TW200907049A - Peroxide activated oxometalate based formulations for removal of etch residue - Google Patents
Peroxide activated oxometalate based formulations for removal of etch residue Download PDFInfo
- Publication number
- TW200907049A TW200907049A TW097105089A TW97105089A TW200907049A TW 200907049 A TW200907049 A TW 200907049A TW 097105089 A TW097105089 A TW 097105089A TW 97105089 A TW97105089 A TW 97105089A TW 200907049 A TW200907049 A TW 200907049A
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- Taiwan
- Prior art keywords
- metal
- formulation
- acid
- cleaning composition
- ammonium
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 110
- 238000009472 formulation Methods 0.000 title claims abstract description 68
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 123
- 239000002184 metal Substances 0.000 claims abstract description 123
- 238000004140 cleaning Methods 0.000 claims abstract description 40
- 238000004377 microelectronic Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 13
- 230000007797 corrosion Effects 0.000 claims abstract description 13
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 239000000356 contaminant Substances 0.000 claims abstract description 8
- 239000013011 aqueous formulation Substances 0.000 claims abstract description 6
- 239000012458 free base Substances 0.000 claims abstract description 4
- 239000003112 inhibitor Substances 0.000 claims abstract description 4
- 239000013020 final formulation Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052681 coesite Inorganic materials 0.000 claims abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract 2
- 229910052682 stishovite Inorganic materials 0.000 claims abstract 2
- 229910052905 tridymite Inorganic materials 0.000 claims abstract 2
- 150000003839 salts Chemical class 0.000 claims description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 24
- -1 peroxyacid salt Chemical class 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 14
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 10
- 239000011609 ammonium molybdate Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical group [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 238000005502 peroxidation Methods 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- CXWDLVFMICKAJK-UHFFFAOYSA-N N.[NH4+].[NH4+].[NH4+].OC(CC([O-])=O)(CC([O-])=O)C([O-])=O Chemical group N.[NH4+].[NH4+].[NH4+].OC(CC([O-])=O)(CC([O-])=O)C([O-])=O CXWDLVFMICKAJK-UHFFFAOYSA-N 0.000 claims description 2
- BKVMXZRBMWKQEG-UHFFFAOYSA-E P(=O)([O-])([O-])[O-].[V+5].[Mo+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[V+5].[Mo+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] BKVMXZRBMWKQEG-UHFFFAOYSA-E 0.000 claims description 2
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- DVUVKWLUHXXIHK-UHFFFAOYSA-N tetraazanium;tetrahydroxide Chemical group [NH4+].[NH4+].[NH4+].[NH4+].[OH-].[OH-].[OH-].[OH-] DVUVKWLUHXXIHK-UHFFFAOYSA-N 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical group OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims 2
- 229910052712 strontium Inorganic materials 0.000 claims 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims 1
- 229910003206 NH4VO3 Inorganic materials 0.000 claims 1
- WSPUSBVIGOVLFH-UHFFFAOYSA-J [Cl-].[Cl-].[Cl-].[Cl-].C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C WSPUSBVIGOVLFH-UHFFFAOYSA-J 0.000 claims 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 238000003556 assay Methods 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 claims 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims 1
- 235000015097 nutrients Nutrition 0.000 claims 1
- MVAOEXBRERPGIT-UHFFFAOYSA-N octamine Chemical compound N.N.N.N.N.N.N.N MVAOEXBRERPGIT-UHFFFAOYSA-N 0.000 claims 1
- 231100000719 pollutant Toxicity 0.000 claims 1
- XGZGDYQRJKMWNM-UHFFFAOYSA-N tantalum tungsten Chemical compound [Ta][W][Ta] XGZGDYQRJKMWNM-UHFFFAOYSA-N 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229920002120 photoresistant polymer Polymers 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 235000012431 wafers Nutrition 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- 238000004380 ashing Methods 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ATOFMGTVIWEKRT-UHFFFAOYSA-N cyclohexane;hydrazine Chemical compound NN.C1CCCCC1 ATOFMGTVIWEKRT-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
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- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 1
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
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- CMHJKGDUDQZWBN-UHFFFAOYSA-N 2-(methylamino)-3-oxobutanoic acid Chemical compound CNC(C(C)=O)C(O)=O CMHJKGDUDQZWBN-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 1
- ZIMXAFGAUMQPMG-UHFFFAOYSA-N 2-[4-[bis(carboxymethyl)amino]butyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCCN(CC(O)=O)CC(O)=O ZIMXAFGAUMQPMG-UHFFFAOYSA-N 0.000 description 1
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 1
- ZFDNAYFXBJPPEB-UHFFFAOYSA-M 2-hydroxyethyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCO ZFDNAYFXBJPPEB-UHFFFAOYSA-M 0.000 description 1
- VYQMXBMNWDFBHM-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate tetramethylazanium Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O VYQMXBMNWDFBHM-UHFFFAOYSA-K 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
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- 229910000072 bismuth hydride Inorganic materials 0.000 description 1
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- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
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- 235000015165 citric acid Nutrition 0.000 description 1
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- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- 229960002433 cysteine Drugs 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
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- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
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- 235000000346 sugar Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 description 1
- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 description 1
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/14—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Steroid Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Dental Preparations (AREA)
Description
200907049 九、發明說明: 【發明所屬之技術領域】 本發月關於伙微電子裝置移除蝕刻殘餘物質之組合物, 該組合物提供較好的耐腐敍性及改良的清洗效率。特別是 本發明提供由過氧化物活化的水性、高驗性金屬氧酸鹽調 配物其在微電子工業特別有用,^對於從具有金屬線路 及m電子基板移純關餘物質特別有效。本發明 亦提供使用上述組合物清洗上述微電子基板及裝置之方 法。 【先前技術】 微電子製造之不可或缺的部分係、制光阻劑將影像從光 罩或線網轉印至所需的電路層。在實現所需影像轉印之 t使用餘刻過程以形成所需結構。用此方法形成之最常 見結構係、金屬線路及通孔。該等金屬線路詩在處於同一 製:層的積體電路各部分之間形成電連接。該等通靡 』牙過電’丨質層然後用導電金屬填充的孔。該等通孔用於 在積體電路的不同垂直層之間建立電連接。在用於形成金 屬線路及通孔的製程中通常使用含i素氣體。 、在蝕刻過程完成後’大部分光阻劑可藉由化學剝離劑溶 液或=藉由氧氣電漿灰化製程移除。問題係該等姓刻過程 產生高度不溶的含金屬的殘餘物質,其可能無法藉由普通 化學剝離劑溶液移除。此外’在灰化製程期間,該等含金 屬的殘餘物質被氧化而變得更難以移除,特別就基於銘之 積體電路而δ。參見”處理蝕刻及植入殘餘物質”,國際半 128860.doc 200907049 1997 年 8 月,56-63 導體(Semiconductor Internati〇nal), 頁。 上述蝕刻過程的一實例係積體電路上金屬線路之圖案 化。在此製程中,光阻劑塗層施加於金屬薄膜上,然後透 過一光罩或線網成像以在光阻劑塗層中選擇性地曝光一圖 案。將該塗層顯影以移除已曝光或者未曝光的光阻劑(取 決於所用光阻劑《色調),並在金屬圖案上產生一光阻 劑。殘留的光阻劑通常在高溫下硬烘烤以移除溶劑並視需 要使δ亥聚合物基質交聯。然後執行實際金屬姓刻步驟。該 飯刻步驟經由氣熊雷艰夕说r t , 孔〜、¥水之作用將未經光阻劑覆蓋的金屬移 除。移除此金屬將圖案從光阻劑層轉印至金屬層。然後用 有機剝離劑溶液或用—氧氣電漿灰化程序將殘留的光阻 劑移除(剝除")。該灰化程序之後通常係使用一液體有機 制離心液之清洗步驟。然而,現有的剝離劑溶液(通常 係驗性剝離劑溶液)將不可溶解的金屬氧化物及其他含金 屬的殘餘物質殘留在積體電路上。 安此㈣製程之另一實例係積體電路上通孔(互連孔)之圖 :在此裝%中’光阻劑塗料施加於電介質薄膜上,然 -圖=光罩或線網成像以在光阻劑塗層令選擇性地曝光 一圖案。將該塗層顯影以移除已曝^者未曝光的光阻劑 ’、於所用光阻劑之色調)’並在金屬圖案上產生一光阻 劑。殘留的光阻劑诵赍乂 >、w 展王尤丨且 φ ± 吊在南溫下硬烘烤以移除溶劑並視需 要使該聚合物基質交聯 此 “ 此崎驟經由氣態電漿的作用…刻步驟。 的作用將未經光阻劑覆蓋的電介 128860.doc 200907049 質移除。移除上述電介質之步驟將圖案從光阻劑層轉印至 電介質層。然後用有機剝離劑溶液或一氧氣電漿灰化步驟 移除(”剝離”)殘留的光阻劑。通常,t亥電介質被蝕刻至下 曰金屬層曝光的位置。鈦或氮化鈦抗反射或擴散壁障層通 常存在於金屬/電介質邊界。此邊界層通常蝕刻透過以曝 露下層金屬。已發現蝕刻透過鈦或氮化鈦層之作用引起鈦 併入在通孔内形成的蝕刻殘餘物質中。氧氣電漿灰化將通
孔殘餘物質氧化使其更難以移除。因此必須隸殘餘物質 移除增強劑加人剝離劑溶液巾以能夠清除該等殘餘物質。 參見”使用現代電漿灰化機移除氮化鈦上生長的二氧化欽 並降低通孔接觸電阻”,Mat, Res. s〇c Sympn,w 卷’ 1998,345_3 52頁。該灰化程序之後通常係、使用一液體 有機剝離劑溶液之清洗步驟。然而,現有的剝離劑溶液 (通常係驗性剝離劑溶液)將不可溶解的金屬氧化物及其他 含金屬的殘餘物質殘留在積體電路上。市面上有一些具有 兩有機溶劑含量的基於㈣的剥離劑及灰化後殘餘物質移 除劑’但其對於其他在通孔中或金屬線路上發現的殘餘物 質不大有效。其等亦需要高溢(通常说或更高)以將殘餘 物質從通孔及金屬線路清除。 在含有金屬薄膜的微電路上使用鹼性剝離劑總是不能生 產出高品質電4,特別是使用含有銘或活性金屬(諸如紹 或欽)與更具正電性金屬(諸如銅或旬之各種組合或合金之 金屬薄膜時。.已觀察到各類金屬腐姓,諸如金屬線路之腐 敍晶鬚、電敍、凹坑、叫π , ^ , 几凹口,其至少部分係由於金屬與驗 I28860.doc 200907049 性剝離劑反應。此外由Lee等人(Proc Interface ,89,第 3 7 149頁)揭示水清洗步驟(用於將有機剝離劑從晶圓移 除)之前很少有腐蝕作用發生。顯然,腐蝕係金屬與清洗 期間所存在的強鹼性水溶液接觸之結果。已知鋁金屬在上 述條件下快速腐蝕,Ambat等人,腐蝕科學,33卷(5), 684頁,1992 。 先鈉用於避免腐蝕問題之方法,使用含有非鹼性有機溶 劑諸如異丙醇之中間清洗液。然而,&等方法費用高且具 有不需要的安全性、化學衛生及環境影響。 在美國專利號6,465,403中,揭示了用於微電子工業之水 性鹼性組合物,其適於藉由移除光阻劑殘餘物質及其他不 需要的污染物以剝離或清洗半導體晶圓基板。該水性組合 物通常含有(a)—種或多種無金屬離子鹼,其量足以產生約 10-13之pH; (b)約0.01重量%至約5重量%(以% 表示) 之水溶性無金屬離子矽酸鹽;((〇約〇 〇1重量%至約ι〇重量 /〇之種或多種金屬螯合劑及(d)視需要之其他成分。 然而,在先前技術中所揭示的組合物中均無法有效地移 除在典型蝕刻製程後殘留的所有有機污染及含金屬的殘餘 物質。利用該等調配物,特別難以移除切的殘餘物質。 因此,需要藉由將無機及有機污染從半導體晶圓基板移除 但不損壞積體電路以清洗上述基板之剝離組合物。隨著單 晶圓工具之廣泛應用,亦需要能夠以較短時間及在比先前 技術中:且合物低的溫度下移除金屬污染及有機污染之調配 物此等組合物不可腐蝕部分構成積體電路之金屬特徵並 128860.doc 200907049 應避免由中間清洗液引起的費減不利結果。在用前-段 落中論述之調配物清洗時,鎮及I呂線路尤其易被腐飯。 【發明内容】 根據本發明’提供—種高度驗性、水性調配物,其包括 ⑷水’(b)至少-種無金屬離子鹼,其量^以產生一具驗 !·生pH ’較好約n至約13 4之鹼性之最終組合物;⑷約 〇.〇1重量。Λ至約5重量%(以% Si〇2表示)之至少一種水溶性 ,金屬離子賴鹽腐餘抑制劑;⑷約QGi重量%至約财 量〇/°之至少一種金屬螯合劑;及(e)超過0至約2.0重量%之 至少一種金屬氧酸鹽。此等調配物與至少一種可與金屬氧 酸鹽反應而形成金屬過氧酸鹽之過氧化物混合,產生一水 I·生驗性微電子清洗組合物。水的量為1〇〇重量調配物 或組合物之餘數。_另外指明,否則在本申請案中提及 之所有百分比係重量百分比,且係基於組合物之總重。 在足以將不需要的污染物及/或殘餘物質從基板表面清 除之溫度下,使該清洗組合物與半導體晶圓基板接觸一段 時間。本發明之組合物提供增強的耐腐蝕性及改良的清洗 效率。 【實施方式】 本發明之高度鹼性、水性調配物包括(a)水,(b)至少一 種無金屬離子鹼,其量係足以產生—具鹼性pH,較好約Η 至約13 ·4之pH之农終s周配物,(c)約〇.〇 1重量。/。至約$重量 %(以% Si%表示)之至少一種水溶性無金屬離子矽酸鹽腐 蝕抑制劑;(d)約0.01重量。/。至約10重量%之至少一種金屬 128860.doc 200907049 聲合劑,及⑷超過0至約2.0重量%之至少—種金屬氧酸 鹽。此等調配物與至少一種可與調配物之金屬氧酸趟反應 的過氧化物混合,因此在使用所得的清洗組合物之前形成 了金屬過氧酸鹽。在足以將不需要的污染物及/或殘餘物 質從基板表面清除之溫度下,使所得的清洗組合物與微電 子裝置如半導體晶圓基板接觸一段時間。 本發明提供一種適於與用於將污染物及殘餘物質從半導 ^ 冑晶圓剝離及清除之過氧化物混合的新的水性調配物,其 中遠等調配物含有水(較好係高純度去離子水)、一種或多 種無金屬離子驗、-種或多種無金屬離子石夕酸鹽腐钱抑制 劑、一種或多種金屬螯合劑及一種或多種金屬氧酸鹽。 〃任何適當的驗可用於本發明之水性調配物。該等驗較好 係氫氧化第三銨,諸如氫氧化四烷銨(包括含有羥基及烷 氧基的烷基,通常烷基或烷氧基具有丨至4個碳原子卜= 等鹼性物質中最佳的係氫氧化四甲基銨及三甲基m 基-虱氧化銨(膽鹼)。其他可用的氫氧化第三銨之實例包 曱土 3經丙基氫氧化録、三甲基小經丁基氯氧化 鉍一甲基-4-經丁基氫氧化銨、三乙基_2_羥乙基氫氧化 銨、三丙基-2-羥乙基氫氧化銨、三丁基。,乙基氫氧化 銨、二曱基乙基m基氫氧化錄、二甲基二(2_經乙美) 氫氧化銨、單甲基三(2_經乙基)氫氧化銨、氫氧化四:基 錢、氫氧化四丙基銨、氫氧化四丁基胺、單甲基-三乙: t氧㈣、單f基三丙基氫氧化銨、單甲基三丁基氫氧I 銨、單乙基三曱基氫氧化銨、單乙基三丁基氫氧化錢、二 Ι 28860.doc ΙΟ 200907049 f基二乙基氫氧化錢'二甲基二丁基氫氧化銨及其類似物 及其混合物。 其他在本發明可發揮功能的鹼包括氫氧化銨、有機胺特 別是烷醇胺,諸如2-胺基乙醇、^胺基_2_丙醇、丨_胺基-% 丙醇、2-(2-胺基乙氧基)乙醇、2_(2_胺基乙基胺基)乙醇、 2-(2-胺基乙基胺基)乙胺及其類似物’其他強有機驗諸如 胍、1,3-戊二胺、4_胺甲基义卜辛二胺、胺基乙基哌嗪、 4-(3-胺丙基)嗎啉、1,2_二胺基環己烷、三(2_胺乙基) 胺、2-甲基-1,5-戊二胺及㈣。含有金屬離子諸如納或卸 之鹼性溶液亦可行,但較不佳,因為可能發生殘餘金屬污 染。亦可使用該等額外的驗性組分特別是氮氧化錄與前述 四烧基氫氧化敍之混合物。 該無金屬離子鹼將以能夠提供最終調配物一高鹼性 PH(通常約η至約13·4之pH)之量應用於該調配物。 任何適當的&金屬離子石夕酸鹽可用於本發明之調配物 中。該矽酸鹽較好係矽酸第三銨’諸如矽酸四烷基銨(包 括含有經基及烧氧基的&基,it常在院基或院氧基中U 至4個碳原子)。最佳的無金屬離子矽酸鹽組分係矽酸四曱 基銨。用於本發明的其他適當❹金屬離子石夕酸鹽源可藉 由將任何-種或多種下列物質溶解在高鹼性清洗劑中就地 產生。用於在清潔劑中產生錢鹽之適當的無金屬離子物 質係固體石夕晶圓、砍酸、朦體二氧化碎、發煙二氧化梦或 任何其他適當形式的矽或二氧化矽。 至少—種無金屬離子矽酸鹽將以約〇〇1至約5重量%,較 128860.doc -11 - 200907049 好約0 · 01至2重量%之量存在於調配物中。 本發明之調配物亦調配有一種或多種適當的金屬螯合劑 配製以增加調配物保留溶液中金屬之能力,並增強晶圓基 板上金屬殘餘物質的溶解。用於此目的之金屬螯合劑之典 型實例係下列有機酸及其異構物及鹽類:乙二胺四乙酸 (EDTA)、丁二胺四乙酸、環己烷_丨,2_二胺四乙酸 (CyDTA)、二乙三胺五乙酸(DETPA)、乙二胺四丙酸、值 乙基)乙二胺三乙酸(HEDTA)、N,N,N,,N,-乙二胺四(次曱基 膦)酸(EDTMP)、三伸乙四胺六乙酸(TTHA)、以二胺基_ 2-羥基丙烷-N,N,N’,N’-四乙酸(DHPTA)、甲基亞胺基二乙 酸、丙二胺四乙酸、氮川三乙酸(NTA)、檸檬酸、酒石 酸、葡萄糖酸、糖二酸、甘油酸、草酸、苯二甲酸、馬來 酸、^杏仁酸、丙二酸、乳酸、水揚酸、兒茶盼、沒食子 酸、沒食子酸丙酯、焦五倍子酚、8-羥基喹啉及半胱氨 酸。 較佳金屬螯合劑係胺基羧酸諸如環己烷_丨,2_二胺四乙酸 (CyDTA)。此類金屬螯合劑對通常在電漿,,灰化”後在金屬 線路及通孔上發現的含鋁殘餘物質具有高親和力。此外, 用於此類金屬螯合劑之pKa通常包括—約12的?反&,其提 高了本發明組合物的性能。 至少一種金屬螯合劑將以約0.01至約1〇重量%,較好約 0.01至約2重量%之量存在於調配物中。 來自週期表V族及vi族之過渡金屬之任何適合的金屬氧 酸鹽可應用於本發明調配物中。該金屬氧酸鹽組分可包括 128860.doc 200907049 一種或多種選自單核金屬氧酸鹽、均多核金屬氧酸鹽及雜 多核金屬氧酸鹽之金屬氧酸鹽。本發明之過渡金屬金屬氧 酸鹽包括鉬(Mo)、鎢(W)、釩(V)、鈮(Nb)、鉻(Cr)或组 (Ta)之金屬氧酸鹽。金屬氧酸鹽以超過〇至約2重量%之 里,較好以約〇.〇1至約2重量之量存在於調配物中。
適合的單核金屬氧酸鹽包括如式[Μ〇ρ]η·ζ+所示之金屬氧 酸鹽,其中Μ為高氧化態前期過渡金屬諸如Cr、ν、Μ〇、 W、Nb及Ta,Ζ係電荷平衡反離子。最佳電荷平衡反離子 係貝子、四烷基銨及銨陽離子。金屬離子諸如鈉或鉀亦可 行,但較不佳’因為可能發生殘餘金屬污染。上述適合的 單核金屬氧酸鹽實例之一係例如(ΝΗ4)2Μ〇〇4,其中ΝσΗ4+ 係電荷平衡反離子,而Μο〇4_係金屬氧酸根。 適合的均多核金屬氧酸鹽包括如式[Mm〇p]n.z+所示之金 屬氧酸鹽’其中Μ為高氧化態前期過渡金屬諸如。、ν、 W、Nb及Ta’且ζ係電荷平衡反離子。該等金屬氧酸 鹽係由單核金屬氧酸鹽藉由與酸縮合所形成。適合的均夕 核金屬氧酸鹽實例之-係⑽4)馬〇24,其中NH/係電二 平衡反離子,❿Μ〇7〇2,係均多核金屬氧酸根。 雜多核金屬氧酸鹽包括如式[XxMm〇p]n-z+所示之金屬:酸 鹽’其中Μ為高氧化態前期過渡金屬諸如。、ν、心、 :、Nb及Ta; X係一雜原子,其可為過渡金屬或者 " 衡反離子適合的雜多核金屬氧酸蜂眚 原子X而w為前期過渡金屬Μ 例之—係、H4SiWl2〇4G,其中Η+係電荷平衡反離子,s = ^ \ rfn W7 -5¾. -tfn ιά λλ- α _ 句雜 128860.doc -13- 200907049 本發明5周配物可含有不損害清洗組合物效果之可選成 分,諸如(例如)界面活性劑、殘餘物質移除劑增強劑及其 類似物。 用於本發明調配物的適合金屬氧酸鹽包括(但不限於)鉬 酸銨((NH4)2Mo〇4)、鎢酸銨((NH4)2W〇4)、鎢酸(h2W〇4)、 偏釩酸銨(NH4V〇3)、七鉬酸銨((NH4)6M〇7〇24)、偏鎢酸銨 ((NH4)6H2W12〇40)、仲鎢酸銨((NH4)i()H2Wi2〇42)、十釩酸 四曱銨((TMA)4H;2V丨0〇28)、十銳酸四甲銨 ((TMA)6Nb10〇28)、重鉻酸銨((NH4)2Cr2〇7)、磷鉬酸銨 ((NHAPMouO4。)、矽鎢酸(H4SiWi2〇4〇)、磷鎢酸 (H3PW12O40)、填酸(h3PMo12〇40)、石夕 |目酸(H4SiMo12〇40) 及鉬釩磷酸鹽(HJMoioVWw)。 本發明之較佳調配物實例包括(但不限於)含有2.丨%氫氧 化四甲銨、0.14%矽酸四甲銨、〇 12%反式·丨,2環己二胺四 乙酸及約0.01至約2%鉬酸銨或矽鎢酸及其餘為水至1〇〇% 之調配物。 上述調配物將與至少一種過氧化物以上述調配物與過氧 化物約5:1至約40:1之比率,較佳以15:1至3〇:1之比率,且 最佳以20:1之比率混合,以提供微電子清洗組合物。可使 用可與上述調配物之金屬氧酸鹽反應形成金屬過氧酸鹽之 任何適合的過氧化物。適合的過氧化物包括過氧化氫;過 氧酸諸如過氧一磷酸(H4P2〇8)、過氧二硫酸(H4S2〇8)、鄰 笨二甲醯亞胺基過氧己酸、過氧乙酸(C2H4〇3)、過氧苯曱 酸、二過氧苯二甲酸及其鹽;及烷基過氧化物諸如過氧化 128860.doc •14· 200907049 苯甲醯、過氧化甲基乙基綱 丁基異丙苯。較佳的過氧化物係過氧化 ^本、過氧化三級 增強的清洗效率據認為係過氧化物^等 質活化之結果。在驗性溶液中,…亥等金屬氣酸鹽物 、Cr' Vv、NbV、及^屬乳酸鹽(金屬f、 金屬過氧酸鹽。該等金屬 ”過聽物反應形成無機 效果。首先,金>1=^ 種方柄強清潔 无金屬過氧酸鹽分解產生單重
高反應性自由基氧化劑,為 =H k该早重悲軋可增進殘餘物質 艨 '—紐a A ^ 、軋化且因此增進殘餘物質的 洛解。已知金屬過氧酸鹽亦為有 ' 高效觸媒。該催化活性可增強 I乳化物乳化之 公& S 5$基於妷之殘餘物質的氧化與 移除。 因為於此Q ☆液中產生的所得金屬過氧酸鹽分解,該等 溶液的壽命通常有限。根據由過氧化錮酸鹽所產生溶液之 紅色’财數第三段落中含有鉬酸銨的較佳調配物,當其與 20:1稀釋比之過氧化氫(鳩)混合時在抑了顯示一介於5 分鐘(2%!目酸銨)與45分鐘(〇.〇1%銦酸錢)之壽命。就前數 第三段落中含有矽鎢酸之較佳調配物而言,根據顏色變 化,由調配物與20%過氧化氫(2〇:1)混合所得之清洗組合 物之壽命長得多,介於45分鐘(2%矽鎢酸)與5小時(〇 〇1% 矽鎢酸)。鋁蝕刻速率之測量隨含有前數第三段落中含有 矽鎢酸(0.5%)之較佳調配物之清洗組合物而變化,其中當 較佳調配物以20:1稀釋比與過氧化氫2〇%混合時,顯示一 僅為3 _ 5小時的槽池壽命,但該組合物可藉由加入過氧化 128860.doc -15- 200907049 氫重新活化。加熱該等組合物引起該等組合物壽命大幅縮 短。 在該等用於半導體及微晶圓工業之清洗組合物中使用金 屬氧酸鹽之另一顧慮係在處理後金屬可能殘留在晶圓表面 上。用XPS(X射線光電子光譜法)測試來自該等組合物的鉬 與鶴之金屬吸收。在將鋁及TEOS晶圓在前數第四段落之 含有鉬酸銨及鎢矽酸鹽的較佳調配物(其與過氧化氫20%以 20:1比率混合)中處理後,在去離子水中清洗1分鐘,然後 在氬氣中乾燥’在任何晶圓表面上觀察不到鉬或鶴。顯示 δ亥專金屬陰離子可輕易地從晶圓表面清洗去,過渡金屬污 染將不會係該等調配物之問題。 本發明清洗組合物之蝕刻速率在25°C下用前數第五段落 之較佳調配物測量’其中調配物中加入稀釋比為2〇:丨之 20%過氧化氫。作為比較,製備一對照調配物而不用任何 金屬氧酸鹽(對照調配物=水、2.1 %氫氧化四曱銨、〇.丨4〇/。 矽酸四曱銨、0,12%反式-u-環己二胺四乙酸)。與對照調 配物相比,所有經測試的含有矽鎢酸或鉬酸銨的較佳清洗 組合物並不明顯降低鋁、鈦及TE〇s蝕刻速率,但鎢餘刻 速率約為用對照調配物所獲得之蝕刻速率的一半。 在銘金屬線路及通孔上測試了該等較佳調配物(其中加 入了稀釋比20:1之20%過氧化氫)之清洗效率。作為一對照 物’使用如一段落之對照調配物。就經測試的銘金屬線路 而言’對照調配物只能在45。(:下在5分鐘後移除所有殘餘 物質’但即使在25。(:下5分鐘後總是觀察到電流腐蝕。對 128860,doc 16 200907049 於兩種較佳調配物’與對照調配物相比,觀察到電流腐蝕 大幅減少,在較低溫度下及在較短處理時間内實現殘餘物 質之移除。對於含有鉬酸銨(0.1%)的較佳調配物,在25C>c 下在僅僅2分鐘内該等金屬線路被清潔但不受腐蝕,對於 含有矽鎢酸(0.5%)的較佳調配物,在25<;(:下2分鐘内該等 金屬線路被完全清潔,但幾乎觀察不到腐蝕。就經測試的 鋁通孔而言,在25。(:下該對照調配物可在僅僅5分鐘内清 潔該等通孔,該調配物含有稀釋比2〇:丨之2〇%過氧化氫。 含有矽鎢酸的較佳調配物容許使用較高的調配物與2〇%過 氧化氫之比率(30:1)而不會觀察到用對照調配物引起的腐 蝕增強。在該情況下,在25t:下在僅僅2分鐘内可以完成 清潔。 通常,含有矽鎢酸及鉬酸銨之較佳調配物顯示優於對照 調配物的腐蝕抑制作用及清洗效率。同樣在兩種情況下, 相對於對照調配物,鎢蝕刻率幾乎下降一半。 雖然已根據具體的實施例描述了本發明,應瞭解在不背 離此處所揭示發明概念之精神及範圍的前提下,可進行改 變 '改良及變更。因此,旨在包含所有屬於附加申請專力 範圍之精神及範圍之内的改變、改良及變更。 128860.doc
Claims (1)
- 200907049 十、申請專利範圍: 1 · 一種用於清泳4電子裝置之與過氧化物組合之驗性水性 調配物,該調配物含有:(a)水;(b)至少一種無金屬離子 驗,其量係足以產生一具有鹼性pH之最終調配物;(c)約 0.01重量%至約5重量%(以% Si〇2表示)之至少一種水溶 性無金屬離子矽酸鹽腐蝕抑制劑;(d)約〇.〇 1重量%至約 10重量%之至少一種金屬螯合劑;及(e)超過〇重量%至約 2.0重量%之至少一種金屬氧酸鹽。 2. 如請求項1之調配物,其中該金屬氧酸鹽係選自由鉬 (Mo)、鎢(W)、鈒(V)、鈮(Nb)、鉻(Cr)及组(Ta)組成之 群的金屬之金屬氧酸鹽。 3. 如請求項2之調配物,其中該金屬氧酸鹽係選自由單核 金屬氧酸鹽、均多核金屬氧酸鹽及雜多核金屬氧酸鹽組 成之群。 4. 如請求項2之調配物’其中該調配物之鹼性pH係約pH 1 1 至約13.4。 5. 如請求項2之調配物,其中該無金屬離子鹼係氫氧化 録’該無金屬離子矽酸鹽係矽酸第三銨,及該金屬螯合 劑係胺基羧酸。 6. 如請求項5之調配物,其中該金屬氧酸鹽係選自由鉬酸 銨((ΝΗ4)2Μο04)、鎢酸銨((NH4)2W04)、鎢酸(h2 w〇4)、 偏釩酸銨(nh4vo3)、七鉬酸銨((nh4)6m〇7o24)、偏鎢酸 銨((NH4)6H2W1204〇)、仲鎢酸銨((NH4)10H2W12〇42)、十釩 酸四曱鈹((TMA)4H2V10〇28)、十銳酸四甲銨 128860.doc 200907049 ((TMA)6Nb10O28)、重鉻酸銨((NH4)2Cr2〇7)、磷鉬酸錢 ((NH4)3PMo1204。)、矽鎢酸(H4SiWi2〇4〇)、磷鎢酸 (H3PW12O40)、磷鉬酸(H3PM〇12〇40)、矽鉬酸 (H4SiMo1204〇)及鉬釩磷酸鹽(H5PM〇igV204())組成之群。 7.如請求項6之調配物,其中該無金屬離子鹼係氫氧化四 曱銨,該無金屬離子矽酸鹽係矽酸四曱銨,該金屬養人 劑係反式-1,2-環己二胺四乙酸,及該金屬氧酸鹽係選自 由鉬酸銨及矽鎢酸組成之群。8 ·如請求項7之調 石夕酸四甲銨、0.12%反式-1,2-環己二胺四乙酸、及約〇 〇ι 至約2。/。金屬氧酸鹽、及其餘為使其全量至ι〇〇%之水。 9. 如請求項8之調配物,其中該金屬氧酸鹽係鉬酸銨。 10. 如請求項8之調配物,其中該含氧鉬酸鹽係矽鎢酸。 11. 種用於清潔微電子裝置的鹼性、水性清洗組合物,該 /月洗組合物含有如請求項丨之調配物與至少一種過氧化 人—考以約5:1至約40:1之調配物與過氧化物之比混 士八:其中該至少一種過氧化物可與金屬氧酸鹽反應形 成金屬過氧酸鹽。 1 2 · —種用於、、备 、主、“ ^减電子裝置的驗性、水性清洗組合物,該 清洗組合物A古 ^ 物,二者有如知求項2之調配物與至少一種過氧化 合,且其/ 5·1至約4〇:1之調配物與過氧化物之比混 成金屬過二:^一種過氧化物可與金屬氧酸鹽反應形 種用於凊潔微電子裝置的驗性、水性清洗組合物,該 128860.doc 200907049 清洗組合物含有如請求 物,二者以約5.!至約4〇1 少一種過氧化 ——約40:1之調配物與過氧化物之比混 :八屬 少一種過氧化物可與金屬氧酸鹽反應形 成金屬過氧酸鹽。 求項η之鹼性、水性清洗組合物,其中該至少一種 過氧化物包括過氧化氫。 15·=求項12之驗性、水性清洗組合物,其中該至少-種 過乳化物包括過氧化氫。 16.=請求項13之鹼性、水性清洗組合物,其中該至少-種 過乳化物包括過氧化氫。 17, I種用於將污染物或殘餘物質從微電子基板清除之方 足’包括將該微電子基板與如請求項"之清洗組合物在 以移除4物或殘餘物f之溫度下接觸—段時間。 ^種用於將污染物或殘餘物質從微電子基板清除之方 足’包括將該微電子基板與如請求項12之清洗組合物在 ^移除污染物或殘餘物f之溫度τ接觸—段時間。 ^種用於將污染物或殘餘物質從微電子基板清除之方 足包括將該微電子基板與如請求項13之清洗組合物在 从移除污染物或殘餘物質之溫度下接觸—段時間。 ·:種用於將污染物或殘餘物質從微電子基板清除之方 足以f微電子基板與如請求項16之清洗組合物在 除〉7染物或殘餘物質之溫度下接觸-段時間。 128860.doc 200907049 七、指定代表圖: (一) 本案指定代表圖為:(無)。 (二) 本代表圖之元件符號簡單說明: 八、本案若有化學式時,請揭示最能顯示發明特徵的化學式: (無)128860.doc
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- 2008-01-28 AT AT08724882T patent/ATE483012T1/de active
- 2008-01-28 DE DE602008002819T patent/DE602008002819D1/de active Active
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- 2008-01-28 PL PL08724882T patent/PL2111445T3/pl unknown
- 2008-01-28 CN CN2008800051913A patent/CN101611130B/zh active Active
- 2008-01-28 PT PT08724882T patent/PT2111445E/pt unknown
- 2008-01-28 CA CA002677964A patent/CA2677964A1/en not_active Abandoned
- 2008-01-28 BR BRPI0808074-7A patent/BRPI0808074A2/pt not_active IP Right Cessation
- 2008-01-28 JP JP2009549586A patent/JP2010518242A/ja active Pending
- 2008-01-28 US US12/522,716 patent/US8183195B2/en not_active Expired - Fee Related
- 2008-01-28 DK DK08724882.9T patent/DK2111445T3/da active
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TWI757381B (zh) * | 2016-11-29 | 2022-03-11 | 南韓商三星電子股份有限公司 | 蝕刻組成物 |
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Publication number | Publication date |
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ATE483012T1 (de) | 2010-10-15 |
MY145938A (en) | 2012-05-31 |
WO2008100377A1 (en) | 2008-08-21 |
DK2111445T3 (da) | 2011-01-17 |
PT2111445E (pt) | 2010-12-29 |
JP2010518242A (ja) | 2010-05-27 |
IL199999A (en) | 2013-03-24 |
CN101611130B (zh) | 2011-05-18 |
US20100035786A1 (en) | 2010-02-11 |
PL2111445T3 (pl) | 2011-04-29 |
CN101611130A (zh) | 2009-12-23 |
IL199999A0 (en) | 2010-04-15 |
CA2677964A1 (en) | 2008-08-21 |
EP2111445B1 (en) | 2010-09-29 |
KR20090110906A (ko) | 2009-10-23 |
ZA200905362B (en) | 2010-05-26 |
EP2111445A1 (en) | 2009-10-28 |
KR101446368B1 (ko) | 2014-10-01 |
TWI441920B (zh) | 2014-06-21 |
ES2356109T8 (es) | 2011-10-11 |
BRPI0808074A2 (pt) | 2014-08-05 |
US8183195B2 (en) | 2012-05-22 |
DE602008002819D1 (de) | 2010-11-11 |
ES2356109T3 (es) | 2011-04-05 |
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