the required amount of thin-film material
- polishing oxides it is desirable of the slurry used to have a high removal rate towards the oxide layer and a low removal rate towards other layers which may be exposed during CMP, such as silicon nitride
- the polishing slurry should be tailored to provide effective polishing at the desired polishing ranges selective to specific thin layer materials, while minimizing, at the same time, surface imperfections, defect, corrosion, erosion and the removal of silicon nitride and other stop layers
- CMP slurries useful for polishing oxides typically contain an abrasive at an alkaline or high pH These slurries either rely on potassium hydroxide or ammonium hydroxide to effectively buffer the high pH While these slurries polish silica at high rates they also polish silicon nitride at high rates Typically, the ratio of these removal rates, t.e., the selectivity is, at most, about 5 to 1 silicon oxide to silicon nitride It is believed that the mechanism of silicon nitride polishing is oxidative hydrolysis of the
- This invention is a chemical mechanical polishing composition that is capable of polishing a silicon dioxide layer at a high rate
- This invention is also a chemical mechanical polishing composition that inhibits the polishing of a silicon nitride film
- this invention is a method of using a chemical mechanical polishing composition that selectively removes silicon dioxide from a substrate while leaving a silicon nitride layer associated with the substrate essentially intact
- this invention is a chemical mechanical polishing composition comprising carboxylic acid, a salt and a soluble cerium compound The composition has a pH from about 3 0 to about 11, and preferably from about 3 8 to about 5 5 and is useful for selectively removing silicon dioxide from layered substrates
- this invention is a chemical mechanical polishing slurry comprising the chemical mechanical polishing composition described above and an abrasive The slurry is especially useful for silicon dioxide film polishing
- the present invention is a method for using a chemical mechanical polishing composition comprising a carboxylic acid, a salt and a soluble cerium compound in an aqueous solution having a pH from about 3 0 to about 11 to selectively remove oxide overfill in preference to a silicon nitride film layer during the manufacture of integrated circuits and semiconductors
- the present invention is directed to a chemical mechanical polishing composition that comprises, a carboxylic acid, a salt, and a soluble cerium compound, having a pH of from about 3.0 to about 1 1.0.
- the chemical mechanical composition may be used alone or it may be combined with a metal oxide abrasive to form a slurry.
- the compositions and slurries of this invention polish oxide layers such as silicon dioxide layers associated with substrates at high rates.
- the compositions of this invention have been found to inhibit silicon nitride polishing.
- the present invention is also directed to novel methods for using the compositions and slurries of this invention to polish oxide layers.
- the "chemical mechanical composition” refers to the combination of at least one carboxylic acid, at least one salt, and at least one soluble cerium compound that may be used in conjunction with an abrasive pad to remove one or more layers of a substrate.
- the term “slurry” or “chemical mechanical polishing slurry” refers to the combination of the chemical mechanical polishing composition and at least one abrasive.
- Carboxylic acids useful in a CMP slurry of the present invention include monofunctional and di-functional carboxylic acids and their salts.
- the carboxylic acid is selected from the group including acetic acid, adipic acid, butyric acid, capric acid, caproic acid, caprylic acid, citric acid, glutaric acid, glycolic acid, formic acid, fumaric acid, lactic acid, lauric acid, malic acid, maleic acid, malonic acid, myristic acid, oxalic acid, palmitic acid, phthalic acid, propionic acid, pyruvic acid, stearic acid, succinic acid, tartaric acid, valeric acid, 2-(2-methyoxyethoxy) acetic acid, 2-[2-(2- methyoxyethoxy)ethyoxy] acetic acid, poly(ethylene glycol)bis(carboxymethyl)ether, and derivatives, including salts thereof.
- a most preferred carboxylic acid is acetic acid.
- the carboxylic acid can comprise greater than 10% of the slurry.
- the carboxylic acid is present in the composition of this invention in an amount ranging from about 0 05 to about 10% by weight In a more preferred embodiment, however, the carboxylic acid is present in the composition of this invention in an amount ranging from about 0 1 to about 3%
- the chemical mechanical composition of the present invention may include a salt
- salt refers to any water soluble salts including organic salts and inorganic salts such as nitrate, phosphate, and sulfate salts Soluble salts also refers to salts that are only partially or marginally soluble in water Preferred salts are nitrate salts
- the salt may be present in the composition in the amount of from about 0 05 to about 6% by weight of the composition It is most preferred that the salt is present in the composition in the amount ranging from about 0 1 to about 4%> by weight
- the chemical mechanical composition of the present invention includes at least one soluble cerium compound
- soluble cerium includes, for purposes of this invention, both cerium added in soluble form and cerium dissolved from colloidal or ground particles
- Non-limiting examples of soluble cerium compounds useful in a composition of the present invention include water soluble hydrated and non-hydrated salts of cerium hydroxide (Ce(OH) 4 ), ammonium cerium sulfate,
- a preferred embodiment of the chemical mechanical composition of the present invention includes ammonium cerium nitrate as both the salt and as the soluble cerium compound
- Other soluble cerium nitrate salts may be incorporated into the composition of this invention as both the soluble cerium compound and as the salt
- Ammonium cerium nitrate may be present in composition of the present invention in an amount ranging from about 0 05 to about 6% weight percent of the overall composition weight
- a more preferred range of ammonium cerium nitrate is from about 0 1 to about 4 0 weight percent
- ceria typically contains a mixture of dissolved Ce 4* and Ce ,+ ions It is preferred that the dissolved ceria is in the form of Ce 3+ ions Adding an oxidizer to the composition of this invention that is capable of oxidizing Ce 4+ to Ce ⁇ * produces a product that exhibits high oxide selectivities and low nitride selectivities
- the oxidizing agent used must have a higher oxidation potential than Ce 4 "
- a preferred oxidizing agent is ammonium persulfate
- the oxidizing agent is useful in an amount ranging from about 0 05 to about 5 0 weight percent
- the oxidizing agent is preferably present in an amount ranging from about 0 1 to about 2 0 weight percent
- the chemical mechanical composition of this invention may optionally include at least one chelating agent It has been found that the addition of a chelating agent to chemical mechanical compositions of this invention improves the cleanability of substrates polished with compositions of this invention It is believed that cleanability of substrates is enhanced because the chelating agent binds free ions in the composition that would otherwise deposit on the wafer
- Useful chelating agents include any chelating agents that bind to free ions in the compositions of this invention
- useful chelating agents include, but are not limited, to polycarboxylic acids such citric acid, EDTA, triethanolamine, and benzonitrile, adipic acid, malonic acid, oxalic acid, phoshonic acids, phosphoric acid and salts thereof
- Chelating agents, if used, should be present in the composition in an amount ranging from about 0 05 to about 5 0 weight percent, and preferably from about 0 1 to about 1 5 weight percent
- the chemical mechanical composition of this invention may be used alone or in conjunction with an abrasive to give a chemical mechanical polishing "slurry "
- Abrasives useful in conjunction with the compositions of the present invention include metal oxide abrasives.
- the metal oxide abrasive may be selected from the group including alumina, titania, zirconia, germania, silica, ceria and mixtures thereof.
- useful abrasives may be the result of mixing precursors of two or more metal oxides to give a chemical admixture of a mixed metal oxide abrasive.
- alumina can be co-formed with silica, or combined alumina/silica.
- Useful metal oxide abrasives may be produced by any techniques known to those skilled in the art, including high temperature processes such as sol-gel, hydrothermal or, plasma process, or by processes for manufacturing fumed or precipitated metal oxides. Pulverized or crushed metal oxide abrasives are also useful in the CMP slurry of this invention and may be manufactured by milling or grinding using conventional manufacturing techniques such as jet-milling, ball milling, bead milling, and other milling and pulverization techniques and process know to one skilled in the art.
- Preferred abrasives suitable for the CMP slurries of this invention are silica and cerium oxide (ceria) with fumed silica being most preferred
- Other suitable silica abrasives can be made by methods such as sol-gel, hydrothermal, plasma process, flame pyrolysis or by other processes for manufacturing metal oxides
- Pulverized abrasives are also suitable for this invention Any pulverized metal oxide abrasive may be used in a CMP slurry of this invention However, pulverized cerium oxide is preferred
- the cerium oxide abrasive is ground in a media mill to give pulverized ceria
- the original cerium oxide particle may be either mined cerium oxide or precipitated and calcined cerium oxide or a combination thereof
- the grinding may be accomplished in an aqueous medium using any type of a grinding or milling apparatus such as by jet milling or ball milling
- a preferred grinding mechanism is a medial mill with either yttria tetragonal zirconia (YTZ) or zirconium silicate media
- the grinding process may use a dispersant or steric stabilizer
- the preferred pulverized metal oxide abrasive will have a narrow particle size distribution with a median particle size (i e , aggregate particle or single particle) of less than about 0 5 microns
- Precipitated cerium oxide is a suitable abrasive for oxide CMP
- Precipitated cerium oxide particles are made from a variety of precursors including acetates, carbonates and hydroxide and nitrate salts of cerium
- the median particle size of precipitated cerium oxide particles may range of from about 10 nm to about 500 nm, with the preferred size of precipitated cerium oxide particles being in the range of from about 30 to about 300 nm
- fumed silica Another preferred abrasive is fumed silica
- feed stock vapor such as silicon tetrachloride for a silica abrasive
- molten particles of roughly spherical shape are formed in the combustion process
- the diameters of the particles are varied through process parameters, and these molten spheres of silica or similar oxide, typically referred to as primary particles, fuse with one another by colliding at their contact points to form branched, three dimensional chain-like aggregates
- the force necessary to break aggregates is considerable and often irreversible During cooling and collecting, the aggregates undergo further collisions that may result in some mechanical entanglement causing the formation of aggregates
- a preferred metal oxide will have a surface area, as calculated from the method of S Brunauer, P H Emmet, and I Teller, J Am Chemical Society, Volume 60, Page 309 (1938) and commonly referred to a BET, ranging from about 5 m 2 /g to about 430 m 2 /g and preferably from about 30 m 2 /g to about 170 m 2 /g Due to stringent purity requirements in the IC industry the preferred metal oxide should be of a high purity High purity means that the total impurity content, from sources such as raw material impurities and trace processing contaminants, is typically less than 1% and preferably less than 0 01% (i e , 100 ppm)
- the metal oxide abrasive consists of metal oxide aggregates having about 99 weight percent of the particles less than about 1 0 micron in diameter, a mean aggregate diameter less than about 0.4 micron and a force sufficient to repel and overcome the van der Waals forces between abrasive aggregates themselves.
- Such metal oxide abrasives have been effective in minimizing or avoiding scratching, pit marks, divots and other surface imperfections during polishing.
- the aggregate size distribution in the present invention may be determined using known techniques such as transmission electron microscopy (TEM).
- the mean aggregate diameter refers to the average equivalent spherical diameter when using TEM image analysis, i.e., based on the cross-sectional area of the aggregate.
- the surface potential or the hydration force of the metal oxide particles must be sufficient to repel and overcome the van der Waals attractive forces between the particles.
- the metal oxide abrasive may consist of discrete metal oxide particles having a particle diameter less than 0.5 micron (500 nm) and a surface area ranging from about 10 m 2 /g to about 250 m 2 /g.
- a CMP slurry of this invention will include from about 2 weight percent to about 25 weight percent metal oxide abrasive and preferably from about 2 weight percent to about 15 weight percent metal oxide abrasive.
- Metal oxide abrasives useful in CMP slurries of the present invention are incorporated into the aqueous medium of the polishing slurry as a concentrated aqueous dispersion of metal oxides comprising from about 3% to about 55% solids, and preferably between 30% and 50% solids.
- the aqueous dispersion of metal oxides may be produced using conventional techniques, such as slowly adding the metal oxide abrasive to an appropriate media, for example, de-ionized water, to form a colloidal dispersion.
- the dispersions are typically completed by subjecting them to high shear mixing conditions known to those skilled in the art.
- the abrasives useful in a CMP slurry of the present invention can be a mixture of the abrasives described above.
- precipitated cerium oxide, pulverized cerium oxide (also referred to a ceria) and fumed silica could be incorporated into a CMP slurry of the present invention.
- Other combinations of abrasives are also useful in the CMP slurry.
- the mixture of abrasives could include any relative proportion of one abrasive to another. For example, a combination of from about 5 to
- the CMP slurry of this invention must have a pH from about 3 0 to about 1 1 0 to be effective More preferably, the slurry pH will range from about 3 5 to about 6 0, and most preferably the pH is from about 3 8 to about 5 5 Slurry pH is adjusted by adding any base to the composition and preferably by adding a non-metal base such as ammonium hydroxide to the slurry
- the chemical mechanical composition of this invention may contain one or more buffering agents
- the purpose of the buffering agent is to help maintain the pH of the composition within the desired range, and most preferably from about 3 8 to about 5.5
- buffering agent that is capable of maintaining the pH of the composition in the desired range may be used Most preferred buffers are ammonium formate or formic acid Buffering agent used in the composition will typically range from about
- a variety of additional optional additives such as surfactants, polymeric stabilizers or other surface active dispersing agents, can be used.
- the surfactant can be anionic, cationic, nonionic, amphoteric and combinations of two or more surfactants can be employed.
- a surfactant may be useful to improve the within-wafer-non- uniformity (WIWNU) of the wafers, thereby improving the surface of the wafer and reducing wafer defects.
- WIWNU within-wafer-non- uniformity
- the amount of an additive used, such as a surfactant, in the present invention should be sufficient to achieve effective steric stabilization of the slurry and will typically vary depending on the particular surfactant selected and the nature of the surface of the metal oxide abrasive. For example, if not enough of a selected surfactant is used, it will have little or no effect on stabilization. On the other hand, too much of the surfactant may result in undesirable foaming and/or flocculation in the slurry. As a result, additives like surfactants should generally be present in a range between about 0.001 % and 10% by weight. Furthermore, the additive may be added directly to the slurry or treated onto the surface of the metal oxide abrasive utilizing known techniques. In either case, the amount of additive is adjusted to achieve the desired concentration in the polishing slurry.
- the chemical mechanical polishing compositions and slurries of this invention are capable of selectively removing the silicon dioxide layer from layered substrates at very high rates. Furthermore, the compositions and slurries of this invention inhibit the polishing of silicon nitride from layered substrates.
- One important application for the chemical mechanical polishing compositions and slurries of this invention is in the manufacture of integrated circuits and semiconductors. In such a polishing application, the compositions and slurries of this invention effectively remove silicon dioxide for shallow trench device isolation.
- compositions and slurries of this invention preferably exhibit oxide removal rate of from about 1200 A/min to about 6000 A/min or more with an oxide to nitride removal selectivity of from about 5 to about 100 or more and preferably from about 15 to about 50 or more.
- compositions and slurries of the present invention may be incorporated in a single package which includes an aqueous composition of at least one carboxylic acid, a soluble cerium compound, a salt, an optional abrasive, and optional additives at the requisite pH.
- an aqueous composition of at least one carboxylic acid, a soluble cerium compound, a salt, an optional abrasive, and optional additives at the requisite pH may be preferable to use at least a two package system where the first package comprises at least one carboxylic acid, a salt and a soluble cerium compound at any pH and the second package comprises the optional abrasive at any pH.
- the components in one container may be in dry form while the component in the other container are in the form of an aqueous dispersion.
- Other two- container combinations of the ingredients of the CMP slurry of this invention are within the knowledge of one having ordinary skill in the area.
- the compositions and slurries of the present invention do not significantly increase the silicon nitride removal rate.
- the composition and slurry of this invention significantly increases the removal rate of silicon dioxide in comparison to known slurries.
- the polishing slurry of the present invention may be used during the various stages of semiconductor integrated circuit manufacture to provide effective removal of silicon oxide layers at desired removal rates while minimizing surface imperfections and defects.
- compositions of this invention were used in an STI polishing protocol as outlined below.
- the CMP slurries were used to chemically-mechanically polish blanket PETEOS and silicon nitride using a ICIOOO/SUBA IV pad stack manufactured by Rodel, Inc.
- the polishing was performed using an IPEC/WESTECH 472 CMP tool at a down force of 9 psi, a slurry flow rate of 140 ml/min., a platen speed of 35 rpm and a carrier speed of 24 rpm.
- a pulverized ceria slurry was prepared in order to evaluate its ability to polish blanket silicon dioxide and nitride wafers.
- Rhodite grade 400HS ceria, having particle sizes approximately 2-4 ⁇ m was purchased from Universal Photonics, Hicksville, New York and pulverized using an agitator bead mill to a primary median particle size of 150 nm Pulverizing was accomplish under wet conditions so that the resulting slurry, pH approximately 7 5 - 8 5, contained 20-30% solids after the pulverizing process
- the slurry was then diluted and the pH adjusted to produce the slurries listed in Table 1
- the slurries were used to polish substrates according to the method described in Example 1
- the pulverized ceria slurries were used for polishing The data indicates that the pulverized ceria slurries yield very high PETEOS (silicon oxide layer) removal rates
- a nitrate stabilized ceria slurry containing precipitated ceria particles, nitric acid, acetic acid, pH 1 8 and 20% solids, was purchased from Nyacol Products (Ashland, MA) The pH of the slurry was adjusted to from about 4 2 - 6 8 by adding ammonium hydroxide. The slurries were used to polish substrates according to the method described in Example 1 The polishing results are reported in Table 2 Table 2
- the polishing data indicates that at the lowest pH (4 2) selectivity is high, but overall oxide removal rates are low
- a colloidal cerium acetate slurry, including soluble Ce and Ce , and acetic acid, (pH 1 8 and 20% solids), was purchased from Nyacol Products (Ashland, MA)
- the pH of the slurry was adjusted to 4 5 and the solids content to 15 %
- the slurry was applied to substrate according to the methods described in Example 1 and the result showed an oxide layer removal rate of 117 A/min and a nitride layer removal rate of 10 5 A/min for an oxide to nitride selectivity of 11 1
- a ceria slurry composed of varying weight percent amounts of the pulverized ceria manufactured as set forth in Example 2 and precipitated ceria purchased from Nyacol Products (Ashland, MA) was formulated as shown in Table 3 The slurries were used to polish substrates according to the methods described in Example 1 and the polishing results are set forth in Table 3, below Table 3
- a slurry, composed of 4 weight percent CAB-O-SIL ® L-90 fumed silica, 1 8 weight percent ammonium cerium nitrate, and 0 6 weight percent acetic acid of varying percentages was formulated as shown in Table 5
- the pH of the slurries varied from between 4 0 to 5 0
- the slurries were applied to substrate according to the methods described in Example 1
- a composition composed of 1 8 wt% ammonium cerium nitrate, 0 8 wt% acetic acid, and deionized water was used to polish PETEOS and silicon nitride wafers according to the method of Example 1
- the pH of the slurry was adjusted to 4 5
- a CMP slurry consisting of 4 Owt % cerium and 4 0wt% silica, having a pH of 4 5 was prepared by combining appropriate amounts of (1) the 20wt% colloidal cerium solution manufactured by Nyacol Products (Ashland, MA) and described in Example 4, (2) L-90 fumed silica manufactured by Cabot Corp and sold under the name CAB-O- SLL ® , and (3) deionized water
- This Example evaluated the polishing effectiveness of compositions of this invention without and with an oxidizing agent Slurries, consisting of 4 0wt% colloidal ceria including Ce 4+ ions, and 4 0wt% silica and having a pH of 4 5 were formulated according to the method set forth in Example 9 The slurries were tested according to the method of Example 2 without and with the addition of 0 15 wt % ammonium persulfate The test results are reported in Table 7, below
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- Condensed Matter Physics & Semiconductors (AREA)
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- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU55328/98A AU5532898A (en) | 1996-12-30 | 1997-12-19 | Composition for oxide cmp |
JP53013898A JP2001507739A (en) | 1996-12-30 | 1997-12-19 | Composition for oxide CMP |
DE69728691T DE69728691T2 (en) | 1996-12-30 | 1997-12-19 | COMPOSITION FOR CHEMICAL-MECHANICAL POLISHING OF OXYDES |
EP97951772A EP0963419B1 (en) | 1996-12-30 | 1997-12-19 | Composition for oxide cmp |
IL13072097A IL130720A0 (en) | 1996-12-30 | 1997-12-19 | Composition for oxide CMP |
AT97951772T ATE264378T1 (en) | 1996-12-30 | 1997-12-19 | COMPOSITION FOR CHEMICAL-MECHANICAL POLISHING OF OXIDES |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US08/774,488 | 1996-12-30 | ||
US08/774,488 US5759917A (en) | 1996-12-30 | 1996-12-30 | Composition for oxide CMP |
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WO1998029515A1 true WO1998029515A1 (en) | 1998-07-09 |
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PCT/US1997/023627 WO1998029515A1 (en) | 1996-12-30 | 1997-12-19 | Composition for oxide cmp |
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US (3) | US5759917A (en) |
EP (1) | EP0963419B1 (en) |
JP (2) | JP2001507739A (en) |
KR (1) | KR20000069823A (en) |
CN (1) | CN1168794C (en) |
AT (1) | ATE264378T1 (en) |
AU (1) | AU5532898A (en) |
DE (1) | DE69728691T2 (en) |
IL (1) | IL130720A0 (en) |
TW (1) | TW505690B (en) |
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WO2001080296A1 (en) * | 2000-04-13 | 2001-10-25 | Showa Denko K.K. | Polishing compound for polishing semiconductor device and method for manufacturing semiconductor device using the same |
US6589100B2 (en) | 2001-09-24 | 2003-07-08 | Cabot Microelectronics Corporation | Rare earth salt/oxidizer-based CMP method |
JPWO2002067309A1 (en) * | 2001-02-20 | 2004-06-24 | 日立化成工業株式会社 | Polishing agent and substrate polishing method |
KR100474540B1 (en) * | 2002-06-24 | 2005-03-10 | 주식회사 하이닉스반도체 | Method for manufacturing metal line contact plug of semiconductor device |
US7253111B2 (en) | 2004-04-21 | 2007-08-07 | Rohm And Haas Electronic Materials Cmp Holding, Inc. | Barrier polishing solution |
EP3049216A4 (en) * | 2013-09-24 | 2017-07-26 | Cabot Microelectronics Corporation | Chemical-mechanical planarization of polymer films |
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Also Published As
Publication number | Publication date |
---|---|
DE69728691T2 (en) | 2004-08-19 |
EP0963419A1 (en) | 1999-12-15 |
EP0963419B1 (en) | 2004-04-14 |
CN1248994A (en) | 2000-03-29 |
US20040089634A1 (en) | 2004-05-13 |
CN1168794C (en) | 2004-09-29 |
US5759917A (en) | 1998-06-02 |
DE69728691D1 (en) | 2004-05-19 |
IL130720A0 (en) | 2000-06-01 |
AU5532898A (en) | 1998-07-31 |
JP2008199043A (en) | 2008-08-28 |
JP2001507739A (en) | 2001-06-12 |
KR20000069823A (en) | 2000-11-25 |
JP5038199B2 (en) | 2012-10-03 |
TW505690B (en) | 2002-10-11 |
ATE264378T1 (en) | 2004-04-15 |
US6984588B2 (en) | 2006-01-10 |
US6689692B1 (en) | 2004-02-10 |
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