TW202037719A - 氧化鈰移除組成物 - Google Patents
氧化鈰移除組成物 Download PDFInfo
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- TW202037719A TW202037719A TW109103971A TW109103971A TW202037719A TW 202037719 A TW202037719 A TW 202037719A TW 109103971 A TW109103971 A TW 109103971A TW 109103971 A TW109103971 A TW 109103971A TW 202037719 A TW202037719 A TW 202037719A
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- Prior art keywords
- acid
- composition
- cerium oxide
- complex compound
- ether
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 78
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 27
- -1 methylene Phosphonic acid Chemical compound 0.000 claims description 75
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 48
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 29
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 13
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 11
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 10
- 229960003237 betaine Drugs 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 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 7
- 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 7
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000000269 nucleophilic effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012459 cleaning agent Substances 0.000 claims description 5
- 230000000536 complexating effect Effects 0.000 claims description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-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
- 239000007800 oxidant agent Substances 0.000 claims description 4
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical group C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 claims description 3
- 241000208340 Araliaceae Species 0.000 claims description 3
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims description 3
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 3
- 229940075419 choline hydroxide Drugs 0.000 claims description 3
- 235000008434 ginseng Nutrition 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 3
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 54
- 238000004377 microelectronic Methods 0.000 abstract description 40
- 239000000356 contaminant Substances 0.000 abstract description 29
- 239000000758 substrate Substances 0.000 abstract description 20
- 238000004140 cleaning Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 7
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract description 6
- 239000008139 complexing agent Substances 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 239000002002 slurry Substances 0.000 description 15
- 238000005498 polishing Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
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- 239000000243 solution Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 3
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- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 description 1
- SIYLLGKDQZGJHK-UHFFFAOYSA-N dimethyl-(phenylmethyl)-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]ammonium Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 SIYLLGKDQZGJHK-UHFFFAOYSA-N 0.000 description 1
- OWMBTIRJFMGPAC-UHFFFAOYSA-N dimethylamino 2-methylprop-2-enoate Chemical compound CN(C)OC(=O)C(C)=C OWMBTIRJFMGPAC-UHFFFAOYSA-N 0.000 description 1
- FRXGWNKDEMTFPL-UHFFFAOYSA-N dioctadecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCCCC FRXGWNKDEMTFPL-UHFFFAOYSA-N 0.000 description 1
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- FFGSPQDSOUPWGY-UHFFFAOYSA-M dodecyl-ethyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC FFGSPQDSOUPWGY-UHFFFAOYSA-M 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical class O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
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- 235000010987 pectin Nutrition 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 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
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- IYPZRUYMFDWKSS-UHFFFAOYSA-N piperazin-1-amine Chemical compound NN1CCNCC1 IYPZRUYMFDWKSS-UHFFFAOYSA-N 0.000 description 1
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- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
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- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
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- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
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- 229920005591 polysilicon Polymers 0.000 description 1
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- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 235000010408 potassium alginate Nutrition 0.000 description 1
- 239000000737 potassium alginate Substances 0.000 description 1
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class 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 description 1
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- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
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- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Polymers CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YNJQKNVVBBIPBA-UHFFFAOYSA-M tetrabutylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC YNJQKNVVBBIPBA-UHFFFAOYSA-M 0.000 description 1
- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical compound CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- LDGFRUUNCRYSQK-UHFFFAOYSA-N triazin-4-ylmethanediamine Chemical group NC(N)C1=CC=NN=N1 LDGFRUUNCRYSQK-UHFFFAOYSA-N 0.000 description 1
- MPSUGQWRVNRJEE-UHFFFAOYSA-N triazol-1-amine Chemical compound NN1C=CN=N1 MPSUGQWRVNRJEE-UHFFFAOYSA-N 0.000 description 1
- GPQCSCQDQNXQSV-UHFFFAOYSA-N tridodecylazanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC GPQCSCQDQNXQSV-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical class CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
Classifications
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Abstract
本發明大體上係關於一種移除組成物及方法,其尤其適用於自上面有氧化鈰粒子及CMP污染物之微電子裝置,尤其具有PETEOS、氮化矽及多晶矽基板之微電子裝置清潔該等粒子及CMP污染物。在一個態樣中,本發明提供利用不含硫及磷原子之錯合劑處理上面有氧化鈰粒子之微電子基板。
Description
本發明大體上係關於用於自上面有氧化鈰粒子及其他化學機械研磨漿料污染物之微電子裝置移除該等粒子及污染物的組成物。
微電子裝置晶圓用於形成積體電路。微電子裝置晶圓包括諸如矽之基板,在基板中區域經圖案化用以沈積具有絕緣、導電或半導電特性之不同材料。
為獲得恰當之圖案化,必須移除用於在基板上形成層之過量材料。此外,為製造功能性且可靠之電路,在後續加工之前製備平整或平坦之微電子晶圓表面很重要。因此,必需移除及/或研磨微電子裝置晶圓之某些表面。
化學機械研磨或平坦化(「CMP」)為一種自微電子裝置晶圓之表面移除材料,且藉由聯合物理方法(諸如磨耗)與化學方法(諸如氧化或螯合)來研磨(例如,平坦化)該表面的方法。CMP以其最基本的形式涉及將具有活性化學物質之研磨漿料施加至研磨墊,該研磨墊在移除、平坦化及研磨製程期間磨光微電子裝置晶圓之表面。為達成快速、均勻移除,利用純物理或純化學作用之移除或研磨方法並不如使用兩者之協同組合般有效。另外,在積體電路之製造中,CMP漿料亦應能夠優先移除包含金屬及其他材料之錯合層之膜,從而可產生用於後續光微影或圖案化、蝕刻及薄膜加工之高度平坦之表面。
在用於使用淺溝槽隔離(STI)製程在矽基板中形成隔離區之生產線前段(front-end-of-the-line;FEOL)方法中,將墊氧化物膜及墊氮化物膜沈積於半導體基板上且圖案化以暴露基板中對應於隔離區之部分。接著,蝕刻基板之暴露區以形成溝槽。其後,使基板經受犧牲氧化製程以移除由基板蝕刻引起之損壞,隨後在溝槽之表面上形成壁氧化物膜。接著,以如內埋於溝槽中之方式將內埋溝槽的氧化物膜(例如,由高密度電漿化學氣相沈積形成之氧化物膜,稱為HDP-氧化物膜)沈積於基板之表面上。隨後,使HDP-氧化物膜之表面經受化學機械研磨,直至暴露墊氮化物膜為止。隨後清潔所得基板且移除在溝槽蝕刻期間用作蝕刻障壁之墊氮化物膜,從而形成隔離區。
相對於含二氧化矽之漿料,對於絕緣體而言使用氧化鈰粒子之CMP漿料通常達成較快研磨速度。此外,基於氧化鈰之漿料由於其在最小氧化物侵蝕的情況下達成STI圖案平坦化之能力而最常使用。不利地,由於氧化鈰粒子相對於氧化矽及氮化矽表面帶相反電荷的ζ電位,故基於氧化鈰之漿料難以自STI結構移除。若製造具有此等殘餘物殘留於晶圓上之裝置,則該等殘餘物將導致短路及電阻增加。在使用氧化鈰漿料進行CMP加工之後,氧化鈰粒子亦為FinFET結構之問題。
當前,用於移除氧化鈰粒子之最有效濕清潔調配物為稀氫氟酸(DHF)。然而,DHF不利地蝕刻氧化矽及其他低k介電材料。
因此,仍需要一種氧化鈰粒子移除組成物及方法,該組成物及方法可有效地自微電子裝置之表面移除氧化鈰粒子,同時不損害諸如氮化矽層、低k介電(例如,氧化矽)層及含鎢層之底層材料。氧化鈰粒子移除組成物亦應有效地自微電子裝置之表面移除CMP漿料污染物。
本發明大體上關於一種移除組成物及方法,其尤其適用於自上面有氧化鈰粒子及CMP污染物之微電子裝置,尤其具有PETEOS、氮化矽及多晶矽基板之微電子裝置清潔該等粒子及CMP污染物。在一個態樣中,本發明提供利用不含硫及磷原子之錯合劑處理上面有氧化鈰粒子之微電子基板。就此而言,氧化鈰粒子可帶正電或帶負電。
本發明大體上係關於適用於自上面有氧化鈰粒子及CMP污染物之微電子裝置移除此類一或多種材料的組成物。使用該等組成物有效移除氧化鈰粒子及CMP污染物,且另外,該等組成物與氮化矽及低k介電(例如,氧化矽)層相容。
在第一態樣中,本發明提供一種組成物,該組成物包含如本文中所闡述之組成物、由其組成或基本上由其組成。在一個實施例中,本發明提供一種pH為約1至約6之組成物,其包含:
(a)鈰-氧鍵斷裂化合物;
(b)pH調節劑;
(c)至少一種清潔劑;
(d)選自酒石酸、乙醯丙酮、麩胺酸、己二酸、甜菜鹼、胺基參(亞甲基膦酸)及氮基三乙酸的氧化鈰錯合化合物;及
(e)水。
在本發明之組成物中,鈰-氧鍵斷裂化合物可為任何用於有效斷裂鈰-氧化學鍵之習知化合物。此類化合物包括氧化劑、還原劑及親核化合物。
如本文中所使用,術語「親核化合物」係指理解為在化學反應中充當親核試劑之化合物。換言之,親核化合物為可向親電試劑供給電子對以形成與反應相關之化學鍵的化學物種。
在一個實施例中,親核化合物為胺。實例包括單乙醇胺(MEA)、嗎啉、異丙基胺、二異丙醇胺、二甘醇胺、三乙胺、N-甲基嗎啉、甲基乙醇胺、N-胺基丙基嗎啉及3-胺基-丙醇。
其他親核化合物包括具有通式NR1
R2
R3
之物種,其中R1
、R2
及R3
可彼此相同或不同且選自氫、直鏈或分支鏈C1
-C6
烷基(例如,甲基、乙基、丙基、丁基、戊基及己基)、直鏈或分支鏈C1
-C6
羥烷基(例如羥甲基、羥乙基、羥丙基、羥丁基、羥戊基及羥己基)及如上文所定義直鏈或分支鏈C1
-C6
羥烷基之C1
-C6
烷基醚。在某些實施例中,R1
、R2
及R3
中之至少一者為直鏈或分支鏈C1
-C6
羥烷基。實例包括但不限於烷醇胺,諸如胺基乙基乙醇胺、N-甲胺基乙醇、胺基乙氧基乙醇、二甲胺基乙氧基乙醇、二乙醇胺、N-甲基二乙醇胺、單乙醇胺(MEA)、三乙醇胺(TEA)、1-胺基-2-丙醇、2-胺基-1-丁醇、異丁醇胺、三乙二胺、其他C1
-C8
烷醇胺及其組合。當胺包括烷基醚組分時,胺可視為烷氧基胺,例如1-甲氧基-2-胺基乙烷。
如本文中所使用,所涵蓋之「還原劑」包括選自次磷酸(H3
PO2
)、抗壞血酸、L(+)抗壞血酸、異抗壞血酸、抗壞血酸衍生物、DEHA(二乙基羥胺)、還原糖(半乳糖)及其組合的化合物。另外,亞磷酸、亞硫酸、硫代硫酸銨及硫代硫酸鉀、木糖、山梨糖醇。可利用N-胺基嗎啉、N-胺基哌嗪、對苯二酚、兒茶酚、四氫富瓦烯、N,N-二甲基苯胺苄胺、羥胺及其他基於硫之還原劑。
如本文中所使用,「氧化劑」對應於(一或多種)氧化暴露之金屬導致金屬腐蝕或金屬上形成氧化物的化合物。氧化劑包括但不限於:過氧化氫;其他過化合物,諸如含有過氧單硫酸根、過硼酸根、過氯酸根、過碘酸根、過硫酸根、過錳酸根及過乙酸根陰離子之鹽及酸;及胺-N-氧化物。
適合之pH調節劑包括氫氧化膽鹼、氫氧化鉀、氫氧化銫、氫氧化四乙銨、氫氧化銨、硝酸、硫酸、胺磺酸、乙醇酸、乳酸及甲磺酸。
如上文所指出,組成物包含至少一種清潔劑。該等清潔劑係選自(i)一或多種水混溶性溶劑及/或(ii)一或多種聚合物及/或檸檬酸中之至少一者。
水混溶性溶劑之實例包括二醇及二醇醚,包括但不限於甲醇、乙醇、異丙醇、丁醇及高級醇(諸如C2
-C4
二醇及C2
-C4
三醇)、四氫糠醇(THFA)、鹵化醇(諸如3-氯-1,2-丙二醇、3-氯-1-丙硫醇、1-氯-2-丙醇、2-氯-1-丙醇、3-氯-1-丙醇、3-溴-1,2-丙二醇、1-溴-2-丙醇、3-溴-1-丙醇、3-碘-1-丙醇、4-氯-1-丁醇、2-氯乙醇)、二氯甲烷、三氯甲烷、乙酸、丙酸、三氟乙酸、四氫呋喃N-甲基吡咯啶酮(NMP)、環己基吡咯啶酮、N-辛基吡咯啶酮、N-苯基吡咯啶酮、甲基二乙醇胺、甲酸甲酯、二甲基甲醯胺(DMF)、二甲亞碸(DMSO)、四亞甲基碸(環丁碸)、二乙醚、苯氧基-2-丙醇(PPh)、苯丙酮、乳酸乙酯、乙酸乙酯、苯甲酸乙酯、乙腈、丙酮、乙二醇、丙二醇(PG)、1,3-丙二醇、二噁烷、丁醯基內酯、碳酸伸丁酯、碳酸伸乙酯、碳酸伸丙酯、二丙二醇、二乙二醇單甲醚、三乙二醇單甲醚、二乙二醇單乙醚、三乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單丁醚(亦即,丁基卡必醇)、三乙二醇單丁醚、乙二醇單己醚、二乙二醇單己醚、乙二醇苯醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二丙二醇二甲醚、二丙二醇乙醚、丙二醇正丙醚、二丙二醇正丙醚(DPGPE)、三丙二醇正丙醚、丙二醇正丁醚、二丙二醇正丁醚、三丙二醇正丁醚、丙二醇苯醚、乙二醇單苯醚、二乙二醇單苯醚、六乙二醇單苯醚、二丙二醇甲醚乙酸酯、四乙二醇二甲醚(TEGDE)、二元酯、丙三醇碳酸酯、N-甲醯基嗎啉、磷酸三乙酯及其組合。
聚合物(若存在)包括但不限於甲基丙烯酸均聚物及與例如丙烯醯胺基甲基丙烷磺酸及順丁烯二酸之共聚物;順丁烯二酸/乙烯基醚共聚物;聚(乙烯吡咯啶酮)/乙酸乙烯酯;均聚物,諸如膦酸化聚乙二醇寡聚物、聚(丙烯酸) (PAA)、聚(丙烯醯胺)、聚(乙酸乙烯酯)、聚(乙二醇) (PEG)、聚(丙二醇) (PPG)、聚(苯乙烯磺酸)、聚(乙烯基磺酸)、聚(乙烯基膦酸)、聚(乙烯基磷酸)、聚(伸乙亞胺)、聚(伸丙亞胺)、聚烯丙胺、聚氧化乙烯(PEO)、聚乙烯吡咯啶酮(PVP)、PPG-PEG-PPG嵌段共聚物、PEG-PPG-PEG嵌段共聚物、聚(乙烯醇)、聚(羥乙基)丙烯酸酯、聚(羥乙基)甲基丙烯酸酯、羥乙基纖維素、甲基羥乙基纖維素、羥丙基纖維素、甲基羥丙基纖維素、三仙膠、海藻酸鉀、果膠、羧甲基纖維素、葡糖胺、聚(二烯丙基二甲銨)氯化物、PEG化(亦即,聚乙二醇化)甲基丙烯酸酯/丙烯酸酯共聚物、聚MADQuat及其共聚物、二甲胺基甲基丙烯酸酯聚合物及其共聚物、三甲銨甲基丙烯酸甲酯聚合物及其共聚物,及其組合。以上共聚物可為無規共聚物或嵌段共聚物。若存在,組成物中之(一或多種)聚合物之量按該組成物之總重量計在約0.0001重量%至約5重量%範圍內。
關於錯合劑,我們已發現如上文所闡述之所有不含磷及硫原子之某些化合物在錯合氧化鈰物種方面有效,其幫助自微電子裝置之表面移除該等氧化鈰物種。在一個實施例中,此等錯合劑係選自酒石酸、乙醯丙酮、麩胺酸、己二酸、氮基三乙酸、胺基參(亞甲基膦酸)、甜菜鹼、IDA(胺基二乙酸)及HEDP(依替膦酸)。
在另一實施例中,錯合劑為乙醯丙酮。
為易於參考,「微電子裝置」對應於半導體基板、平板顯示器、相變記憶體裝置、太陽電池板及其他包括太陽能基板、光伏打及微機電系統(MEMS)的產品,其經製造用於微電子應用、積體電路應用或電腦晶片應用。太陽能基板包括但不限於矽、非晶矽、多晶矽、單晶矽、CdTe、硒化銅銦、硫化銅銦及鎵上砷化鎵(gallium arsenide on gallium)。太陽能基板可經摻雜或未經摻雜。應理解,術語「微電子裝置」並不意謂以任何方式限制,且包括最終將變為微電子裝置或微電子組件之任何基板。
如本文中所使用,「氧化鈰粒子」對應於可用於化學機械研磨漿料之基於鈰之研磨粒子,其包括例如具有式Ce2
O3
及CeO2
之氧化鈰。應瞭解「氧化鈰粒子」可包含氧化鈰、由氧化鈰組成或基本上由氧化鈰組成。
如本文中所使用,「污染物」對應於存在於CMP漿料中之化學物質、研磨漿料之反應副產物、CMP後殘餘物、存在於濕式蝕刻組成物中之化學物質、濕式蝕刻組成物之反應副產物及為CMP製程、濕式蝕刻、電漿蝕刻或電漿灰化製程之副產物的任何其他材料。
如本文中所使用,「CMP後殘餘物」對應於來自研磨漿料之粒子,例如存在於漿料中之化學物質、研磨漿料之反應副產物、富碳粒子、研磨墊粒子、刷去載粒子、建構粒子之裝備材料、本質上為金屬、有機、有機金屬、有機矽或無機之例如含矽材料、含鈦材料、含氮材料、含氧材料、高分子殘餘物材料、含銅殘餘物材料(包括氧化銅殘餘物)、含鎢殘餘物材料、含鈷殘餘物材料、諸如氯及氟之蝕刻氣體殘餘物及其組合及為CMP製程之副產物之任何其他材料。
如本文中所使用,術語「低k介電材料」對應於在分層微電子裝置中用作介電材料的任何材料,其中該材料具有小於約3.5之介電常數。在某些實施例中,低k介電材料包括低極性材料,諸如含矽有機聚合物、含矽混合有機/無機材料、有機矽酸鹽玻璃(OSG)、TEOS、氟化矽酸鹽玻璃(FSG)、二氧化矽、碳氧化矽、氮氧化矽、氮化矽、摻碳氧化物(CDO)或摻碳玻璃,例如來自Novellus Systems, Inc.之CORAL™、來自Applied Materials, Inc.之BLACK DIAMOND™(例如用於PECVD之BD1、BD2及BD3名稱)、來自Dow之SiLK™介電樹脂(藉由多官能環戊二烯酮與含乙炔材料反應產生之基於交聯聚苯之聚合物;參見例如,以引用之方式併入本文中之美國專利第5,965,679號)及Nanopore, Inc.之NANOGLASS™(二氧化矽氣凝膠/乾凝膠(稱為奈米多孔性二氧化矽)及其類似者。應瞭解低k介電材料可具有不同密度及不同孔隙。
如本文中所使用,術語「蝕刻劑」係指:氫氟酸(HF);氟矽酸(H2
SiF6
);氟硼酸;氟矽酸銨鹽((NH4
)2
SiF6
);六氟磷酸四甲銨;氟化銨;二氟化銨;四氟硼酸四級銨及四氟硼酸四級鏻及其組合。
如其中所使用,術語「金屬腐蝕抑制劑」係指非離子型界面活性劑,諸如PolyFox PF-159 (OMNOVA溶液)、聚(乙二醇)(「PEG」)、聚(丙二醇)(「PPG」)、環氧乙烷/環氧丙烷嵌段共聚物,諸如Pluronic F-127 (BASF)、聚山梨醇酯聚氧乙烯(20)脫水山梨糖醇單油酸酯(Tween 80)、聚氧乙烯(20)脫水山梨糖醇單硬脂酸酯(Tween 60)、聚氧乙烯(20)脫水山梨糖醇單棕櫚酸酯(Tween 40)、聚氧乙烯(20)脫水山梨糖醇單月桂酸酯(Tween 20)、聚氧丙烯/聚氧乙烯嵌段共聚物(例如,Pluronic L31、Plutonic 31R1、Pluronic 25R2及Pluronic 25R4)及其組合;及與諸如以下唑類組合之此類化合物:5-胺基四唑、5-苯基-苯并三唑、1H-四唑-5-乙酸、1-苯基-2-四唑啉-5-硫酮、苯并咪唑、甲基四唑、Bismuthiol I、胞嘧啶、鳥嘌呤、胸腺嘧啶、吡唑、亞胺基二乙酸(IDA)、丙硫醇、苯并羥肟酸、檸檬酸、抗壞血酸、5-胺基-1,3,4-噻二唑-2-硫醇(ATDT)、苯并三唑(BTA)、1,2,4-三唑(TAZ)、甲苯基三唑、5-甲基-苯并三唑(mBTA)、5-苯基-苯并三唑、5-硝基-苯并三唑、苯并三唑甲酸、3-胺基-5-巰基-1,2,4-三唑、1-胺基-1,2,4-三唑、羥基苯并三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-1,2,3-三唑、1-胺基-5-甲基-1,2,3-三唑、3-胺基-1,2,4-三唑(3-ATA)、3-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯硫醇-苯并三唑、鹵基-苯并三唑(鹵基=F、Cl、Br或I)、萘三唑、2-巰基苯并咪唑(MBI)、2-巰基苯并噻唑、4-甲基-2-苯基咪唑、2-巰基噻唑啉、5-胺基-1,2,4-三唑(5-ATA)、十二烷基硫酸鈉(SDS)、ATA-SDS、3-胺基-5-巰基-1,2,4-三唑、伸戊基四唑、5-苯基-1H-四唑、5-苄基-1H-四唑、Ablumine O、2-苄基吡啶、丁二醯亞胺、2,4-二胺基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑啶酮、1,5-五亞甲基四唑、1-苯基-5-巰基四唑、二胺基甲基三嗪、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、4-胺基-4H-1,2,4-三唑、3-胺基-5-甲硫基-1H-1,2,4-三唑、苯并噻唑、咪唑、吲二唑(indiazole)、腺嘌呤、丁二醯亞胺、腺苷、咔唑、糖精、尿酸、安息香肟(benzoinoxime)、陽離子四級鹽(例如苯紮氯銨、氯化苄基二甲基十二烷基銨、溴化肉豆蔻基三甲基銨、溴化十二烷基三甲基銨、氯化十六烷基吡錠、Aliquot 336 (Cognis)、氯化苄基二甲基苯基銨、Crodaquat TES (Croda. Inc.)、Rewoquat CPEM (Witco)、對甲苯磺酸十六烷基三甲基銨、氫氧化十六烷基三甲基銨、二氯化1-甲基-1'-十四烷基-4,4'-二吡錠、溴化烷基三甲基銨、鹽酸胺丙啉、氫氧化苄乙銨、苄索氯銨、氯化苄基二甲基十六烷基銨、氯化苄基二甲基十四烷基銨、溴化苄基十二烷基二甲基銨、氯化苄基十二烷基二甲基銨、氯化鯨蠟基吡錠、對甲苯磺酸膽鹼鹽、溴化二甲基二(十八烷基)銨、溴化十二烷基乙基二甲基銨、氯化十二烷基三甲基銨、溴化乙基十六烷基二甲基銨、吉拉德氏試劑(Girard's reagent)、磷酸二氫十六烷基(2-羥乙基)二甲基銨、溴化十六烷基吡錠、溴化十六烷基三甲基銨、氯化十六烷基三甲基銨、甲基苄索氯銨、Hyamine® 1622、Luviquat™、N,N',N'-聚氧乙烯(10)-N-動物脂-1,3-二胺基丙烷液體、奧芬溴銨、溴化四庚基銨、溴化肆(癸基)銨、溴化噻唑啉、氯化三(十二烷基)銨、溴化三甲基十八烷基銨、四氟硼酸1-甲基-3-正辛基咪唑鎓、四氟硼酸1-癸基-3-甲基咪唑鎓、氯化1-癸基-3-甲基咪唑鎓、溴化三(十二烷基)甲基銨、氯化二甲基二硬脂銨、溴化鯨蠟基三甲銨、溴化肉豆蔻基三甲基銨及氯化六羥季銨)、陰離子界面活性劑(例如,十二烷基苯磺酸、十二烷基苯磺酸鈉、十二烷基膦酸(DDPA)及其組合)。
如本文中所使用,術語「鈍化劑」係指減少低k層之化學侵蝕且保護晶圓免受額外氧化的化合物。硼酸為低k鈍化劑之一個實例,但出於此目的已知其他羥基添加劑,例如3-羥基-2-萘甲酸、丙二酸、亞胺基二乙酸、五硼酸銨、脲、甲基三乙氧基矽烷及其混合物。
「實質上不含」在本文中某些實施例中定義為小於2 wt.%、小於1 wt.%、小於0.5 wt.%或小於0.1 wt.%。「不含」意欲在某些實施例中對應於小於0.001 wt.%以考慮環境污染且在另一實施例中為0.0 wt.%。
在一些實施例中,組成物實質上不含(a)腐蝕抑制劑;(b)蝕刻劑;及(c)鈍化劑。在其他實施例中,組成物不含(a)腐蝕抑制劑;(b)蝕刻劑;及(c)鈍化劑。
如下文實驗部分中所展示,我們已發現某些化合物在錯合氧化鈰物種方面出人意料地有效。因此,在另一態樣中,本發明提供一種用於錯合二氧化鈰之方法,該方法包含在pH為約1至約6下摻合其與選自酒石酸、乙醯丙酮、麩胺酸、己二酸、IDA(亞胺基二乙酸)、甜菜鹼、HEDP及氮基三乙酸的氧化鈰錯合化合物。在其他實施例中,一種用於錯合二氧化鈰之方法包含在pH為約4至約6下摻合其與選自酒石酸、乙醯丙酮、麩胺酸、己二酸及氮基三乙酸的氧化鈰錯合化合物。
如本文中所使用,「約」意欲對應於所述值之+/- 0.5%。
如本文中所使用,術語「緩衝劑」係指常見緩衝劑,諸如磷酸鹽(例如磷酸氫二銨、磷酸二氫銨、磷酸銨)及碳酸鹽,諸如碳酸氫鉀及碳酸鉀。若存在,按該組成物之總重量計,組成物包含約0.1 wt%至約20 wt%之緩衝物種。
如本文中所使用,用於自上面有氧化鈰粒子及CMP污染物之微電子裝置移除該等粒子及污染物之「適合性」對應於自微電子裝置至少部分移除該等粒子/污染物。清潔功效由微電子裝置上之物件之減少來評定。例如,可使用原子力顯微鏡來進行清潔前分析及清潔後分析。樣品上之粒子可記錄為像素範圍。直方圖(例如,Sigma Scan Pro)可應用於以特定強度(例如,231-235)過濾像素及計數粒子之數目。粒子減少可使用以下計算:
清潔功效=( 清潔前物件之數目 - 清潔後物件之數目 )
×100
清潔前物件之數目
值得注意地,清潔功效之測定方法僅提供用於實例且並不意欲受限於該實例。可替代地,清潔功效可視為由粒子物質所覆蓋之總表面的百分比。例如,可對AFM進行編程以執行z平面掃描以識別在某一高度臨限值以上所關注之表面形貌區域,且隨後計算由所關注之該等區域覆蓋之總表面面積。熟習此項技術者將容易理解,由清洗後所關注之該等區域覆蓋之面積愈小,移除組成物愈有效。在某些實施例中,使用本文中所描述之組成物,自微電子裝置移除至少75%之粒子/污染物,移除至少90%、至少95%或至少99%之粒子/污染物。
如下文更充分地描述,本文中所描述之組成物可以廣泛多種特定調配物形式體現。
在所有此類組成物中,其中參考重量百分比範圍(包括零下限)論述組成物之特定組分,應理解該等組分可存在或不存在於組成物之各種特定實施例中,且在存在該等組分之實例中,以採用該等組分之組成物的總重量計,其可以低至0.00001重量百分比之濃度存在。
為了將pH調節至所需終點,可利用諸如氫氧化膽鹼之鹼性化合物。
另外,組成物可按需要含有其他添加劑,諸如界面活性劑。
如本文中所使用,術語「界面活性劑」係指降低兩種液體之間或液體與固體之間表面張力(或界面張力)之有機化合物,其通常為含有疏水性基團(例如,烴(例如,烷基)「尾」)及親水性基團之有機兩親媒性化合物。若存在,用於本文中所描述之組成物中之界面活性劑包括但不限於兩性鹽、陽離子界面活性劑、陰離子界面活性劑、兩性離子界面活性劑、非離子界面活性劑及其組合,包括但不限於癸基磷酸、十二烷基膦酸(DDPA)、十四烷基膦酸、十六烷基膦酸、雙(2-乙基己基)磷酸鹽、十八烷基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、膦醯基乙酸、十二烷基苯磺酸(DDBSA)、其他R1苯磺酸或其鹽(其中R1
為直鏈或分支鏈C8
-C18
烷基)、十二烯基丁二酸、二(十八烷基)磷酸氫鹽、十八烷基磷酸二氫鹽、十二胺、十二烯基丁二酸單二乙醇醯胺、月桂酸、棕櫚酸、油酸、檜酸、12羥基硬脂酸、十八烷基膦酸(ODPA)、十二烷基磷酸鹽。所涵蓋之非離子界面活性劑包括但不限於聚氧乙烯月桂基醚、十二烯基丁二酸單二乙醇醯胺、乙二胺肆(乙氧基化物-嵌段-丙氧基化物)四醇、聚乙二醇、聚丙二醇、聚乙二醇或聚丙二醇醚、基於環氧乙烷及環氧丙烷之嵌段共聚物、聚氧丙烯蔗糖醚、第三辛基苯氧基聚乙氧基乙醇、10-乙氧基-9,9-二甲基癸-1-胺、分支鏈聚氧乙烯(9)壬基苯基醚、分支鏈聚氧乙烯(40)壬基苯基醚、二壬基苯基聚氧乙烯、壬基苯酚烷氧基化物、聚氧乙烯山梨糖醇六油酸酯、聚氧乙烯山梨糖醇四油酸酯、聚乙二醇脫水山梨糖醇單油酸酯、脫水山梨糖醇單油酸酯、醇烷氧基化物、烷基-聚葡萄糖苷、全氟丁酸乙酯、1,1,3,3,5,5-六甲基-1,5-雙[2-(5-降冰片烯-2-基)乙基]三矽氧烷、單體十八烷基矽烷衍生物、經矽氧烷改質之聚矽氮烷、聚矽氧-聚醚共聚物及乙氧基化含氟界面活性劑。所涵蓋之陽離子界面活性劑包括但不限於溴化鯨蠟基三甲銨(CTAB)、十七烷氟辛烷磺酸、四乙銨、氯化硬脂基三甲銨、溴化4-(4-二乙胺基苯基氮雜)-1-(4-硝基苄基)吡錠、氯化十六烷基吡錠單水合物、苯紮氯銨、苄索氯銨、氯化苄基二甲基十二烷基銨、氯化苄基二甲基十六烷基銨、溴化十六烷基三甲基銨、氯化二甲基二(十八烷基)銨、氯化十二烷基三甲基銨、對甲苯磺酸十六烷基三甲基銨、溴化二(十二烷基)二甲基銨、氯化二(氫化動物脂)二甲基銨、溴化四庚基銨、溴化肆(癸基)銨及奧芬溴銨、鹽酸胍(C(NH2
)3
Cl)或三氟甲磺酸鹽(諸如三氟甲磺酸四丁銨)、氯化二甲基二(十八烷基)銨、溴化二甲基二(十六烷基)銨、氯化二(氫化動物脂)二甲銨及乙基硫酸聚氧乙烯(16)動物脂乙基銨。所涵蓋之陰離子界面活性劑包括但不限於聚(丙烯酸鈉鹽)、聚丙烯酸銨、聚氧乙烯月桂基醚鈉、二己基磺基丁二酸鈉、十二烷基硫酸鈉、二辛基磺基丁二酸鹽、2-磺基丁二酸鹽、2,3-二巰基-1-丙磺酸鹽、二環己基磺基丁二酸鈉鹽、7-乙基-2-甲基-4-十一烷基硫酸鈉、磷酸鹽含氟界面活性劑、含氟界面活性劑及聚丙烯酸酯。兩性離子界面活性劑包括但不限於炔二醇或經改質之炔二醇、環氧乙烷烷基胺、N,N-二甲基十二烷胺N-氧化物、椰油胺丙酸鈉、3-(N,N-二甲基肉豆蔻基銨基)丙磺酸鹽及(3-(4-庚基)苯基-3-羥丙基)二甲銨基丙磺酸鹽。
關於組成量,其他添加劑與組分(a)、(b)、(c)、(d)、(e)之重量百分比比率在一個實施例中在約0.001:1至約10:1範圍內,且在其他實施例中在約0.1:1至約5:1範圍內。基於本文中所揭示之pH值及熟習此項技術者之知識,pH調節劑之量視製備移除組成物供使用時所尋求之最終pH而定。
組分之重量百分比比率範圍將含括組成物之所有可能經濃縮或經稀釋之實施例。為彼目的,在一個實施例中,提供可經稀釋以用作清潔溶液之經濃縮之移除組成物。濃縮組成物或「濃縮物」有利地准許使用者(例如,CMP製程工程師)在使用時將濃縮物稀釋至所需濃度及pH。經濃縮之水性組成物之稀釋可在約1:1至約49:1或約1:1至約100:1範圍內,其中水性組成物在工具處或恰好在工具之前經溶劑(例如,去離子水)稀釋。熟習此項技術者應瞭解,在稀釋之後,本文中所揭示之組分之重量百分比比率之範圍應保持不變。
就基板而言,本發明之組成物被認為適用於清潔如本文中所闡述之低k介電材料。
在又另一實施例中,本文中所描述之組成物進一步包含氧化鈰粒子及/或CMP污染物。氧化鈰粒子及污染物在清潔已開始之後變為組成物之組分且將溶解且/或懸浮於組成物中。
藉由簡單添加相應成分且混合至均質狀態容易地調配出移除組成物。此外,組成物可易於調配為單封裝調配物或在使用時或使用前混合之多部分調配物,例如,多部分調配物之個別部分可在工具處或在工具上游之儲槽中混合。各別成分之濃度可以組成物之特定倍數廣泛變化,亦即更稀或更濃,且應瞭解,本文中所描述之組成物可以各種方式且可替代地包含符合本文中之揭示內容之成分的任何組合、由其組成或基本上由其組成。
當應用於微電子製造操作時,本文中所描述之組成物有效地用於自微電子裝置之表面清潔氧化鈰粒子及/或CMP污染物(例如,CMP後殘餘物及污染物)。在某些實施例中,在粒子移除之前,水性移除組成物移除至少85%、至少90%、至少95%或至少99%之存在於裝置上之氧化鈰粒子。
在CMP後粒子及污染物移除應用中,本文中所描述之水性移除組成物可與多種習知清潔工具(諸如超高頻音波及電刷洗滌)一起使用,該等工具包括但不限於Verteq單晶圓超高頻音波Goldfinger、OnTrak系統DDS(雙側洗滌器)、SEZ或其他單晶圓噴霧沖洗、Applied Materials Mirra-Mesa™/Reflexion™/Reflexion LK™及超高頻音波分批濕式清洗台系統。
在使用本文中所描述之組成物以自上面有氧化鈰粒子及CMP污染物之微電子裝置移除該等粒子及污染物時,通常在約20℃至約90℃或約20℃至約50℃範圍內之溫度下使水性移除組成物與裝置接觸約5秒至約10分鐘,或約1秒至20分鐘,或約15秒至約5分鐘之時間。此類接觸時間及溫度為說明性的,且在該方法之廣泛實踐內可採用有效地自裝置至少部分移除氧化鈰粒子及CMP污染物的任何其他適合之時間及溫度條件。「至少部分清潔」與「實質上移除」在某些實施例中均對應於移除至少85%、至少90%、至少95%或至少99%之在粒子移除之前存在於裝置上之氧化鈰粒子。
在達成所需粒子移除作用之後,水性移除組成物可容易地自先前已施加有該水性移除組成物之裝置移除,正如在本文中所描述之組成物之給定最終用途應用中所需且有效的。在一個實施例中,沖洗溶液包括去離子水。其後,可使用氮氣或旋轉乾燥循環來乾燥該裝置。
另一態樣係關於根據本文中所描述之方法製得之改良微電子裝置且關於含有此類微電子裝置之產品。
另一態樣係關於一種經再循環水性移除組成物,其中該移除組成物可經再循環直至如熟習此項技術者容易地確定,粒子及/或污染物負載達至水性移除組成物可容納之最大量為止。
又一態樣係關於製造包含微電子裝置之物品的方法,該方法包含使微電子裝置與水性移除組成物接觸持續足以自上面有氧化鈰粒子及CMP污染物之微電子裝置移除該等粒子及污染物的時間及使用本文中所描述之移除組成物將該微電子裝置併入至該物品中。
在另一態樣中,提供一種自上面有氧化鈰粒子及CMP污染物之微電子裝置移除該等粒子及污染物之方法。因此在另一態樣中,本發明提供一種用於自上面有氧化鈰粒子及化學機械研磨污染物之微電子裝置移除該等粒子及污染物之方法,該方法包含:
(i)使該微電子裝置與本發明之該組成物接觸;及
(ii)用包含去離子水之水性溶液至少部分自該微電子裝置移除該等粒子及污染物。
本發明可藉由其較佳實施例之以下實例進一步說明,但應理解,除非另外具體指示,否則僅出於說明之目的包括此等實例且不意欲限制本發明之範疇。
實驗部分
將固定量之CeO2
-漿料添加至各經稀釋之組成物中。對於各組成物將混合物攪拌持續相同時間量。將其過濾且自溶液分離固體殘餘物。溶液中溶解的氧化鈰離子經由ICP-OES方法量測。
支持資料ICP-OES溶解度資料
檸檬酸 = 1% + 抗壞血酸 = 6% + 添加劑 | |
2% | 添加劑 |
實例1 | 氮基三乙酸 |
實例2 | 甜菜鹼 |
實例3 | 麩胺酸 |
實例4 | 蘋果酸 |
實例5 | EDTA |
實例6 | 三胺五乙酸 |
實例7 | 己二酸 |
實例8 | 檸檬酸 |
實例9 | 酒石酸 |
實例10 | 乙醯丙酮 |
實例11 | 三乙二醇單丁醚 |
實例12 | 草酸 |
實例13 | 鄰苯二甲酸 |
實例14 | 富馬酸(Fumaric acid) |
實例 | 所添加之氧化鈰% |
實例1 | 1.52 |
實例2 | 2.76 |
實例3 | 0.95 |
實例4 | 2.73 |
實例5 | 1.06 |
實例6 | 1.35 |
實例7 | 0.91 |
實例8 | 1.22 |
實例9 | 1.29 |
實例10 | 2.78 |
實例11 | 1.74 |
實例12 | 0.40 |
實例13 | 1.20 |
實例14 | 1.02 |
檸檬酸 = 1% + DEHA = 1% + TGME = 2.5% | ||
實例15 | IDA | |
實例16 | HEDP | |
檸檬酸 = 1% + H3PO2 = 1% + TGME = 2.5% | ||
實例17 | 甜菜鹼 | |
實例18 | HEDP |
實例 | 所添加之氧化鈰% |
實例15 | 1.22 |
實例16 | 2.75 |
實例17 | 1.13 |
實例18 | 3.09 |
Claims (10)
- 一種pH為約1至約6之組成物,其包含: (a)鈰-氧鍵斷裂化合物; (b)pH調節劑; (c)至少一種清潔劑; (d)選自酒石酸、乙醯丙酮、麩胺酸、己二酸、甜菜鹼、氮基三乙酸、亞胺基二乙酸(IDA)、依替膦酸(HEDP)及胺基參(亞甲基膦酸)的氧化鈰錯合化合物;及 (e)水。
- 如請求項1之組成物,其中鈰-氧鍵斷裂化合物係選自親核化合物、氧化劑及還原劑。
- 如請求項1之組成物,其中該pH調節劑係選自氫氧化膽鹼、氫氧化鉀、氫氧化銫、氫氧化四乙銨、氫氧化銨、硝酸、硫酸、胺磺酸、乙醇酸、乳酸及甲磺酸。
- 如請求項1之組成物,其中該氧化鈰錯合化合物為胺基參(亞甲基膦酸)。
- 如請求項1之組成物,其中該氧化鈰錯合化合物為乙醯丙酮。
- 如請求項1之組成物,其中該氧化鈰錯合化合物為亞胺基二乙酸。
- 如請求項1之組成物,其中該氧化鈰錯合化合物為依替膦酸。
- 如請求項1之組成物,其中該氧化鈰錯合化合物為甜菜鹼。
- 如請求項1之組成物,其中該清潔劑係選自水混溶性有機溶劑及聚合物。
- 一種用於錯合氧化鈰之方法,該方法包含在pH為約1至約6下將其與選自酒石酸、乙醯丙酮、麩胺酸、己二酸、甜菜鹼、氮基三乙酸、亞胺基二乙酸(IDA)、依替膦酸(HEDP)及胺基參(亞甲基膦酸)的氧化鈰錯合化合物摻合。
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