TW202328497A - 選擇性濕式蝕刻組合物及方法 - Google Patents
選擇性濕式蝕刻組合物及方法 Download PDFInfo
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- TW202328497A TW202328497A TW111139799A TW111139799A TW202328497A TW 202328497 A TW202328497 A TW 202328497A TW 111139799 A TW111139799 A TW 111139799A TW 111139799 A TW111139799 A TW 111139799A TW 202328497 A TW202328497 A TW 202328497A
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- Prior art keywords
- ammonium
- hydroxide
- acid
- composition
- triazole
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 48
- 239000011733 molybdenum Substances 0.000 claims abstract description 48
- 239000007800 oxidant agent Substances 0.000 claims abstract description 40
- 238000004377 microelectronic Methods 0.000 claims abstract description 26
- 239000008139 complexing agent Substances 0.000 claims abstract description 21
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 15
- -1 tetraethylammonium halide Chemical class 0.000 claims description 21
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003112 inhibitor Substances 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 16
- 238000005260 corrosion Methods 0.000 claims description 16
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000003002 pH adjusting agent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 13
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 10
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 10
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 10
- 239000012964 benzotriazole Substances 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 9
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 239000006174 pH buffer Substances 0.000 claims description 7
- 239000006179 pH buffering agent Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 claims description 6
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 6
- WXSBVEKBZGNSDY-UHFFFAOYSA-N 5-phenyl-2h-benzotriazole Chemical compound C1=CC=CC=C1C1=CC2=NNN=C2C=C1 WXSBVEKBZGNSDY-UHFFFAOYSA-N 0.000 claims description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- CWRVKFFCRWGWCS-UHFFFAOYSA-N Pentrazole Chemical compound C1CCCCC2=NN=NN21 CWRVKFFCRWGWCS-UHFFFAOYSA-N 0.000 claims description 6
- OIRDTQYFTABQOQ-KQYNXXCUSA-N adenosine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O OIRDTQYFTABQOQ-KQYNXXCUSA-N 0.000 claims description 6
- HIMXGTXNXJYFGB-UHFFFAOYSA-N alloxan Chemical compound O=C1NC(=O)C(=O)C(=O)N1 HIMXGTXNXJYFGB-UHFFFAOYSA-N 0.000 claims description 6
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 6
- PYIGXCSOLWAMGG-UHFFFAOYSA-M methyl(triphenyl)phosphanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 PYIGXCSOLWAMGG-UHFFFAOYSA-M 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 229960005152 pentetrazol Drugs 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003760 tallow Substances 0.000 claims description 6
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 claims description 6
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 claims description 6
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 5
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 claims description 5
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 5
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 5
- 229940075419 choline hydroxide Drugs 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 241000208340 Araliaceae Species 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims description 4
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 4
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000008434 ginseng Nutrition 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- UKLQXHUGTKWPSR-UHFFFAOYSA-M oxyphenonium bromide Chemical compound [Br-].C=1C=CC=CC=1C(O)(C(=O)OCC[N+](C)(CC)CC)C1CCCCC1 UKLQXHUGTKWPSR-UHFFFAOYSA-M 0.000 claims description 4
- 229960001125 oxyphenonium bromide Drugs 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 4
- 239000001230 potassium iodate Substances 0.000 claims description 4
- 229940093930 potassium iodate Drugs 0.000 claims description 4
- 235000006666 potassium iodate Nutrition 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- NHAZGSRLKBTDBF-UHFFFAOYSA-N 1,2,4-triazol-1-amine Chemical compound NN1C=NC=N1 NHAZGSRLKBTDBF-UHFFFAOYSA-N 0.000 claims description 3
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 3
- NXRIDTLKJCKPOG-UHFFFAOYSA-N 1,4-dihydroimidazole-5-thione Chemical compound S=C1CN=CN1 NXRIDTLKJCKPOG-UHFFFAOYSA-N 0.000 claims description 3
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 3
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 3
- AIACLXROWHONEE-UHFFFAOYSA-N 2,3-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=C(C)C(=O)C=CC1=O AIACLXROWHONEE-UHFFFAOYSA-N 0.000 claims description 3
- JUNAPQMUUHSYOV-UHFFFAOYSA-N 2-(2h-tetrazol-5-yl)acetic acid Chemical compound OC(=O)CC=1N=NNN=1 JUNAPQMUUHSYOV-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 3
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 claims description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical group NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 3
- XGWWZKBCQLBJNH-UHFFFAOYSA-N 3-methylsulfanyl-1h-1,2,4-triazol-5-amine Chemical compound CSC1=NN=C(N)N1 XGWWZKBCQLBJNH-UHFFFAOYSA-N 0.000 claims description 3
- AGWWTUWTOBEQFE-UHFFFAOYSA-N 4-methyl-1h-1,2,4-triazole-5-thione Chemical compound CN1C=NN=C1S AGWWTUWTOBEQFE-UHFFFAOYSA-N 0.000 claims description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 3
- YZTYEGCWRPJWEE-UHFFFAOYSA-N 5-(benzotriazol-2-yl)pentan-1-amine Chemical compound C1=CC=CC2=NN(CCCCCN)N=C21 YZTYEGCWRPJWEE-UHFFFAOYSA-N 0.000 claims description 3
- HHDRWGJJZGJSGZ-UHFFFAOYSA-N 5-benzyl-2h-tetrazole Chemical compound C=1C=CC=CC=1CC=1N=NNN=1 HHDRWGJJZGJSGZ-UHFFFAOYSA-N 0.000 claims description 3
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 3
- HCEKEODXLSQFDV-UHFFFAOYSA-N 5-methyltriazol-1-amine Chemical compound CC1=CN=NN1N HCEKEODXLSQFDV-UHFFFAOYSA-N 0.000 claims description 3
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 claims description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 3
- AJNQPSCMOSUVKK-UHFFFAOYSA-N 5-propan-2-yl-1h-1,2,4-triazole Chemical compound CC(C)C=1N=CNN=1 AJNQPSCMOSUVKK-UHFFFAOYSA-N 0.000 claims description 3
- 229930024421 Adenine Natural products 0.000 claims description 3
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical group N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 239000002126 C01EB10 - Adenosine Substances 0.000 claims description 3
- PJWWRFATQTVXHA-UHFFFAOYSA-N Cyclohexylaminopropanesulfonic acid Chemical compound OS(=O)(=O)CCCNC1CCCCC1 PJWWRFATQTVXHA-UHFFFAOYSA-N 0.000 claims description 3
- YXHXDEBLSQQHQE-UHFFFAOYSA-N N.N.OP(O)=O Chemical compound N.N.OP(O)=O YXHXDEBLSQQHQE-UHFFFAOYSA-N 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 claims description 3
- 229960000643 adenine Drugs 0.000 claims description 3
- 229960005305 adenosine Drugs 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 claims description 3
- YCNIBOIOWCTRCL-UHFFFAOYSA-N azane;2,2,2-trifluoroacetic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)F YCNIBOIOWCTRCL-UHFFFAOYSA-N 0.000 claims description 3
- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 claims description 3
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 claims description 3
- YNTQKXBRXYIAHM-UHFFFAOYSA-N azanium;butanoate Chemical compound [NH4+].CCCC([O-])=O YNTQKXBRXYIAHM-UHFFFAOYSA-N 0.000 claims description 3
- YUUVAZCKXDQEIS-UHFFFAOYSA-N azanium;chlorite Chemical compound [NH4+].[O-]Cl=O YUUVAZCKXDQEIS-UHFFFAOYSA-N 0.000 claims description 3
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 3
- NFCRBQADEGXVDL-UHFFFAOYSA-M cetylpyridinium chloride monohydrate Chemical compound O.[Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NFCRBQADEGXVDL-UHFFFAOYSA-M 0.000 claims description 3
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 claims description 3
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 claims description 3
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims description 3
- SMSCVBBYKOFGCY-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SMSCVBBYKOFGCY-UHFFFAOYSA-M 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
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- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- PZJJEOFNVNZTOM-UHFFFAOYSA-N benzyl(tetradecyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCCCNCC1=CC=CC=C1 PZJJEOFNVNZTOM-UHFFFAOYSA-N 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
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- QDYLMAYUEZBUFO-UHFFFAOYSA-N cetalkonium chloride Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 QDYLMAYUEZBUFO-UHFFFAOYSA-N 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- KENBDIBVUKXMTB-UHFFFAOYSA-N heptadecyl(trimethyl)azanium Chemical compound CCCCCCCCCCCCCCCCC[N+](C)(C)C KENBDIBVUKXMTB-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- DJQJFMSHHYAZJD-UHFFFAOYSA-N lidofenin Chemical compound CC1=CC=CC(C)=C1NC(=O)CN(CC(O)=O)CC(O)=O DJQJFMSHHYAZJD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
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- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- HIQXJRBKNONWAH-UHFFFAOYSA-N methylidenephosphane Chemical compound P=C HIQXJRBKNONWAH-UHFFFAOYSA-N 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JIVZKJJQOZQXQB-UHFFFAOYSA-N tolazoline Chemical compound C=1C=CC=CC=1CC1=NCCN1 JIVZKJJQOZQXQB-UHFFFAOYSA-N 0.000 description 1
- 229960002312 tolazoline Drugs 0.000 description 1
- VRFQDZQUTDJJMF-UHFFFAOYSA-N toluene;2h-triazole Chemical compound C1=CNN=N1.CC1=CC=CC=C1 VRFQDZQUTDJJMF-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- ITHPEWAHFNDNIO-UHFFFAOYSA-N triphosphane Chemical compound PPP ITHPEWAHFNDNIO-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
提供用於蝕刻微電子裝置基板上之含鉬膜之組合物及方法。微電子裝置基板與本發明之組合物接觸達足以至少部分地移除該含鉬膜之時間。該組合物包含至少一種氧化劑、至少一種錯合劑、至少一種陽離子表面活性劑，且具有約7.5至約13之pH。該蝕刻劑組合物在室溫下以約20至50 Å/分鐘之蝕刻速率選擇性地移除鉬，同時具有經改良之移除均勻性。
Description
本發明概言之係關於自微電子裝置基板蝕刻或移除含鉬材料。
通常，鎢及基於鎢之材料在3D-NAND之製造中用作電極。然而，已發現鎢材料對各種蝕刻劑組合物敏感。舉例而言，在使用W電極之製程中，發現用於電極隔離(所謂的「W凹陷」)之包括磷酸及硝酸之酸性組合物引起鎢層之部分蝕刻。
目前，正尋找3D-NAND結構在記憶體裝置中之效用。為在記憶體性能方面達成更佳效率，3D-NAND製造商已研究可在記憶體裝置中獲得優良性能之其他材料。具體而言，許多3D-NAND製造商已利用鉬代替W層。因此，製造商需要可選擇性地移除凹陷中之Mo而不移除諸如TEOS及氧化鋁之材料之蝕刻劑組合物。特別感興趣者係以一蝕刻速率選擇性地移除鉬，使得每一凹陷在受控蝕刻條件下達成實質上相同目標蝕刻深度之蝕刻劑組合物。
提供用於選擇性蝕刻微電子裝置基板上之含鉬膜之組合物及方法。使微電子裝置基板與本發明之組合物接觸達足以至少部分地移除含鉬膜之時間。組合物包含以下各項、由其組成或基本上由其組成：至少一種氧化劑、至少一種陽離子表面活性劑、水及達成約7至約13之pH所需之一定量之pH調節劑。蝕刻劑組合物在室溫下以約20至50 Å/分鐘之蝕刻速率選擇性地移除鉬，同時具有經改良之移除均勻性。
除非上下文另外明確指明，否則如本說明書及隨附申請專利範圍中所用，單數形式「一(a, an)」及「該」包括複數個指示物。除非上下文另外明確指明，否則如本說明書及隨附申請專利範圍中所用，術語「或」通常以其包括「及/或」之意義使用。
術語「約」通常係指認為與所列舉值相當之數值範圍(例如，具有相同功能或結果)。在多種情況下，術語「約」可包括捨入至最接近的有效數字之數值。
由端點列舉之數值範圍包含歸屬於該範圍內之所有數值(例如，1至5包含1、1.5、2、2.75、3、3.80、4及5等)。
本發明提供選擇性蝕刻組合物，其包含：
至少一種氧化劑；
至少一種陽離子表面活性劑；
水；及
達成約7至約13之pH所需之一定量之pH調節劑，且視情況包含以下各項中之一或多者：
至少一種錯合劑，
至少一種pH緩衝劑，或
至少一種氧化劑穩定劑。
本發明之組合物可用於自微電子裝置基板之表面蝕刻(亦即，移除)含鉬膜。具體而言，組合物顯示對含鉬材料之優良選擇性，同時限制對包含TEOS及氧化鋁之表面的損害。
如本文所用，術語「微電子裝置」對應於經製造用於微電子、積體電路或電腦晶片應用之半導體基板，其包括3D NAND結構、平板顯示器及微機電系統(MEMS)。應理解，術語「微電子裝置」並不意欲以任何方式進行限制且包括含有例如負通道金屬氧化物半導體(nMOS)及/或正通道金屬氧化物半導體(pMOS)電晶體且最終將變成微電子裝置或微電子總成之任何基板。該等微電子裝置通常含有至少一個基板，該基板可選自例如矽、SiO
2、Si
3N
4、OSG、FSG、碳化矽、氫化碳化矽、氮化矽、氫化氮化矽、碳氮化矽、氫化碳氮化矽、氮化硼、抗反射塗層、光阻劑、鍺、含鍺、含硼、Ga/As、撓性基板、多孔無機材料、金屬(例如銅及鋁)及擴散障壁層(例如但不限於TiN、Ti(C)N、TaN、Ta(C)N、Ta、W或WN)。該等膜與各種後續處理步驟(例如化學機械拋光(CMP)及各向異性蝕刻製程)相容。
微電子裝置包含含鉬材料。如本文所用，「含鉬材料」及「鉬」包括基於材料之總重量包含大於50重量%元素鉬之任何材料。含鉬材料之實例包括(但不限於)純鉬(Mo)及含有鉬之合金或混合物以及鉬氧化物及碳化物。舉例而言，已知在微電子裝置製造期間所沈積之鉬亦可含有通常小於5 wt%之鋁(Mo-Al)或鈦(Mo-Ti)，且「鉬」將包括該等材料。熟習此項技術者將理解，各種鉬物種之化學式可基於鉬離子之氧化態而變，其中鉬之常見氧化態係-3、-1、+1、+2、+3、+4、+5或+6。
組合物之氧化劑係能夠在例如鹼性pH條件下將鉬氧化以產生可溶性鉬物種之彼等物種。實例包括過氧化氫(H
2O
2)、FeCl
3、FeF
3、Fe(NO
3)
3、Sr(NO
3)
2、CoF
3、MnF
3、oxone、(2KHSO
5•KHSO
4•K
2SO
4)、硝酸(HNO
3)、過氧單硫酸銨、亞氯酸銨(NH
4ClO
2)、氯酸銨(NH
4ClO
3)、碘酸銨(NH
4IO
3)、硝酸銨(NH
4NO
3)、過硼酸銨(NH
4BO
3)、過氯酸銨(NH
4ClO
4)、過碘酸銨(NH
4IO
4)、過硫酸銨((NH
4)
2S
2O
8)、次氯酸銨(NH
4ClO)、鎢酸銨((NH
4)
10H
2(W
2O
7))、過硫酸鈉(Na
2S
2O
8)、次氯酸鈉(NaClO)、過硼酸鈉、碘酸鉀(KIO
3)、過錳酸鉀(KMnO
4)、過硫酸鉀(K
2S
2O
8)、次氯酸鉀(KClO)、亞氯酸四甲銨((N(CH
3)
4)ClO
2)、氯酸四甲銨((N(CH
3)
4)ClO
3)、碘酸四甲銨((N(CH
3)
4)IO
3)、過硼酸四甲銨((N(CH
3)
4)BO
3)、過氯酸四甲銨((N(CH
3)
4)ClO
4)、過碘酸四甲銨((N(CH
3)
4)IO
4)、過硫酸四甲銨((N(CH
3)
4)S
2O
8)、過氧單硫酸四丁銨、過氧單硫酸、尿素過氧化氫((CO(NH
2)
2)H
2O
2)、過乙酸(CH
3(CO)OOH)、第三丁基過氧化氫、硝基苯磺酸鹽、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯苯醌、四氧嘧啶、過碘酸及其組合。在一個實施例中，氧化劑選自過氧化氫、尿素-過氧化氫、過硫酸銨、過碘酸、過乙酸或第三丁基過氧化氫。
氧化劑可以有效自微電子裝置、尤其在其他金屬層之存在下移除鉬之任何量存在。在一個實施例中，蝕刻劑組合物可包含約0.1重量%至約5重量%之氧化劑。在其他實施例中，氧化劑之量係約0.1重量%至約2重量%或約0.1重量%至約1重量%。氧化劑可直接引入至組合物中或可製備成氧化劑溶液之一部分且隨後在接觸微電子裝置之前與剩餘組分組合。後者將藉由最小化其暴露於鹼性條件之時間量來進一步防止氧化劑之分解。
組合物包含至少一種pH調節劑，其量係達成至少約7之組合物pH所需的。在一個實施例中，組合物之pH係約7.5至約13且在另一實施例中約8至約11。適宜pH調節劑之實例包括(但不限於)鹼金屬氫氧化物、鹼土金屬氫氧化物、氫氧化四烷基銨(例如氫氧化四甲銨(TMAH)、氫氧化四乙銨(TEAH)、氫氧化四丙銨(TPAH)及氫氧化四丁銨(TBAH))、氫氧化三丁基甲銨(TBMAH)、氫氧化苄基三甲銨(BTMAH)、氫氧化膽鹼、氫氧化乙基三甲銨、氫氧化參(2-羥基乙基)甲銨、氫氧化二乙基二甲銨、氫氧化四烷基鏻(例如氫氧化四丁鏻(TBPH)、氫氧化四甲鏻、氫氧化四乙鏻及氫氧化四丙鏻)、氫氧化苄基三苯鏻、氫氧化甲基三苯鏻、氫氧化乙基三苯鏻、氫氧化正丙基三苯鏻及其組合。在一個實施例中，pH調節劑選自氫氧化四甲銨或氫氧化膽鹼。
在某些實施例中，本文所利用之pH調節劑係以約0.1重量%至約10重量%、或約0.1重量%至約8重量%、或約0.1重量%至約5重量%之量存在。
本文所述之組合物可缺乏氨或氫氧化銨或實質上缺乏氨或氫氧化銨。在另一實施例中，蝕刻劑組合物不含氨及氫氧化銨。該等儘管有效地使pH升高至期望位準，但存在大量健康及環境問題且將顯著增加處置及減輕該等問題之成本。
陽離子表面活性劑通常係四級銨鹽之鹽且可用於鈍化表面以使能夠選擇性及均勻地去除含鉬材料。實例性陽離子表面活性劑包括(但不限於)溴化十六烷基三甲銨(cetyl trimethylammonium bromide, CTAB) (亦稱為溴化十六烷基三甲銨(hexadecyltrimethyl ammonium bromide))、氯化十六烷基三甲銨(CTAC)、十七氟辛磺酸、鹵化四乙銨、氯化硬脂醯基三甲銨、溴化4-(4-二乙基胺基苯基偶氮基)-1-(4-硝基苄基)吡啶鎓、氯化十六烷基吡啶鎓一水合物、氯化苄烷銨、氯化本索寧、氯化苄基二甲基十二烷基銨、氯化苄基二甲基十六烷基銨、溴化十六烷基三甲銨、氯化二甲基二(十八烷基)銨、氯化十二烷基三甲銨、溴化二(十二烷基)二甲銨、氯化二(氫化牛脂)二甲銨、溴化四庚銨、溴化四(癸基)銨、及奧芬溴銨(oxyphenonium bromide)、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(氫化牛脂)二甲銨、氯化六羥季銨、氯化三甲基十四烷基銨、氯化癸基三甲基銨及氯化苄基二甲銨(BDAC)。
除上文所討論之組分以外，本揭示內容之組合物可進一步包含存在之可選額外組分、由其組成或基本上由其組成，以進一步改良及/或增強組合物用於自微電子裝置選擇性移除鉬之性能。舉例而言，蝕刻劑組合物可視情況進一步包含至少一種錯合劑、至少一種pH緩衝劑或至少一種氧化劑穩定劑中之一或多者。組合物可單獨或以任何組合包含該等組分中之一或多者。舉例而言，組合物可包含錯合劑及pH緩衝劑二者。此外，或另外，組合物可進一步包含在氧化劑之前或與其組合添加至組合物之氧化劑穩定劑。
如本文所用，「錯合劑」包括熟習此項技術者理解為錯合劑、螯合劑及/或鉗合劑之彼等化合物。當存在時，錯合劑將化學上結合或物理上固持欲使用本文所述之組合物自微電子裝置移除之鉬原子及/或離子，以改良此材料之蝕刻速率。適宜錯合劑包括(但不限於)胺基乙基乙醇胺、N-甲基胺基乙醇、胺基乙氧基乙醇、二甲基胺基乙氧基乙醇、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、4-(2-羥基乙基)嗎啉(HEM)、乙二胺四乙酸(EDTA)、間-二甲苯二胺(MXDA)、亞胺基二乙酸(IDA)、2-(羥基乙基)亞胺基二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲脲、尿素、尿素衍生物、尿酸、丙胺酸、精胺酸、天冬醯胺、天冬胺酸、半胱胺酸、麩胺酸、麩醯胺酸、組胺酸、異白胺酸、白胺酸、離胺酸、甲硫胺酸、苯丙胺酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸、1-羥基亞乙基-1,1-二膦酸(HEDP)、1,5,9-三氮雜環十二烷-N,N',N"-參(亞甲基膦酸) (DOTRP)、1,4,7,10-四氮雜環十二烷-N,N',N",N'"-四(亞甲基膦酸) (DOTP)、氮基參(亞甲基)三膦酸、二伸乙基三胺五(亞甲基膦酸)(DETAP)、胺基三(亞甲基膦酸)、雙(六亞甲基)三胺五亞甲基膦酸、1,4,7-三氮雜環壬烷-N,N',N"-參(亞甲基膦酸)(NOTP)、羥乙基二磷酸鹽、氮基參(亞甲基)膦酸、2-膦醯基-丁烷-1,2,3,4-四甲酸、羧基乙基膦酸、胺基乙基膦酸、草甘膦、乙二胺四(亞甲基膦酸)、苯基膦酸、草酸、琥珀酸、馬來酸、蘋果酸、丙二酸、己二酸、苯二甲酸、乳酸、檸檬酸、檸檬酸鈉、檸檬酸鉀、檸檬酸銨、1,2,3-丙三甲酸、三羥甲基丙酸、酒石酸、葡糖醛酸、2-羧基吡啶、4,5-二羥基-1,3-苯二磺酸二鈉鹽及其組合。在一個實施例中，錯合劑選自1-羥基亞乙基-1,1-二膦酸(HEDP)、乳酸或檸檬酸。
錯合劑可以有效改良鉬之蝕刻速率之任何量存在。舉例而言，當使用時，組合物可包含約0.1重量%至約20重量%之錯合劑。在另一實施例中，錯合劑之量係約0.5重量%至約15重量%且在另一實施例中約1.0重量%至約10重量%。
當存在時，pH緩衝劑可用於維持及穩定組合物之pH，由其當用於選擇性移除含鉬材料時。pH緩衝劑可為金屬腐蝕抑制劑，其保護金屬層免於氧化，由此在鉬層之移除期間穩定pH，或其可為銨鹽，其可對組合物進行緩衝免於pH變化，以延長組合物之儲放壽命。亦可使用該等之組合。
舉例而言，在一個可選實施例中，組合物包含至少一種金屬腐蝕抑制劑作為pH緩衝劑。金屬腐蝕抑制劑可包含一或多種腐蝕抑制劑、由其組成或基本上由其組成，該等腐蝕抑制劑包括(但不限於) 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、吡唑、5-胺基-1,3,4-噻二唑-2-硫醇(ATDT)、苯并三唑(BTA)、1,2,4-三唑(TAZ)、1,2,3-三唑、甲苯三唑、5-甲基-苯并三唑(mBTA)、5-苯基-苯并三唑、5-硝基-苯并三唑、苯并三唑羧酸、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-苯基硫醇-苯并三唑、鹵基-苯并三唑(鹵基=F、Cl、Br或I)、萘并三唑、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)、3-胺基-5-巰基-1,2,4-三唑、戊四唑、5-苯基-1H-四唑、5-苄基-1H-四唑、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、吲唑、腺嘌呤、腺苷、咔唑、N-環己基-3-胺基丙磺酸及其組合。較佳地，金屬腐蝕抑制劑包含pKa為約9之唑化合物。舉例而言，金屬腐蝕抑制劑可為甲苯三唑。
可選金屬腐蝕抑制劑可以有效保護金屬層免於腐蝕且不顯著影響鉬之蝕刻速率之任何量存在。因此，腐蝕抑制劑在蝕刻劑組合物中之量係提供基本上不依賴於抑制劑之Mo蝕刻速率之量。具體而言，在使用時，蝕刻劑組合物可包含約0.001重量%至約1.0重量%之腐蝕抑制劑。在一個實施例中，腐蝕抑制劑之量係約0.05重量%至約0.5重量%且在另一實施例中約0.01重量%至約0.10重量%。
在另一可選實施例中，選擇性蝕刻組合物包含銨鹽作為pH緩衝劑。適宜銨鹽包括例如乙酸銨、碳酸氫銨、丁酸銨、三氟乙酸銨、磷酸氫二銨、磷酸二氫銨、膦酸銨及其組合之鹽。
在另一可選實施例中，組合物進一步包含在氧化劑之前或與其組合添加至組合物之氧化劑穩定劑。實例性穩定劑包括甘胺酸、絲胺酸、脯胺酸、白胺酸、丙胺酸、天冬醯胺、天冬胺酸、麩醯胺酸、纈胺酸、及離胺酸、氮基三乙酸、亞胺基二乙酸、乙二胺四乙酸(EDTA)、(1,2-伸環己基二氮基)四乙酸(CDTA)、尿酸、四乙二醇二甲醚、二伸乙基三胺五乙酸、丙二胺四乙酸、乙二胺二琥珀酸、磺胺及其組合。在一個實施例中，氧化劑穩定劑選自CDTA及EDTA。在一個實施例中，組合物可包含約0.0001重量%至約1.0重量%之氧化劑穩定劑。在其他實施例中，組合物中所存在氧化劑穩定劑之量係約0.0005重量%至約0.5重量%、或約0.001重量%至約0.1重量%。
如上文所討論，組合物可為水性組合物或可為半水性組合物。因此，在一些實施例中，組合物包含水而沒有額外溶劑，而在其他實施例中，組合物進一步包含水與至少一種水溶性或水可混溶有機溶劑。包含至少一種與水組合之溶劑可為組合物之性能提供額外改良，例如所得經蝕刻鉬表面之經改良平面性。適宜溶劑包括例如甲醇、乙醇、異丙醇、丁醇、戊醇、己醇、2-乙基-1-己醇、庚醇、辛醇、乙二醇、丙二醇、丁二醇、碳酸丁二酯、碳酸乙二酯、碳酸丙二酯、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、三乙二醇單丁醚、乙二醇單己醚、二乙二醇單己醚、乙二醇苯基醚、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、二丙二醇乙基醚、丙二醇正丙基醚、二丙二醇正丙基醚(DPGPE)、三丙二醇正丙基醚、丙二醇正丁基醚、二丙二醇正丁基醚、三丙二醇正丁基醚、丙二醇苯基醚、2,3-二氫十氟戊烷、乙基全氟丁醚、甲基全氟丁醚、碳酸烷基酯、碳酸伸烷基酯、4-甲基-2-戊醇、二乙二醇異丙基甲醚及其組合。在一個實施例中，至少一種溶劑包含丙二醇。在使用時，溶劑可以所用總溶劑(水加溶劑)之約10重量%至約90重量%、或總溶劑之約30重量%至約85重量%或總溶劑之約50重量%至約85重量%之量存在，其中剩餘者為水。
應瞭解，通常實踐係製得濃縮形式之組合物，在使用前進行稀釋。舉例而言，該組合物可以更濃縮形式製造，且然後在製造商處、在使用前及/或在工廠使用期間用至少一種溶劑稀釋。稀釋比率可在約0.1份稀釋劑
:1份組合物濃縮物至約100份稀釋劑
:1份組合物濃縮物。進一步應理解，本文所述之組合物包括氧化劑，其隨時間可能不穩定。因此，濃縮形式可實質上不含氧化劑，且氧化劑可在使用前及/或在工廠使用期間由製造商引入至濃縮物或稀釋組合物中。
本文所述之組合物易於藉由簡單添加各別成分並混合至均勻狀態來調配。此外，該等組合物可容易地調配成單包裝調配物或在使用時或使用前混合之多部分調配物，較佳多部分調配物。多部分調配物之個別部分可在工具處或在混合區/區域(例如在線混合器或工具上游之儲存罐)中混合。請考慮，多部分調配物之各個部分可含有混合在一起時形成期望組合物之任何成分/組分。各別成分之濃度可在組合物之特定倍數中廣泛變化，即更稀或更濃縮，且應理解，組合物可不同地及另一選擇地包含與本文揭示內容一致之成分的任何組合，由其組成或基本上由其組成。
因此，在另一態樣中，本發明提供套組，其在一或多個容器包含一或多種適用於形成本文所述組合物之組分。套組之容器必須適於儲存及運輸該等移除組合物組分，例如NOWPak®容器(Advanced Technology Materials, Inc., Danbury, Conn., USA)。含有組合物之組分的一或多個容器較佳包括用於使該一或多個容器中之組分處於流體連通狀態以進行摻和及分配之構件。舉例而言，就NOWPak®容器而言，可將氣體壓力施加至該一或多個容器中之內襯外部，以使內襯中之至少一部分內容物排出並因此使能夠流體連通以進行摻和及分配。或者，氣體壓力可施加至習用可加壓容器之頂隙，或可使用幫浦以使能夠流體連通。另外，系統較佳包括分配埠用於將經摻和組合物分配至加工工具。
可使用實質上化學惰性、無雜質、撓性及彈性聚合物膜材料(例如高密度聚乙烯)製作該一或多個容器之內襯。。期望內襯材料在加工時不需要共擠出或障壁層，且不需要任何顏料、UV抑制劑或可不利地影響內襯中欲處理組分之純度要求之加工助劑。期望內襯材料之清單包括包含以下各項之膜：原生(即無添加劑)聚乙烯、原生聚四氟乙烯(PTFE)、聚丙烯、聚胺基甲酸酯、聚二氯亞乙烯、聚氯乙烯、聚縮醛、聚苯乙烯、聚丙烯腈、聚丁烯等。該等內襯襯墊材料之較佳厚度在約5密爾(0.005英吋)至約30密爾(0.030英吋)之範圍內，例如，20密爾(0.020英吋)之厚度。
關於套組之容器，以下專利及專利申請案之揭示內容以其各別整體內容引用的方式併入本文中：標題為「APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS」之美國專利第7,188,644號及標題為「RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM」之美國專利第6,698,619號，其每一者以引用的方式併入本文中。
在另一態樣中，本發明提供自其上具有含鉬膜之微電子裝置基板蝕刻鉬之方法，該方法包含使該微電子裝置基板與組合物接觸達足以至少部分地移除含鉬膜之時間段，該組合物包含：
至少一種氧化劑；
至少一種陽離子表面活性劑；
水；及
達成約7至約13之pH所需之一定量之pH調節劑，且視情況包含以下各項中之一或多者：
至少一種錯合劑，
至少一種pH緩衝劑，或
至少一種氧化劑穩定劑。
在本發明之方法中，組合物係如本文所闡述。
實例 實例 1
表1中所示之組合物係藉由以下製備：將各種組分組合併使用(TEAH)作為pH調節劑將pH調整至9.5至11.5。將混合物在室溫下攪拌15 min以獲得澄清溶液。
將類似於圖1之簡化繪圖中所示之鉬分層圖案試件放置於配備有攪拌棒及熱電偶之500 mL鐵氟龍(Teflon)燒杯中之200 gm規定組合物中。對於此組實驗，溫度設定為50℃，以600 rpm攪拌。當溫度穩定時，將試件放置於溶液中持續規定時間且隨後移除至靜態DIW沖洗持續30 sec，隨後流動DIW持續1 min。將經沖洗試件用內部氮氣乾燥並藉由SEM進行分析。在分層圖案之頂部、中部及底部獲取之結果顯示於表1中。
表 1
PAN = H
3PO
4/CH
3COOH/HNO
3SC-1 = H
2O
2；NH
4OH；H
2O
SPM = H
2O
2；H
2SO
4；H
2O
對照組合物 = H
2O、過碘酸、乳酸、TEAH
BDAC = 氯化苄基二甲銨
| 調配物 | 頂部 | 中部 | 底部 | 處理溫度/時間 | 差異(頂部減去底部) |
| PAN | 565 | 128 | -9 | 35℃/1分鐘 | 574 |
| SC-1 | 12 | 9.7 | 3.2 | 30℃/5分鐘 | 8.8 |
| SPM | 11 | 8 | 7 | 30℃/8分鐘 | 4 |
| 對照 | 55 | 48 | 41 | 50℃/15分鐘 | 14 |
| 對照+ BDAC | 32 | 32 | 31 | 50℃/15分鐘 | 1 |
| 對照 | 32 | 24 | 21 | 40℃/25分鐘 | 11 |
| 對照+ BDAC | 22 | 21 | 21 | 40℃/25分鐘 | 1 |
自此數據可看出，已知蝕刻組合物PAN、SC-1及SPM (比較實例)顯示較高蝕刻速率、但不期望之均勻性。包括BDAC (一種陽離子表面活性劑)之試樣顯示出對微觀及宏觀均勻性之重大影響。另外，預期藉由調整陽離子表面活性劑之濃度可達成目標凹陷值及加工時間。
實例 2
本揭示內容之組合物係類似於實例1中所闡述之彼等製備且顯示於表2中。
表 2
A = 去離子水；B= 35% TEAH；C= 51.9%過碘酸；D= 85%乳酸；
E= 0.2%氯化苄烷銨；F= 0.2% BTEAC；G= 0.2%氯化六羥季銨；H= 0.2%氯化二甲基二(十八烷基)銨；I= 氯化癸基三甲銨；J= 0.2%氯化十二烷基三甲銨；K= 0.2%氯化三甲基十四烷基銨；L= 0.2%氯化十六烷基三甲銨
| 調配物編號↓ | A | B | C | D | E | F | G | H | I | J | K | L | pH | Rz |
| 對照 | 91.9 | 6.0 | 1.2 | 1.0 | -- | -- | -- | -- | -- | -- | -- | -- | 9.3 | 5.9 |
| 1 | 86.9 | 6.0 | 1.2 | 1.0 | 5.0 | -- | -- | -- | -- | -- | -- | -- | 9.4 | 3.5 |
| 2 | 41.6 | 6.2 | 1.2 | 1.0 | 50.0 | -- | -- | -- | -- | -- | -- | -- | 10.6 | 3.7 |
| 3 | 91.6 | 2.2 | 1.2 | -- | 5.0 | -- | -- | -- | -- | -- | -- | -- | 9.4 | 3.4 |
| 4 | 93.6 | 4.8 | 0.6 | 1.0 | -- | -- | -- | -- | -- | -- | -- | -- | 9.4 | 4.9 |
| 5 | 91.9 | 6.0 | 1.2 | 1.0 | -- | 5.0 | -- | -- | -- | -- | -- | -- | 9.1 | 5.4 |
| 6 | 91.9 | 6.0 | 1.2 | 1.0 | -- | -- | 5.0 | -- | -- | -- | -- | -- | 9.0 | 5.4 |
| 7 | 91.9 | 6.0 | 1.2 | 1.0 | -- | -- | -- | 5.0 | -- | -- | -- | -- | 8.8 | 5.4 |
| 8 | 91.9 | 6.0 | 1.2 | 1.0 | -- | -- | -- | -- | -- | -- | -- | -- | 11.5 | 2.9 |
| 9 | 91.9 | 6.0 | 1.2 | 1.0 | -- | -- | -- | -- | 5.0 | -- | -- | -- | 11.4 | 3.0 |
| 10 | 91.9 | 6.0 | 1.2 | 1.0 | -- | -- | -- | -- | -- | 5.0 | -- | -- | 11.4 | 3.5 |
| 11 | 91.9 | 6.0 | 1.2 | 1.0 | -- | -- | -- | -- | -- | -- | 5.0 | -- | 11.5 | 2.4 |
| 12 | 91.9 | 6.0 | 1.2 | 1.0 | -- | -- | -- | -- | -- | -- | -- | 5.0 | 11.3 | 4.6 |
如表2中所示之數據，使用本揭示內容之組合物蝕刻表面之表面粗糙度低於由對照組合物產生之表面粗糙度。蝕刻前之表面粗糙度為3.4。另外，圖2係顯示該等組合物之Z範圍的條形圖，其指示使用本揭示內容之組合物經受蝕刻之含鉬膜的經改良粗糙度參數。(Rz係連續取樣長度之粗糙度深度之平均值。Z係取樣長度內最高峰之高度與最低谷深度之總和。)。此外，圖3顯示一些該等表面之掃描電子顯微照片(SEM)，其顯示用不含陽離子表面活性劑之組合物蝕刻之試樣之粗糙度(Rz)要高得多。
本揭示內容之其他組合物亦顯示於3中，其亦導致經改良表面粗糙度。
表 3
A = 去離子水；B= 35% TEAH；C= 51.9%過碘酸；
E= 0.2%氯化苄烷銨；N = 20% TMAH；O = 氯化苄基十二烷基二甲銨；P = 氯化苄基十四烷基銨；Q = 1,2,4 三唑；R = 磷酸氫二銨；S = 碳酸氫銨
態樣
| 調配物編號↓ | A | B | C | D | E | N | O | P | Q | R | S | -- | pH | Rz |
| 13 | 81.2 | 6.4 | 1.9 | -- | 10 | -- | -- | -- | 0.5 | -- | -- | -- | 11.0 | 3.9 |
| 14 | 82.6 | -- | 1.9 | -- | -- | 5.0 | 10 | -- | 0.5 | -- | -- | -- | 9.8 | 3.5 |
| 15 | 82.8 | 4.8 | 1.9 | -- | -- | -- | 10 | -- | 0.5 | -- | -- | -- | 9.9 | 3.3 |
| 16 | 81.1 | 6.5 | 1.9 | -- | -- | -- | 10 | -- | 0.5 | -- | -- | -- | 11.1 | 3.9 |
| 17 | 81.0 | 6.6 | 1.9 | -- | -- | -- | -- | 10 | 0.5 | -- | -- | -- | 11.1 | 3.8 |
| 18 | 81.7 | 5.9 | 1.9 | -- | -- | -- | 10 | -- | -- | 0.5 | -- | -- | 10.0 | 3.2 |
| 19 | 85.1 | 3.5 | 1.2 | -- | -- | -- | 10 | -- | 0.1 | -- | 0.1 | -- | 11.4 | 3.8 |
在第一態樣中，本揭示內容提供選擇性蝕刻組合物，其包含：
至少一種氧化劑，
至少一種陽離子表面活性劑，
水，及
達成約7至約13之pH所需之一定量之pH調節劑，
且視情況包含以下各項中之一或多者：
至少一種錯合劑，
至少一種pH緩衝劑，或
至少一種氧化劑穩定劑，
其中該選擇性蝕刻組合物自微電子裝置相對於氧化鋁移除含鉬膜。
在第二態樣中，本揭示內容提供第一態樣之組合物，其中該氧化劑選自過氧化氫、FeCl
3、FeF
3、Fe(NO
3)
3、Sr(NO
3)
2、CoF
3、MnF
3、過硫酸氫鉀複合鹽、(2KHSO
5•KHSO
4•K
2SO
4)、硝酸、過氧單硫酸銨、亞氯酸銨(NH
4ClO
2)、氯酸銨(NH
4ClO
3)、碘酸銨(NH
4IO
3)、硝酸銨(NH
4NO
3)、過硼酸銨(NH
4BO
3)、過氯酸銨(NH
4ClO
4)、過碘酸銨(NH
4IO
4)、過硫酸銨((NH
4)
2S
2O
8)、次氯酸銨(NH
4ClO)、鎢酸銨((NH
4)
10H
2(W
2O
7))、過硫酸鈉(Na
2S
2O
8)、次氯酸鈉(NaClO)、過硼酸鈉、碘酸鉀(KIO
3)、過錳酸鉀(KMnO
4)、過硫酸鉀(K
2S
2O
8)、次氯酸鉀(KClO)、亞氯酸四甲銨((N(CH
3)
4)ClO
2)、氯酸四甲銨((N(CH
3)
4)ClO
3)、碘酸四甲銨((N(CH
3)
4)IO
3)、過硼酸四甲銨((N(CH
3)
4)BO
3)、過氯酸四甲銨((N(CH
3)
4)ClO
4)、過碘酸四甲銨((N(CH
3)
4)IO
4)、過硫酸四甲銨((N(CH
3)
4)S
2O
8)、過氧單硫酸四丁銨、過氧單硫酸、尿素過氧化氫((CO(NH
2)
2)H
2O
2)、過乙酸、第三丁基過氧化氫、硝基苯磺酸鹽、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯苯醌、四氧嘧啶、過碘酸及其組合。
在第三態樣中，本揭示內容提供第一或第二態樣之組合物，其中該氧化劑選自過氧化氫、過碘酸、第三丁基過氧化氫、碘酸鉀及過乙酸。
在第四態樣中，本揭示內容提供第一至第四態樣之組合物，其中該陽離子表面活性劑選自溴化十六烷基三甲銨、氯化十六烷基三甲銨、十七氟辛磺酸、鹵化四乙銨、氯化硬脂醯基三甲銨、溴化4-(4-二乙基胺基苯基偶氮基)-1-(4-硝基苄基)吡啶鎓、氯化十六烷基吡啶鎓一水合物、氯化苄烷銨、氯化本索寧、氯化苄基二甲基十二烷基銨、氯化苄基二甲基十六烷基銨、溴化十六烷基三甲銨、氯化二甲基二(十八烷基)銨、氯化十二烷基三甲銨、溴化二(十二烷基)二甲銨、氯化二(氫化牛脂)二甲銨、溴化四庚銨、溴化四(癸基)銨、及奧芬溴銨、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(氫化牛脂)二甲銨、氯化苄基二甲銨及溴化苄基二甲銨。
在第五態樣中，本揭示內容提供第一至第四態樣之組合物，其中該陽離子表面活性劑選自氯化苄基二甲銨、溴化十六烷基三甲銨、氯化六羥季銨、氯化三甲基十四烷基銨、氯化癸基三甲銨及氯化苄基二甲基十二烷基銨。
在第六態樣中，本揭示內容提供第一至第五態樣之組合物，其中該pH調節劑選自鹼金屬氫氧化物、鹼土金屬氫氧化物、氫氧化四甲銨(TMAH)、氫氧化四乙銨(TEAH)、氫氧化四丙銨(TPAH)、氫氧化四丁銨(TBAH)、氫氧化三丁基甲銨(TBMAH)、氫氧化苄基三甲銨(BTMAH)、氫氧化膽鹼、氫氧化乙基三甲銨、氫氧化參(2-羥基乙基)甲銨、氫氧化二乙基二甲銨、氫氧化四丁鏻(TBPH)、氫氧化四甲鏻、氫氧化四乙鏻、氫氧化四丙鏻、氫氧化苄基三苯鏻、氫氧化甲基三苯鏻、氫氧化乙基三苯鏻、氫氧化正丙基三苯鏻及其組合。
在第七態樣中，本揭示內容提供第一至第六態樣之組合物，其中該pH調節劑選自氫氧化四甲銨、氫氧化膽鹼或其組合。
在第八態樣中，本揭示內容提供第一至第七態樣之組合物，其中該組合物包含至少一種錯合劑。
在第九態樣中，本揭示內容提供第一至第八態樣之組合物，其中該錯合劑選自胺基乙基乙醇胺、N-甲基胺基乙醇、胺基乙氧基乙醇、二甲基胺基乙氧基乙醇、二乙醇胺、N-甲基二乙醇胺、單乙醇胺、三乙醇胺、1-胺基-2-丙醇、2-胺基-1-丁醇、異丁醇胺、三乙二胺、4-(2-羥基乙基)嗎啉、乙二胺四乙酸、間-二甲苯二胺、亞胺基二乙酸、2-(羥基乙基)亞胺基二乙酸、氮基三乙酸、硫脲、1,1,3,3-四甲脲、尿素、尿素衍生物、尿酸、丙胺酸、精胺酸、天冬醯胺、天冬胺酸、半胱胺酸、麩胺酸、麩醯胺酸、組胺酸、異白胺酸、白胺酸、離胺酸、甲硫胺酸、苯丙胺酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸、1-羥基亞乙基-1,1-二膦酸、1,5,9-三氮雜環十二烷-N,N',N"-參(亞甲基膦酸)、1,4,7,10-四氮雜環十二烷-N,N',N",N'"-四(亞甲基膦酸)、氮基參(亞甲基)三膦酸、二伸乙基三胺五(亞甲基膦酸)、胺基三(亞甲基膦酸)、雙(六亞甲基)三胺五亞甲基膦酸、1,4,7-三氮雜環壬烷-N,N',N"-參(亞甲基膦酸)、羥乙基二磷酸鹽、氮基參(亞甲基)膦酸、2-膦醯基-丁烷-1,2,3,4-四甲酸、羧基乙基膦酸、胺基乙基膦酸、草甘膦、乙二胺四(亞甲基膦酸)、苯基膦酸、草酸、琥珀酸、馬來酸、蘋果酸、丙二酸、己二酸、苯二甲酸、乳酸、檸檬酸、檸檬酸鈉、檸檬酸鉀、檸檬酸銨、1,2,3-丙三甲酸、三羥甲基丙酸、酒石酸、葡糖醛酸、2-羧基吡啶、4,5-二羥基-1,3-苯二磺酸二鈉鹽及其組合。
在第十態樣中，本揭示內容提供第一至第九態樣之組合物，其中該錯合劑選自1-羥基亞乙基-1,1-二膦酸、乳酸及檸檬酸。
在第十一態樣中，本揭示內容提供第一至第十態樣之組合物，其中該至少一種pH緩衝劑係金屬腐蝕抑制劑或銨鹽。
在第十二態樣中，本揭示內容提供第十一態樣之組合物，其中該金屬腐蝕抑制劑選自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、吡唑、5-胺基-1,3,4-噻二唑-2-硫醇、苯并三唑、1,2,4-三唑、1,2,3-三唑、甲苯三唑、5-甲基-苯并三唑、5-苯基-苯并三唑、5-硝基-苯并三唑、苯并三唑羧酸、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-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、鹵基-苯并三唑、萘并三唑、2-巰基苯并咪唑、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、3-胺基-5-巰基-1,2,4-三唑、戊四唑、5-苯基-1H-四唑、5-苄基-1H-四唑、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、吲唑、腺嘌呤、腺苷、咔唑、N-環己基-3-胺基丙磺酸及其組合。
在第十三態樣中，本揭示內容提供第十一或第十二態樣之組合物，其中該金屬腐蝕抑制劑係甲苯三唑。
在第十四態樣中，本揭示內容提供第十一態樣之組合物，其中該銨鹽選自乙酸銨、碳酸氫銨、丁酸銨、三氟乙酸銨、磷酸氫二銨、磷酸二氫銨、膦酸銨及其組合之鹽。
在第十五態樣中，本揭示內容提供第一至第十四態樣之組合物，其進一步包含氧化劑穩定劑。
在第十六態樣中，本揭示內容提供第十五態樣之組合物，其中該氧化劑穩定劑選自甘胺酸、絲胺酸、脯胺酸、白胺酸、丙胺酸、天冬醯胺、天冬胺酸、麩醯胺酸、纈胺酸、及離胺酸、氮基三乙酸、亞胺基二乙酸、艾提壯酸(etidronic acid)、乙二胺四乙酸(EDTA)、(1,2-伸環己基二氮基)四乙酸(CDTA)、尿酸、四乙二醇二甲醚、二伸乙基三胺五乙酸、丙二胺四乙酸、乙二胺二琥珀酸、磺胺及其組合。
在第十七態樣中，本揭示內容提供第十五或第十六態樣之組合物，其中該氧化劑穩定劑選自乙二胺四乙酸、(1,2-伸環己基二氮基)四乙酸及四乙二醇二甲醚。
在第十八態樣中，本揭示內容提供第一至第十七態樣之組合物，其進一步包含至少一種有機溶劑。
在第十九態樣中，本揭示內容提供第十八態樣之組合物，其中該有機溶劑係丙二醇。
在第二十態樣中，本揭示內容提供自其上具有含鉬膜及氧化鋁之微電子裝置基板蝕刻鉬之方法，該方法包含使該微電子裝置基板與組合物接觸達足以相對於該氧化鋁至少部分地移除該含鉬膜之時間段，該組合物包含：
至少一種氧化劑，
至少一種陽離子表面活性劑，
水，及
達成約7至約13之pH所需之一定量之pH調節劑，
且視情況包含以下各項中之一或多者：
至少一種錯合劑，
至少一種pH緩衝劑，或
至少一種氧化劑穩定劑。
在如此闡述本揭示內容之幾個說明性實施例後，熟習此項技術者將易於理解，在隨附申請專利範圍之範圍內，可製得及使用其他實施例。本文件所涵蓋之揭示內容之眾多優點已在上述說明中闡釋。然而，應瞭解，此揭示內容在許多方面中僅係說明性的。本揭示內容之範圍當然係由表達隨附申請專利範圍之語言來界定。
圖1係具有鉬、TEOS及氧化鋁表面之微電子裝置基板之簡化繪圖。實例中闡述之數據表徵相對於裝置之深度自頂部至中部、及至底部蝕刻之數量及均勻性。
圖2係顯示實例中所反映各實驗之Z範圍之條形圖，其指示使用本發明之組合物進行蝕刻之含鉬膜之經改良粗糙度參數。(Rz係連續取樣長度之粗糙度深度之平均值。Z係取樣長度內最高峰之高度與最低谷深度之總和。)
圖3係實例中所說明之各種試樣表面之掃描電子顯微照片(SEM)，其顯示用不含陽離子表面活性劑之組合物蝕刻之試樣的粗糙度(Rz)要高得多。
Claims (11)
- 一種選擇性蝕刻組合物，其包含： 至少一種氧化劑， 至少一種陽離子表面活性劑， 水，及 達成約7至約13之pH所需之一定量之pH調節劑， 且視情況包含以下各項中之一或多者： 至少一種錯合劑， 至少一種pH緩衝劑，或 至少一種氧化劑穩定劑， 其中該選擇性蝕刻組合物自微電子裝置相對於氧化鋁移除含鉬膜。
- 如請求項1之組合物，其中該氧化劑選自過氧化氫、FeCl 3、FeF 3、Fe(NO 3) 3、Sr(NO 3) 2、CoF 3、MnF 3、過硫酸氫鉀複合鹽(oxone)、(2KHSO 5•KHSO 4•K 2SO 4)、硝酸、過氧單硫酸銨、亞氯酸銨(NH 4ClO 2)、氯酸銨(NH 4ClO 3)、碘酸銨(NH 4IO 3)、硝酸銨(NH 4NO 3)、過硼酸銨(NH 4BO 3)、過氯酸銨(NH 4ClO 4)、過碘酸銨(NH 4IO 4)、過硫酸銨((NH 4) 2S 2O 8)、次氯酸銨(NH 4ClO)、鎢酸銨((NH 4) 10H 2(W 2O 7))、過硫酸鈉(Na 2S 2O 8)、次氯酸鈉(NaClO)、過硼酸鈉、碘酸鉀(KIO 3)、過錳酸鉀(KMnO 4)、過硫酸鉀(K 2S 2O 8)、次氯酸鉀(KClO)、亞氯酸四甲銨((N(CH 3) 4)ClO 2)、氯酸四甲銨((N(CH 3) 4)ClO 3)、碘酸四甲銨((N(CH 3) 4)IO 3)、過硼酸四甲銨((N(CH 3) 4)BO 3)、過氯酸四甲銨((N(CH 3) 4)ClO 4)、過碘酸四甲銨((N(CH 3) 4)IO 4)、過硫酸四甲銨((N(CH 3) 4)S 2O 8)、過氧單硫酸四丁銨、過氧單硫酸、尿素過氧化氫((CO(NH 2) 2)H 2O 2)、過乙酸、第三丁基過氧化氫、硝基苯磺酸鹽、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯苯醌、四氧嘧啶、過碘酸及其組合。
- 如請求項1之組合物，其中該陽離子表面活性劑選自溴化十六烷基三甲銨、氯化十六烷基三甲銨、十七氟辛磺酸、鹵化四乙銨、氯化硬脂醯基三甲銨、溴化4-(4-二乙基胺基苯基偶氮基)-1-(4-硝基苄基)吡啶鎓、氯化十六烷基吡啶鎓一水合物、氯化苄烷銨、氯化本索寧、氯化苄基二甲基十二烷基銨、氯化苄基二甲基十六烷基銨、溴化十六烷基三甲銨、氯化二甲基二(十八烷基)銨、氯化十二烷基三甲銨、溴化二(十二烷基)二甲銨、氯化二(氫化牛脂)二甲銨、溴化四庚銨、溴化四(癸基)銨、及奧芬溴銨(oxyphenonium bromide)、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(氫化牛脂)二甲銨、氯化苄基二甲銨及溴化苄基二甲銨。
- 如請求項1之組合物，其中該pH調節劑選自鹼金屬氫氧化物、鹼土金屬氫氧化物、氫氧化四甲銨(TMAH)、氫氧化四乙銨(TEAH)、氫氧化四丙銨(TPAH)、氫氧化四丁銨(TBAH)、氫氧化三丁基甲銨(TBMAH)、氫氧化苄基三甲銨(BTMAH)、氫氧化膽鹼、氫氧化乙基三甲銨、氫氧化參(2-羥基乙基)甲銨、氫氧化二乙基二甲銨、氫氧化四丁鏻(TBPH)、氫氧化四甲鏻、氫氧化四乙鏻、氫氧化四丙鏻、氫氧化苄基三苯鏻、氫氧化甲基三苯鏻、氫氧化乙基三苯鏻、氫氧化正丙基三苯鏻及其組合。
- 如請求項1之組合物，其中該組合物包含至少一種錯合劑。
- 如請求項1之組合物，其中該組合物所包含的至少一種pH緩衝劑係金屬腐蝕抑制劑或銨鹽。
- 如請求項6之組合物，其中該金屬腐蝕抑制劑選自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、吡唑、5-胺基-1,3,4-噻二唑-2-硫醇、苯并三唑、1,2,4-三唑、1,2,3-三唑、甲苯三唑、5-甲基-苯并三唑、5-苯基-苯并三唑、5-硝基-苯并三唑、苯并三唑羧酸、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-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、鹵基-苯并三唑、萘并三唑、2-巰基苯并咪唑、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、3-胺基-5-巰基-1,2,4-三唑、戊四唑、5-苯基-1H-四唑、5-苄基-1H-四唑、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、吲唑、腺嘌呤、腺苷、咔唑、N-環己基-3-胺基丙磺酸及其組合。
- 如請求項6之組合物，其中該銨鹽選自乙酸銨、碳酸氫銨、丁酸銨、三氟乙酸銨、磷酸氫二銨、磷酸二氫銨、膦酸銨及其組合之鹽。
- 如請求項1之組合物，其進一步包含氧化劑穩定劑。
- 如請求項1之組合物，其進一步包含至少一種有機溶劑。
- 一種自其上具有含鉬膜及氧化鋁之微電子裝置基板蝕刻鉬之方法，該方法包含使該微電子裝置基板與組合物接觸達足以相對於該氧化鋁至少部分地移除該含鉬膜之時間段，該組合物包含： 至少一種氧化劑， 至少一種陽離子表面活性劑， 水，及 達成約7至約13之pH所需之一定量之pH調節劑， 且視情況包含以下各項中之一或多者： 至少一種錯合劑， 至少一種pH緩衝劑，或 至少一種氧化劑穩定劑。
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