TW201619354A - 具有鍺化矽及鎢相容性之用於蝕刻氮化鈦之組成物 - Google Patents
具有鍺化矽及鎢相容性之用於蝕刻氮化鈦之組成物 Download PDFInfo
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- TW201619354A TW201619354A TW104130763A TW104130763A TW201619354A TW 201619354 A TW201619354 A TW 201619354A TW 104130763 A TW104130763 A TW 104130763A TW 104130763 A TW104130763 A TW 104130763A TW 201619354 A TW201619354 A TW 201619354A
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- Prior art keywords
- ammonium
- composition
- acid
- ether
- glycol
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- MTVLEKBQSDTQGO-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol Chemical compound CCOC(C)COC(C)CO MTVLEKBQSDTQGO-UHFFFAOYSA-N 0.000 claims description 2
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 claims description 2
- PCFUWBOSXMKGIP-UHFFFAOYSA-N 2-benzylpyridine Chemical compound C=1C=CC=NC=1CC1=CC=CC=C1 PCFUWBOSXMKGIP-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 claims description 2
- DVGVMQVOCJNXNJ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;4-methylbenzenesulfonate Chemical compound C[N+](C)(C)CCO.CC1=CC=C(S([O-])(=O)=O)C=C1 DVGVMQVOCJNXNJ-UHFFFAOYSA-M 0.000 claims description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 2
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 2
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 claims description 2
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 claims description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims description 2
- MVVJINIUPYKZHR-UHFFFAOYSA-N 3-[[4-[5-(methoxymethyl)-2-oxo-1,3-oxazolidin-3-yl]phenoxy]methyl]benzonitrile Chemical compound O=C1OC(COC)CN1C(C=C1)=CC=C1OCC1=CC=CC(C#N)=C1 MVVJINIUPYKZHR-UHFFFAOYSA-N 0.000 claims description 2
- AGWWTUWTOBEQFE-UHFFFAOYSA-N 4-methyl-1h-1,2,4-triazole-5-thione Chemical compound CN1C=NN=C1S AGWWTUWTOBEQFE-UHFFFAOYSA-N 0.000 claims description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 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 2
- 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 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 2
- HCEKEODXLSQFDV-UHFFFAOYSA-N 5-methyltriazol-1-amine Chemical compound CC1=CN=NN1N HCEKEODXLSQFDV-UHFFFAOYSA-N 0.000 claims description 2
- WXSBVEKBZGNSDY-UHFFFAOYSA-N 5-phenyl-2h-benzotriazole Chemical compound C1=CC=CC=C1C1=CC2=NNN=C2C=C1 WXSBVEKBZGNSDY-UHFFFAOYSA-N 0.000 claims description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 claims description 2
- CWRVKFFCRWGWCS-UHFFFAOYSA-N Pentrazole Chemical compound C1CCCCC2=NN=NN21 CWRVKFFCRWGWCS-UHFFFAOYSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- QAVSBTRWFAEYSZ-UHFFFAOYSA-N [Br-].[SH3+].[NH4+].[Br-] Chemical compound [Br-].[SH3+].[NH4+].[Br-] QAVSBTRWFAEYSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003082 abrasive agent Substances 0.000 claims description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 2
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 claims description 2
- HHEFNVCDPLQQTP-UHFFFAOYSA-N ammonium perchlorate Chemical compound [NH4+].[O-]Cl(=O)(=O)=O HHEFNVCDPLQQTP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229960001716 benzalkonium Drugs 0.000 claims description 2
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 2
- 229960001950 benzethonium chloride Drugs 0.000 claims description 2
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 2
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 2
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 claims description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 2
- SGZVXLFVBKDMJH-UHFFFAOYSA-M dihydrogen phosphate;hexadecyl-(2-hydroxyethyl)-dimethylazanium Chemical compound OP(O)([O-])=O.CCCCCCCCCCCCCCCC[N+](C)(C)CCO SGZVXLFVBKDMJH-UHFFFAOYSA-M 0.000 claims description 2
- 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 claims description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- FFGSPQDSOUPWGY-UHFFFAOYSA-M dodecyl-ethyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC FFGSPQDSOUPWGY-UHFFFAOYSA-M 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- AENSXLNDMRQIEX-UHFFFAOYSA-L oxido sulfate;tetrabutylazanium Chemical compound [O-]OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC AENSXLNDMRQIEX-UHFFFAOYSA-L 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 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 2
- 229960001125 oxyphenonium bromide Drugs 0.000 claims description 2
- YZCRWWDMRZKXNS-UHFFFAOYSA-N pentan-1-imine Chemical compound CCCCC=N YZCRWWDMRZKXNS-UHFFFAOYSA-N 0.000 claims description 2
- 229960005152 pentetrazol Drugs 0.000 claims description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229960001922 sodium perborate Drugs 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 2
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 claims description 2
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 claims description 2
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 claims description 2
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 claims description 2
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 claims description 2
- WBWDWFZTSDZAIG-UHFFFAOYSA-M thonzonium bromide Chemical compound [Br-].N=1C=CC=NC=1N(CC[N+](C)(C)CCCCCCCCCCCCCCCC)CC1=CC=C(OC)C=C1 WBWDWFZTSDZAIG-UHFFFAOYSA-M 0.000 claims description 2
- 229940051002 thonzonium bromide Drugs 0.000 claims description 2
- MPSUGQWRVNRJEE-UHFFFAOYSA-N triazol-1-amine Chemical compound NN1C=CN=N1 MPSUGQWRVNRJEE-UHFFFAOYSA-N 0.000 claims description 2
- XDUVTZGINNGNAG-UHFFFAOYSA-M tridodecyl(methyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC XDUVTZGINNGNAG-UHFFFAOYSA-M 0.000 claims description 2
- GPQCSCQDQNXQSV-UHFFFAOYSA-N tridodecylazanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC GPQCSCQDQNXQSV-UHFFFAOYSA-N 0.000 claims description 2
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims 2
- VGRFVJMYCCLWPQ-UHFFFAOYSA-N germanium Chemical compound [Ge].[Ge] VGRFVJMYCCLWPQ-UHFFFAOYSA-N 0.000 claims 2
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- WSVPFJBQFXKCNU-UHFFFAOYSA-N (2,3,4,5-tetrachlorophenyl)hydrazine Chemical compound NNC1=CC(Cl)=C(Cl)C(Cl)=C1Cl WSVPFJBQFXKCNU-UHFFFAOYSA-N 0.000 claims 1
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 claims 1
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims 1
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 claims 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims 1
- STCBHSHARMAIOM-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;chloride Chemical compound Cl.CN1C=CN=C1 STCBHSHARMAIOM-UHFFFAOYSA-N 0.000 claims 1
- SNUDAELCXNZQPV-UHFFFAOYSA-N 1-methyl-4-(1-tetradecylpyridin-1-ium-4-yl)pyridin-1-ium Chemical compound C1=C[N+](CCCCCCCCCCCCCC)=CC=C1C1=CC=[N+](C)C=C1 SNUDAELCXNZQPV-UHFFFAOYSA-N 0.000 claims 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 claims 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims 1
- OKIYPFZZDQLNMP-UHFFFAOYSA-N 5-pentyl-2h-tetrazole Chemical compound CCCCCC=1N=NNN=1 OKIYPFZZDQLNMP-UHFFFAOYSA-N 0.000 claims 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims 1
- DBASYWOABBGWNL-UHFFFAOYSA-N NN.S1CCCC1 Chemical compound NN.S1CCCC1 DBASYWOABBGWNL-UHFFFAOYSA-N 0.000 claims 1
- LUWCAKUSTOCTLV-UHFFFAOYSA-N [Br+].C(CCCCCCCCCCCCCCCCC)[N+](C)(C)C Chemical compound [Br+].C(CCCCCCCCCCCCCCCCC)[N+](C)(C)C LUWCAKUSTOCTLV-UHFFFAOYSA-N 0.000 claims 1
- RUJMFYVXRLKDHV-UHFFFAOYSA-N [Cl+].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 Chemical compound [Cl+].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 RUJMFYVXRLKDHV-UHFFFAOYSA-N 0.000 claims 1
- DBOSSOAPVPPGMK-UHFFFAOYSA-N [Cl-].C[NH+](C)C.CCCCCCCCCCCCCCCC Chemical compound [Cl-].C[NH+](C)C.CCCCCCCCCCCCCCCC DBOSSOAPVPPGMK-UHFFFAOYSA-N 0.000 claims 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 1
- YUUVAZCKXDQEIS-UHFFFAOYSA-N azanium;chlorite Chemical compound [NH4+].[O-]Cl=O YUUVAZCKXDQEIS-UHFFFAOYSA-N 0.000 claims 1
- 150000001565 benzotriazoles Chemical class 0.000 claims 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 claims 1
- YYEAHKWERFGUKU-UHFFFAOYSA-N chloromethylbenzene;n,n-dimethyldodecan-1-amine Chemical compound ClCC1=CC=CC=C1.CCCCCCCCCCCCN(C)C YYEAHKWERFGUKU-UHFFFAOYSA-N 0.000 claims 1
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000002009 diols Chemical class 0.000 claims 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims 1
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- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 description 1
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- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31144—Etching the insulating layers by chemical or physical means using masks
Landscapes
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Weting (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
本發明係關於適用於自其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置相對於金屬傳導(例如,鎢及銅)及絕緣材料選擇性移除該等材料之組成物。該等組成物包含至少一種氧化劑、至少一種蝕刻劑、及至少一種有機溶劑,其可包含各種腐蝕抑制劑來確保選擇性。
Description
本發明係關於一種用於在半導體基板、金屬導體、及絕緣體材料(例如,低k介電質)之存在下選擇性蝕刻氮化鈦及/或光阻蝕刻殘留物之組成物及方法,及更特定言之係關於一種以高於銅、鎢、鍺化矽、鍺、及低k介電材料之經暴露層或下方層之蝕刻速率及選擇性有效且有效率地蝕刻氮化鈦及/或光阻蝕刻殘留物之組成物及方法。
光阻遮罩常在半導體工業中用來將諸如半導體或介電質之材料圖案化。在一項應用中,光阻遮罩在雙重鑲嵌(dual damascene)製程中用來在微電子裝置之後段金屬化中形成互連體。雙重鑲嵌製程涉及在覆蓋金屬導體層(諸如銅層)的低k介電層上形成光阻遮罩。隨後根據光阻遮罩蝕刻低k介電層以形成暴露金屬導體層的通孔及/或溝渠。一般稱為雙重鑲嵌結構的通孔及溝渠通常係使用兩個微影步驟界定。然後在將傳導性材料沈積至通孔及/或溝渠中以形成互連體之前自低k介電層移除光阻遮罩。
隨著微電子裝置之尺寸減小,變得愈來愈難達成通孔及溝渠的臨界尺寸。因此,使用金屬硬遮罩來提供通孔及溝渠的更佳剖面控制。金屬硬遮罩可包含鈦或氮化鈦,且於形成雙重鑲嵌結
構的通孔及/或溝渠後藉由濕式蝕刻製程移除。濕式蝕刻製程必須使用可有效地移除金屬硬遮罩及/或光阻蝕刻殘留物而不會影響下方半導體基板、金屬導體層及低k介電材料的移除化學物質。換言之,移除化學物質需對半導體基板、金屬導體層及低k介電層具高度選擇性。
因此,本發明之一目的為提供用於相對於所存在之半導體基板、金屬導體層及低k介電層選擇性地移除硬遮罩材料,同時無損於硬遮罩之蝕刻速率的經改良組成物。
本發明係關於一種用於相對於所存在之半導體基板、金屬導體層及低k介電層選擇性地蝕刻硬遮罩層及/或光阻蝕刻殘留物之組成物及方法。更明確言之,本發明係關於一種相對於銅、鎢、鍺化矽、鍺、及低k介電層選擇性地蝕刻氮化鈦及/或光阻蝕刻殘留物之組成物及方法。
在一態樣中,描述一種用於自其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置之表面選擇性地移除該等材料之組成物,該組成物包含至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、至少一種Ge/SiGe鈍化劑、水、及至少一種有機溶劑,其中該組成物實質上不含過氧化氫,且其中該至少一種Ge/SiGe鈍化劑包括選自由下列所組成之群之物質:丙酮酸、1,2-己二醇、草乙酸、殺藻胺(benzalkonium chloride)、聚丙烯酸、葡萄糖、乙醯乙酸、乙醯丙酸、2-酮基戊二酸酯、聚乙二醇(例如,PEG 200)、氯化十二烷基三甲基銨(DTAC)、及其組合。
在另一態樣中,描述一種自其上具有氮化鈦材料之微
電子裝置之表面蝕刻該材料之方法,該方法包括使該表面與包含至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、至少一種Ge/SiGe鈍化劑、水、及至少一種有機溶劑之組成物接觸,其中該組成物實質上不含過氧化氫,其中該至少一種Ge/SiGe鈍化劑包括選自由下列所組成之群之物質:丙酮酸、1,2-己二醇、草乙酸、殺藻胺、聚丙烯酸、葡萄糖、乙醯乙酸、乙醯丙酸、2-酮基戊二酸酯、聚乙二醇(例如,PEG 200)、氯化十二烷基三甲基銨(DTAC)、及其組合,且其中該組成物相對於半導體基板、金屬、及絕緣材料自表面選擇性地移除氮化鈦材料。
本發明之其他態樣、特徵及具體例將可由隨後之揭示內容及隨附之申請專利範圍而更完整明瞭。
一般而言,本發明係關於用於相對於所存在之半導體基板、金屬導體層及低k介電層選擇性地蝕刻硬遮罩層及/或光阻蝕刻殘留物之組成物及方法。更明確言之,本發明係關於一種用於相對於銅、鎢、鍺化矽、鍺、及低k介電層選擇性地蝕刻氮化鈦及/或光阻蝕刻殘留物之組成物及方法。其他可能存在於微電子裝置上之材料不應被該等組成物實質上地移除或腐蝕。
為容易參考起見,「微電子裝置」係相當於經製造用於微電子、積體電路、能量收集、或電腦晶片應用中之半導體基板、平板顯示器、相變記憶裝置、太陽能面板及包括太陽能電池裝置、光伏打元件、及微機電系統(MEMS)之其他產品。應明瞭術語「微
電子裝置」、「微電子基板」及「微電子裝置結構」並不具任何限制意味,且其包括任何最終將成為微電子裝置或微電子組件的基板或結構。微電子裝置可為圖案化、毯覆式、控制及/或測試裝置。
文中所使用之「硬遮罩覆蓋層」或「硬遮罩」係相當於在電漿蝕刻步驟期間沈積於介電材料上方以對其提供保護的材料。硬遮罩覆蓋層傳統上係氮化矽、氧氮化矽、氮化鈦、氧氮化鈦、鈦及其他類似化合物。
文中所使用之「氮化鈦」及「TiNx」係相當於純氮化鈦以及包括不同化學計量及氧含量之不純的氮化鈦(TiOxNy)。
文中所使用之「約」係意指相當於所述值之±5%。
文中所定義之「低k介電材料」係相當於在層狀微電子裝置中用作介電材料之任何材料,其中該材料具有低於約3.5之介電常數。較佳地,低k介電材料包括低極性材料諸如含矽有機聚合物、含矽有機/無機混合材料、有機矽酸鹽玻璃(OSG)、TEOS、氟化矽酸鹽玻璃(FSG)、二氧化矽、及摻碳氧化物(CDO)玻璃。應明瞭低k介電材料可具有不同密度及不同孔隙度。
文中所定義之「金屬導體層」包括銅、鎢、鈷、鉬、鋁、釕、包含其等之合金、及其組合。
文中所定義之「胺」物質包括至少一種第一、第二、及第三胺,其限制條件為(i)同時包括羧酸基及胺基之物質,(ii)包括胺基之表面活性劑,及(iii)其中之胺基為取代基(例如,連接至芳基或雜環部分)之物質不被視為根據此定義之「胺」。胺之化學式可以NR1R2R3表示,其中R1、R2及R3可彼此相同或不同且係選自由氫、直鏈或分支鏈C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊
基、己基)、C6-C10芳基(例如,苄基)、直鏈或分支鏈C1-C6烷醇(例如,甲醇、乙醇、丙醇、丁醇、戊醇、己醇)、及其組合所組成之群,其限制條件為R1、R2及R3不可皆為氫。
如熟悉技藝人士所可輕易明瞭,文中所定義之「光阻蝕刻殘留物」係相當於任何包含光阻材料之殘留物,或作為在蝕刻或灰化步驟後之光阻副產物的材料。
「實質上不含」在本文係定義為小於2重量%,較佳小於1重量%,更佳小於0.5重量%,再更佳小於0.1重量%,及最佳0重量%。
本文所使用之「氟化物」物質係相當於包括離子氟化物(F-)之物質。應明瞭可包括氟化物物質作為氟化物物質或於原位產生。
本文所使用之「氯化物」物質係相當於包括離子氯化物(Cl-)之物質,其限制條件為包括氯陰離子之表面活性劑不被視為根據此定義之「氯化物」。
如本文所使用之術語「半水性」係指水與有機溶劑組分之混合物。半水性移除組成物不可實質上地損壞在移除硬遮罩層及/或光阻蝕刻殘留物時所存在的金屬導體層及低k介電層。
本文所定義之強鹼係有至少一個pKa大於11之任何鹼,而弱鹼係有至少一個pKa小於11之任何鹼。
如本文所定義之「半導體基板」包括,但不限於,裸矽;多晶矽;鍺;SiGe;III/V族化合物,諸如氮化鋁、氮化鎵、砷化鎵、磷化銦;榍石(titanite);II/IV族化合物;II/VI族化合物,諸如CdSe、CdS、ZnS、ZnSe及CdTe;碳化矽;藍寶石;矽/藍寶
石;碳;經摻雜玻璃;未經摻雜玻璃;鑽石;GeAsSe玻璃;多晶形矽(經摻雜或未經摻雜);單晶矽(經摻雜或未經摻雜);非晶矽、二砷化銅銦(鎵);及其組合。舉例來說,鍺及SiGe由於其電子性質而對於各種MOS技術而言被認為係替代矽作為用來形成基板及/或閘電極之首選半導體材料的適當替代物。
本發明之組成物可以如更完整說明於下文之相當多樣的特定調配物具體實施。
在所有該等組成物中,當參照包括零下限之重量百分比範圍論述組成物之特定組分時,當明瞭在組成物之各種特定具體例中可存在或不存在該等組分,且在存在該等組分之情況中,其可以基於其中使用該等組分之組成物之總重量計低至0.001重量百分比之濃度存在。
本發明之具體例包括用於移除硬遮罩及/或光阻蝕刻殘留物之化學物質。在一具體例中,該組成物係移除介電層上之金屬硬遮罩及/或光阻蝕刻殘留物之濕式蝕刻溶液,且其相對於在介電層下方之半導體基板、金屬導體層及介電層本身具高度選擇性。在一更特定具體例中,該組成物係移除氮化鈦層及/或光阻蝕刻殘留物之濕式蝕刻溶液,其相對於銅、鎢、鍺化矽、鍺、鍺、及低k介電材料中之至少一者具高度選擇性。
因此,在一態樣中,描述一種用於自其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置之表面選擇性地移除該等材料之組成物,該組成物包含至少一種氧化劑、至少一種蝕刻劑、及至少一種Ge/SiGe鈍化劑,其中該組成物實質上不含過氧化氫。在一具體例中,用於自其上具有氮化鈦及/或光阻蝕刻殘留材料之
微電子裝置之表面移除該等材料之組成物包含以下組分,由其等所組成,或基本上由其等所組成:至少一種氧化劑、至少一種蝕刻劑、至少一種Ge/SiGe鈍化劑、水、及至少一種有機溶劑,其中該組成物實質上不含過氧化氫。在另一具體例中,用於自其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置之表面移除該等材料之組成物包含以下組分,由其等所組成,或基本上由其等所組成:至少一種氧化劑、至少一種蝕刻劑、水、至少一種Ge/SiGe鈍化劑、及至少一種腐蝕抑制劑,其中該組成物實質上不含過氧化氫。在又另一具體例中,用於自其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置之表面移除該等材料之組成物包含以下組分,由其等所組成,或基本上由其等所組成:至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、至少一種Ge/SiGe鈍化劑、至少一種pH調節劑、水、及至少一種有機溶劑,其中該組成物實質上不含過氧化氫。在一具體例中,基於組成物之總重量,組成物中之水量係在約0.1重量%至約50重量%、較佳約1重量%至約30重量%、及再更佳約5重量%至約20重量%之範圍內。在另一具體例中,基於組成物之總重量,組成物中至少一種有機溶劑之量係在約0.1重量%至約50重量%、較佳約1重量%至約30重量%、及再更佳約5重量%至約20重量%之範圍內。其他經涵蓋包含於本文所述組成物中之組分包括,但不限於,至少一種矽石來源、至少一種低k鈍化劑、至少一種表面活性劑、至少一種碘清除劑、及其組合。有利地,此等組成物在約45℃至約60℃範圍內之溫度下具有大於50:1之TiN對鎢之選擇性及小於約2埃/分鐘(Å min-1)之鎢移除速率,再更佳為大於75:1之TiN對鎢之選擇性及小於約2埃/分鐘之鎢移除速率。
此外,此等組成物在約45℃至約60℃範圍內之溫度下具有大於50:1之TiN對SiGe之選擇性及小於約3埃/分鐘之SiGe移除速率,再更佳為大於75:1之TiN對SiGe之選擇性及小於約3埃/分鐘之銅移除速率。此等組成物實質上不含如本文所定義之胺、化學機械拋光研磨材料、金屬鹵化物、及其組合。此等組成物具有在0至4範圍內之pH值。
添加蝕刻劑以提高氮化鈦之蝕刻速率。涵蓋的蝕刻劑包括,但不限於,HF、氟化銨、氟化氫銨(ABF)、四氟硼酸、六氟矽酸(HFSA)、其他含B-F或Si-F鍵之化合物、四氟硼酸四丁銨(TBA-BF4)、氟化四烷基銨(NR1R2R3R4F)、諸如氫氧化四烷基銨(NR1R2R3R4OH)之強鹼(其中R1、R2、R3、R4可彼此相同或不同且係選自由氫、直鏈或分支鏈C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)、C1-C6烷氧基(例如,羥乙基、羥丙基)經取代或未經取代之芳基(例如,苄基)組成之群)、弱鹼、及其組合。較佳地,氟化物來源包含四氟硼酸、六氟矽酸、H2ZrF6、H2TiF6、HPF6、氟化銨、氟化氫銨、氟化四甲基銨、氫氧化四甲基銨、六氟矽酸銨、六氟鈦酸銨、或氟化銨與氟化四甲基銨之組合。或者,或在氟化物來源之外,蝕刻劑可包含強鹼諸如氫氧化四甲基銨(TMAH)、氫氧化四乙基銨(TEAH)、氫氧化四丙基銨(TPAH)、氫氧化四丁基銨(TBAH)、氫氧化苄基三甲基銨(BTMAH)、氫氧化鉀、氫氧化銨、氫氧化苄基三乙基銨(BTEAH)、氫氧化四丁基鏻(TBPH)、氫氧化(2-羥乙基)三甲基銨、氫氧化(2-羥乙基)三乙基銨、氫氧化(2-羥乙基)三丙基銨、氫氧化(1-羥丙基)三甲基銨、氫氧化乙基三甲基銨、氫氧化二乙基二甲基銨(DEDMAH)、1,1,3,3-四甲基胍(TMG)、碳酸
胍、精胺酸、及其組合。最佳地,蝕刻劑包含HF、氟化氫銨、六氟矽酸、四氟硼酸、或其組合。
包括氧化劑來氧化TiNx中之Ti3+。本文涵蓋的氧化劑包括,但不限於,FeCl3、FeF3、Fe(NO3)3、Sr(NO3)2、CoF3、MnF3、發氧方(oxone,2KHSO5˙KHSO4˙K2SO4)、過碘酸、碘酸、氧化釩(V)、氧化釩(IV、V)(V6O13)、釩酸銨、多原子銨鹽(例如,過氧單硫酸銨、亞氯酸銨(NH4ClO2)、氯酸銨(NH4ClO3)、碘酸銨(NH4IO3)、硝酸銨(NH4NO3)、過硼酸銨(NH4BO3)、過氯酸銨(NH4ClO4)、過碘酸銨(NH4IO4)、過硫酸銨((NH4)2S2O8)、次氯酸銨(NH4ClO))、鎢酸銨((NH4)10H2(W2O7))、多原子鈉鹽(例如,過硫酸鈉(Na2S2O8)、次氯酸鈉(NaClO)、過硼酸鈉)、多原子鉀鹽(例如,碘酸鉀(KIO3)、過錳酸鉀(KMnO4)、過硫酸鉀、硝酸(HNO3)、過硫酸鉀(K2S2O8)、次氯酸鉀(KClO))、多原子四甲銨鹽(例如,亞氯酸四甲銨((N(CH3)4)ClO2)、氯酸四甲銨((N(CH3)4)ClO3)、碘酸四甲銨((N(CH3)4)IO3)、過硼酸四甲銨((N(CH3)4)BO3)、過氯酸四甲銨((N(CH3)4)ClO4)、過碘酸四甲銨((N(CH3)4)IO4)、過硫酸四甲銨((N(CH3)4)S2O8))、多原子四丁銨鹽(例如,過氧單硫酸四丁銨)、過氧單硫酸、硝酸鐵(Fe(NO3)3)、尿素過氧化氫((CO(NH2)2)H2O2)、過乙酸(CH3(CO)OOH)、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯苯醌、四氧嘧啶(alloxan)、N-甲基啉N-氧化物(NMMO)、三甲胺N-氧化物、及其組合。當氧化劑係鹽時,其可為水合或無水。氧化劑可在製造商處、在將組成物引入至裝置晶圓之前、或者在裝置晶圓處(即在原位)引入至組成物。較佳地,組成物之氧化劑包含氧化釩(IV、V)(V6O13)、氧化釩、釩酸銨、碘酸銨、過碘酸銨、碘酸、過
碘酸、或其組合。
添加金屬腐蝕抑制劑以阻斷氧化劑之氧化活性及因此防止金屬(包括,但不限於,銅及鎢)腐蝕。此處涵蓋的金屬腐蝕抑制劑包括,但不限於,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(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-胺基四唑、伸戊基四唑、5-苯基-1H-四唑、5-苄基-1H-四唑、Ablumine O(Taiwan Surfactant)、2-苄基吡啶、琥珀醯亞胺、順丁烯二醯亞胺、酞二醯亞胺、戊二醯亞胺、2,4-二胺基-6-甲基-1,3,5-三、噻唑、三、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、二胺甲基三、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、苯并噻唑、咪唑、吡唑、吲二唑(indiazole)、腺苷酸、咔唑、糖精、及安息香肟。其他的腐蝕抑制劑包括陽離子性四級表面活性劑鹽類諸如殺藻胺、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、Aliquat 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’-聯吡錠、溴化烷基三甲基銨、鹽酸安保寧(amprolium hydrochloride)、氫氧化苯乙
基銨(benzethonium hydroxide)、氯化苯乙基銨(benzethonium chloride)、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、膽鹼對甲苯磺酸鹽、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、吉拉德試劑(Girard’s reagent)、十六烷基(2-羥乙基)二甲基磷酸二氫銨、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、氯化甲基苯乙基銨、Hyamine® 1622、LuviquatTM、N,N,,N’-聚氧伸乙基(10)-N-牛脂-1,3-二胺基丙烷液體、溴化羥苯乙胺(oxyphenonium bromide)、溴化四庚基銨、溴化肆(癸基)銨、通佐溴銨(thonzonium bromide)、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、氯化二甲基二硬脂基銨、及氯化六羥季銨(hexamethonium chloride)。其他腐蝕抑制劑包括非離子性表面活性劑諸如PolyFox PF-159(OMNOVA Solutions)、聚(乙二醇)(「PEG」)、聚(丙二醇)(「PPG」)、PEG-PPG共聚物諸如Pluronic F-127(BASF)、陰離子性表面活性劑諸如十二烷基苯磺酸、十二烷基苯磺酸鈉、及其組合。四級鹽可同時作為腐蝕抑制劑(尤其針對銅及鎢)及濕潤劑。熟悉技藝人士當明瞭雖然四級鹽最常可以氯化物或溴化物自市面購得,但可容易地將鹵陰離子與諸如硫酸根、甲磺酸根、硝酸根、氫氧根等非鹵陰離子進行離子交換。該等經轉變的四級鹽亦涵蓋於此。在一特佳具體例中,已知5-甲基-1H-苯并三唑可阻斷氧化劑對銅之氧化活性。或者,或除5-甲基-1H-苯并三唑(mBTA)之外,較
佳的腐蝕抑制劑包括吡唑、苯并三唑、腺苷酸、糖精、陽離子性四級表面活性劑鹽類,更佳為溴化肉豆蔻基三甲基銨、殺藻胺、對甲苯磺酸十六烷基三甲基銨、及氫氧化十六烷基三甲基銨、四唑諸如5-苄基-1H-四唑、及其組合。
該至少一種有機溶劑包括至少一種可與水相混溶之有機溶劑,包括,但不限於: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、1,2-及1,3-丙二醇、1,2-、1,3-、及1,4-丁二醇、二丙二醇、二甘醇(DEG)、二甘醇單甲醚、三甘醇單甲醚、二甘醇單乙醚、三甘醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二甘醇單丁醚、三甘醇單丁醚、乙二醇單己醚、二甘醇單己醚、乙二醇苯基醚、丙二醇甲基醚、二丙二醇甲基醚(DPGME)、三丙二醇甲基醚(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、四氫呋喃甲醇(THFA)、碳酸丁二酯(BC)、碳酸乙二酯、碳酸丙二酯(PC)、2,3-二氫十氟戊烷、乙基全氟丁基醚、甲基全氟丁基醚、4-甲基-2-戊醇、四亞甲二醇二甲基醚、二甲亞碸(DMSO)、四氫噻吩碸、甲磺酸(MSA)、及其組合。較佳地,該至少一種有機溶劑包括碳酸丁二酯(BC)、碳酸乙二酯、碳酸丙二酯(PC)、二甘醇單丁醚、二甘醇單己醚、乙二醇、1,2-及1,3-丙二醇、二丙二醇、二甘醇(DEG)、DMSO、或其組合。在一特定較佳具體例中,組成物包含至少兩種有機溶劑。
該至少一種Ge/SiGe鈍化劑包括,但不限於,丙酮酸、1,2-己二醇、草乙酸、殺藻胺、聚丙烯酸、葡萄糖、乙醯乙酸、
乙醯丙酸、2-酮基戊二酸酯、聚乙二醇(例如,PEG 200)、氯化十二烷基三甲基銨(DTAC)、及其組合。較佳地,該至少一種Ge/SiGe鈍化劑包括丙酮酸。
該至少一種pH調節劑,當存在時,包括,但不限於,四氟硼酸、硫酸、硝酸、氫氯酸、氫溴酸、氫碘酸、過氯酸、及其組合。
文中所述之組成物可視需要包括至少一種低k鈍化劑來降低低k介電層之化學侵蝕及保護晶圓免於額外氧化。較佳的低k鈍化劑包括,但不限於,硼酸、硼酸鹽(諸如五硼酸銨、四硼酸鈉)、3-羥基-2-萘甲酸、丙二酸、及亞胺二乙酸。當存在時,基於組成物之總重量,組成物包括約0.01重量%至約2重量%低k鈍化劑。較佳地,基於下方低k材料之總重量,使用文中所述之組成物蝕刻/移除小於2重量%之下方低k材料,更佳小於1重量%,最佳小於0.5重量%。
文中所述之組成物可視需要包括至少一種矽石來源以降低蝕刻劑來源之活性。在一具體例中,該至少一種矽石來源包含烷氧矽烷。所涵蓋的烷氧矽烷具有通式SiR1R2R3R4,其中R1、R2、R3及R4係彼此相同或不同且係選自由直鏈C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)、分支鏈C1-C6烷基、C1-C6烷氧基(例如,甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基)、苯基、及其組合所組成之群。熟悉技藝人士應明瞭為表徵為烷氧矽烷,R1、R2、R3或R4中之至少一者必需為C1-C6烷氧基。所涵蓋的烷氧矽烷包括甲基三甲氧矽烷、二甲基二甲氧矽烷、苯基三甲氧矽烷、四乙氧矽烷(TEOS)、N-丙基三甲氧矽烷、N-丙基三乙氧
矽烷、己基三甲氧矽烷、己基三乙氧矽烷、及其組合。可替代烷氧矽烷或在烷氧矽烷之外使用的其他矽石來源包括六氟矽酸銨、矽酸鈉、矽酸四甲銨(TMAS)、及其組合。較佳地,含矽化合物包含TEOS、TMAS、矽酸鈉、或其組合。當存在時,基於組成物之總重量,組成物包括約0.001重量%至約5重量%矽石來源。
當氧化劑包含碘酸鹽或過碘酸鹽時,可視情況將碘清除劑添加至組成物。雖然不希望受限於理論,但據認為當碘酸鹽或過碘酸鹽經還原時,碘累積,其提高銅蝕刻之速率。碘清除劑包括,但不限於,酮,更佳為具有位在羰基之α位之氫的酮,諸如4-甲基-2-戊酮、2,4-二甲基-3-戊酮、環己酮、5-甲基-3-庚酮、3-戊酮、5-羥基-2-戊酮、2,5-己二酮、4-羥基-4-甲基-2-戊酮、丙酮、丁酮、2-甲基-2-丁酮、3,3-二甲基-2-丁酮、4-羥基-2-丁酮、環戊酮、2-戊酮、3-戊酮、1-苯基乙酮、苯乙酮、二苯甲酮、2-己酮、3-己酮、2-庚酮、3-庚酮、4-庚酮、2,6-二甲基-4-庚酮、2-辛酮、3-辛酮、4-辛酮、二環己基酮、2,6-二甲基環己酮、2-乙醯基環己酮、2,4-戊二酮、薄荷酮、及其組合。較佳地,碘清除劑包括4-甲基-2-戊酮、2,4-二甲基-3-戊酮、或環己酮。當存在時,基於組成物之總重量,組成物包括約0.001重量%至約2重量%碘清除劑。
為確保潤濕,尤其當pH低時,可將表面活性劑添加至組成物,其較佳係抗氧化的氟化陰離子性表面活性劑。於本發明組成物中涵蓋的陰離子性表面活性劑包括,但不限於,氟表面活性劑諸如ZONYL® UR及ZONYL® FS-62(DuPont Canada Inc.,Mississauga,Ontario,Canada)、及氟烷基磺酸銨諸如NovecTM 4300(3M)。當所使用之蝕刻劑包含氟化物時,涵蓋使用可用作表面活性
劑及蝕刻劑之長鏈氟化四烷基銨。
在另一具體例中,本文所述之任何組成物可進一步包含氮化鈦及/或光阻蝕刻材料殘留物,其中該殘留物係懸浮及/或溶解於組成物中。
在一具體例中,第一態樣之組成物包含以下組分,由其等所組成,或基本上由其等所組成:至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、至少一種Ge/SiGe鈍化劑、水、及至少一種有機溶劑,其中該組成物實質上不含過氧化氫,該等組分係以基於組成物之總重量計之以下範圍存在:
在組成物之一特佳具體例中,該至少一種氧化劑包括氧化釩
(IV、V)(V6O13)、氧化釩、釩酸銨、碘酸銨、過碘酸銨、碘酸、過碘酸、或其組合;該至少一種蝕刻劑包括HF、氟化氫銨、六氟矽酸、四氟硼酸、或其組合;該至少一種腐蝕抑制劑包括5-甲基-1H-苯并三唑、吡唑、苯并三唑、溴化肉豆蔻基三甲基銨、殺藻胺、對甲苯磺酸十六烷基三甲基銨、氫氧化十六烷基三甲基銨、5-苄基-1H-四唑、或其組合;該至少一種Ge/SiGe鈍化劑包括丙酮酸,及該至少一種有機溶劑包括碳酸丁二酯(BC)、碳酸乙二酯、碳酸丙二酯(PC)、乙二醇、1,2-及1,3-丙二醇、二丙二醇、二甘醇(DEG)、DMSO、二甘醇單丁醚、二甘醇單己醚、或其組合。
在另一具體例中,第一態樣之組成物包含以下組分,由其等所組成,或基本上由其等所組成:至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、至少一種Ge/SiGe鈍化劑、水、至少一種pH調節劑、及至少一種有機溶劑,其中該組成物實質上不含過氧化氫,該等組分係以基於組成物之總重量計之以下範圍存在:
在組成物之一特佳具體例中,該至少一種氧化劑包括氧化釩(IV、V)(V6O13)、氧化釩、釩酸銨、碘酸銨、過碘酸銨、碘酸、過碘酸、或其組合;該至少一種蝕刻劑包括HF、氟化氫銨、或其組合;該至少一種腐蝕抑制劑包括5-甲基-1H-苯并三唑、吡唑、苯并三唑、溴化肉豆蔻基三甲基銨、殺藻胺、對甲苯磺酸十六烷基三甲基銨、氫氧化十六烷基三甲基銨、5-苄基-1H-四唑、或其組合;該至少一種Ge/SiGe鈍化劑包括丙酮酸,該至少一種pH調節劑包括四氟硼酸、硫酸、或其組合,及該至少一種有機溶劑包括碳酸丁二酯(BC)、碳酸乙二酯、碳酸丙二酯(PC)、乙二醇、1,2-及1,3-丙二醇、二丙二醇、二甘醇(DEG)、DMSO、二甘醇單丁醚、二甘醇單己醚、或其組合。
在又另一具體例中,第一態樣之組成物包含以下組分,由其等所組成,或基本上由其等所組成:至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、至少一種Ge/SiGe鈍化劑、水、至少一種pH調節劑、及至少一種有機溶劑,其中該組成物實質上不含過氧化氫,該等組分係以基於組成物之總重量計之以下範圍存在:
在組成物之一特佳具體例中,該至少一種氧化劑包括氧化釩(IV、V)(V6O13)、氧化釩、釩酸銨、碘酸銨、過碘酸銨、碘酸、過碘酸、或其組合;該至少一種蝕刻劑包括HF、氟化氫銨、或其組合;該至少一種腐蝕抑制劑包括5-甲基-1H-苯并三唑、吡唑、苯并三唑、溴化肉豆蔻基三甲基銨、殺藻胺、對甲苯磺酸十六烷基三甲基銨、氫氧化十六烷基三甲基銨、5-苄基-1H-四唑、或其組合;該至少一種Ge/SiGe鈍化劑包括丙酮酸,該至少一種pH調節劑包括氫氯酸、硫酸、或其組合,及該至少一種有機溶劑包括碳酸丁二酯(BC)、碳酸乙二酯、碳酸丙二酯(PC)、乙二醇、1,2-及1,3-丙二醇、二丙二醇、二甘醇(DEG)、DMSO、二甘醇單丁醚、二甘醇單己醚、或其組合。
在又另一具體例中,第一態樣之組成物包含以下組
分,由其等所組成,或基本上由其等所組成:至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、至少一種Ge/SiGe鈍化劑、水、至少一種pH調節劑、至少一種低k鈍化劑、及至少一種有機溶劑,其中該組成物實質上不含過氧化氫,該等組分係以基於組成物之總重量計之以下範圍存在:
在組成物之一特佳具體例中,該至少一種氧化劑包括氧化釩(IV、V)(V6O13)、氧化釩、釩酸銨、碘酸銨、過碘酸銨、碘酸、過碘酸、或其組合;該至少一種蝕刻劑包括HF、氟化氫銨、或其組合;該至少一種腐蝕抑制劑包括5-甲基-1H-苯并三唑、吡唑、苯并
三唑、溴化肉豆蔻基三甲基銨、殺藻胺、對甲苯磺酸十六烷基三甲基銨、氫氧化十六烷基三甲基銨、5-苄基-1H-四唑、或其組合;該至少一種Ge/SiGe鈍化劑包括丙酮酸,該至少一種pH調節劑包括氫氯酸、硫酸、或其組合,該至少一種低k鈍化劑包括硼酸,及該至少一種有機溶劑包括碳酸丁二酯(BC)、碳酸乙二酯、碳酸丙二酯(PC)、乙二醇、1,2-及1,3-丙二醇、二丙二醇、二甘醇(DEG)、DMSO、二甘醇單丁醚、二甘醇單己醚、或其組合。
當明瞭一般實務係製造濃縮形式的組成物以在使用之前稀釋。舉例來說,組成物可以更為濃縮的形式製造,其後再在製造商處、在使用前、及/或在工廠在使用期間以至少一種溶劑(例如,水及/或至少一種有機溶劑)稀釋。稀釋比率可在約0.1份稀釋劑:1份組成物濃縮物至約100份稀釋劑:1份組成物濃縮物範圍內。應進一步明瞭文中所述之組成物包括可能隨時間而不安定的氧化劑。因此,該濃縮形式可實質上不含氧化劑,且氧化劑可由製造商在使用之前及/或在工廠在使用期間引入至濃縮物或經稀釋的組成物。
文中所述之組成物係經由簡單地添加各別成分及混合至均勻狀態而容易地調配得。此外,可輕易地將組成物調配為單一包裝調配物或在使用點處或使用點前混合的多份調配物,較佳係多份調配物。可將多份調配物之個別份於工具處或於混合區域/範圍(諸如線上混合器)或於工具上游之儲槽中混合。涵蓋多份調配物之各個份可包含成分/組分之任何組合,其當混合在一起時形成期望的組成物。各別成分的濃度可在組成物的特定倍數內寬廣地改變,即更稀或更濃,且當明瞭組成物可變化及替代地包含與本文之
揭示內容一致之成分的任何組合,由其所組成,或基本上由其所組成。
因此,第二態樣係關於一種套組,其包括存於一或多個容器中之一或多種適於形成文中所述之組成物的組分。套組之容器必需適於儲存及運送該等組成物組分,例如,NOWPak®容器(Advanced Technology Materials,Inc.,Danbury,Conn.,USA)。容納組成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流體相通,以進行摻混及配送的構件。舉例來說,參照NOWPak®容器,可對該一或多個容器中之襯裡的外側施加氣體壓力,以導致襯裡之至少一部分的內容物排出,且因此可流體相通而進行摻混及配送。或者,可對習知之可加壓容器的頂部空間施加氣體壓力,或可使用泵於達成流體相通。此外,系統較佳包括用於將經摻混之組成物配送至製程工具的配送口。
較佳使用實質上化學惰性、不含雜質、可撓性及彈性的聚合薄膜材料,諸如高密度聚乙烯,於製造該一或多個容器的襯裡。理想的襯裡材料不需要共擠塑或障壁層以進行加工,且不含任何會不利影響待置於襯裡中之組分之純度需求的顏料、UV抑制劑、或加工劑。理想襯裡材料的清單包括含純粹(無添加劑)聚乙烯、純粹聚四氟乙烯(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、聚丁烯等等的薄膜。此等襯裡材料的較佳厚度係在約5密爾(mil)(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,將以下專利及專利申請案之揭示內容的各別全體以引用的方式併入本文:美國專利第7,188,644號,
標題「使超純液體中之顆粒產生減至最小的裝置及方法(APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS)」;美國專利第6,698,619號,標題「可回收及再利用的桶中袋流體儲存及配送容器系統(RETURNABLE AND REUSABLE,BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM)」;及2008年5月9日提出申請之PCT/US08/63276,標題「材料摻混及分佈用的系統及方法(SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION)」。
在第三態樣中,本發明係關於使用文中所述之組成物自其上具有氮化鈦材料之微電子裝置之表面蝕刻該材料之方法。舉例來說,可移除氮化鈦材料,而不實質地損壞/移除存在於微電子裝置上之半導體基板、金屬導體及絕緣體材料。因此,在一較佳具體例中,描述一種使用文中所述之組成物自其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置之表面相對於半導體基板、金屬導體及絕緣體材料選擇性及實質地移除該等材料之方法。在另一較佳具體例中,描述一種使用文中所述之組成物自其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置之表面相對於金屬導體(例如,銅)、鎢、鍺、鍺化矽、及絕緣體材料選擇性及實質地移除該等材料之方法。
在應用時,組成物係以任何適當方式施用至其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置的表面,例如,經由將組成物噴塗於裝置之表面上,經由將包括氮化鈦及/或光阻蝕刻殘留材料之裝置浸泡(於靜態或動態體積之組成物中),經由使裝置
與其上吸收有組成物之另一材料(例如,墊、或纖維吸收性塗布器元件)接觸,經由使包括氮化鈦及/或光阻蝕刻殘留材料之裝置與循環的組成物接觸,或藉由任何其他藉以使組成物與氮化鈦及/或光阻蝕刻殘留材料進行移除接觸之適當手段、方式或技術。該應用可係於批式或單一晶圓裝置中用於動態或靜態清洗。有利地,藉由其相對可能存在於微電子裝置結構上且暴露至組成物之其他材料(諸如半導體基板、金屬及絕緣材料(即低k介電質))針對氮化鈦及/或光阻蝕刻殘留材料之選擇性之文中所述的組成物以高度有效且高度選擇性的方式達成氮化鈦及/或光阻蝕刻殘留材料之至少部分移除。
在使用文中所述之組成物於自其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置結構移除該等材料時,典型上使該組成物與裝置結構在單一晶圓工具中在約20℃至約100℃範圍內,較佳約45℃至約60℃之溫度下接觸約0.3分鐘至約30分鐘,較佳約0.5分鐘至約3分鐘之足夠時間。該等接觸時間及溫度係為說明性,可使用任何其他可有效地自裝置結構至少部分地移除氮化鈦及/或光阻蝕刻殘留材料之適宜時間及溫度條件。
在一具體例中,組成物係在傳遞至裝置結構的期間線上加熱。藉由於線上,而非於浴槽本身中加熱,組成物壽命增長。
於達成期望的移除作用後,可輕易地將組成物自其先前經施用的微電子裝置移除,例如,藉由可能係在文中所述組成物的給定最終應用中所期望且有效的沖洗、洗滌、或其他移除步驟。舉例來說,裝置可經包括去離子水的沖洗溶液沖洗及/或乾燥(例如,旋轉乾燥、N2、蒸氣乾燥等)。
組成物較佳相對於半導體基板、金屬導體及絕緣(即低k介電質)材料選擇性地蝕刻氮化鈦材料。在一具體例中,在50℃下氮化鈦之蝕刻速率高(高於50埃/分鐘,較佳高於約35埃/分鐘),且同時在相同溫度下金屬(例如,Cu及W)之蝕刻速率低(低於10埃/分鐘,較佳低於約5埃/分鐘)及低k介電質之蝕刻速率低(低於約10埃/分鐘,較佳低於約5埃/分鐘)。
第四態樣係關於根據文中所述方法製得之經改良的微電子裝置及包含此等微電子裝置之產品。
第五態樣係關於製造包含微電子裝置之物件的方法,該方法包括使微電子裝置與組成物接觸足夠的時間以自其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置之表面蝕刻移除該等材料,及將該微電子裝置併入該物件中,其中該組成物包含以下組分,由其等所組成,或基本上由其等所組成:至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、至少一種Ge/SiGe鈍化劑、水、及至少一種有機溶劑,其中該組成物實質上不含過氧化氫。該組成物可進一步包含氮化鈦材料,由其所組成或基本上由其所組成。
本發明之第六態樣係關於一種製造物件,其包括以下各物,由其等所組成或基本上由其等所組成:微電子裝置基板、該基板上之氮化鈦層、及文中所述之組成物。
本發明之特徵及優點由以下論述的說明性實施例作更完整展示。
製備包含0.8重量% HBF4(作為pH調節劑)、0.5重量
%吡唑、0.01重量%過碘酸(50%)、及表1中列舉之其他組分(以重量%計)的調配物。使SiGe、鎢、TiN及PETEOS試樣在各調配物中於50℃下浸泡所指示的時間並測定蝕刻速率。
可看見丙酮酸使SiGe蝕刻速率保持為相當低。若無額外的V6O13氧化劑,則SiGe蝕刻速率高至12.5埃/分鐘。
製備包含0.8重量% HBF4(作為pH調節劑)、0.5重量%吡唑、及表2中列舉之其他組分(以重量%計)的調配物,其中兩種氧化劑中之至少一者係以至少0.001重量%之量存在。使SiGe、鎢、TiN及PETEOS試樣在各調配物中於50℃下浸泡所指示的時間並測定蝕刻速率。
蝕刻劑對於移除TiN、以及Ge/SiGe鈍化劑之重要性於表2中輕易地證實。
製備表3中列舉的調配物Y及Z。使SiGe、鎢、TiN、PETEOS、及低k介電質(BD-II)試樣在各調配物中於60℃下浸泡所指示的時間並測定蝕刻速率。
雖然本發明已參照本發明之特定態樣、特徵及說明性具體例描述於文中,但當明瞭本發明之效用並不因此受限,而係可延伸至涵蓋熟悉本發明領域人士基於文中之揭示內容當可明白的
許多其他變化、修改及替代具體例。相應地,後文所主張之本發明意欲經廣泛地解釋及詮釋為包括於其精神及範疇內之所有該等變化、修改及替代具體例。
Claims (21)
- 一種用於自其上具有氮化鈦及/或光阻蝕刻殘留材料之微電子裝置之表面選擇性地移除該等材料之組成物,該組成物包含至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、至少一種Ge/SiGe鈍化劑、水、及至少一種有機溶劑,其中該組成物實質上不含過氧化氫,其中該至少一種Ge/SiGe鈍化劑包括選自由下列所組成之群之物質:丙酮酸、1,2-己二醇、草乙酸、殺藻胺(benzalkonium chloride)、聚丙烯酸、葡萄糖、乙醯乙酸、乙醯丙酸、2-酮基戊二酸酯、聚乙二醇(如PEG 200)、氯化十二烷基三甲基銨(DTAC)、及其組合。
- 如請求項1之組成物,其中,該蝕刻劑包括選自由下列所組成之群之物質:H2ZrF6、H2TiF6、HPF6、HF、氟化銨、氟化氫銨、四氟硼酸、六氟矽酸、四氟硼酸四丁銨(TBA-BF4)、六氟矽酸銨、六氟鈦酸銨、氟化四烷基銨(NR1R2R3R4F)、氫氧化四烷基銨(NR1R2R3R4OH)其中R1、R2、R3、R4可彼此相同或不同且係選自由直鏈或分支鏈C1-C6烷基所組成之群、弱鹼、及其組合,較佳為選自由下列所組成之群之物質:HF、氟化氫銨、四氟硼酸、六氟矽酸、及其組合。
- 如前述請求項中任一項之組成物,其中,該氧化劑包括選自由下列所組成之群之物質:FeCl3(包括水合及未水合兩者)、Fe(NO3)3、Sr(NO3)2、CoF3、FeF3、MnF3、發氧方(oxone,2KHSO5˙KHSO4˙K2SO4)、過碘酸、碘酸、氧化釩(V)、氧化釩(IV、V)、釩酸銨、過氧單硫酸銨、亞氯酸銨(NH4ClO2)、氯酸銨(NH4ClO3)、碘酸銨(NH4IO3)、硝酸銨(NH4NO3)、過硼酸銨(NH4BO3)、過氯酸銨 (NH4ClO4)、過碘酸銨(NH4IO3)、過硫酸銨((NH4)2S2O8)、次氯酸銨(NH4ClO)、鎢酸銨((NH4)10H2(W2O7))、過硫酸鈉(Na2S2O8)、次氯酸鈉(NaClO)、過硼酸鈉、碘酸鉀(KIO3)、過錳酸鉀(KMnO4)、過硫酸鉀、硝酸(HNO3)、過硫酸鉀(K2S2O8)、次氯酸鉀(KClO)、亞氯酸四甲銨((N(CH3)4)ClO2)、氯酸四甲銨((N(CH3)4)ClO3)、碘酸四甲銨((N(CH3)4)IO3)、過硼酸四甲銨((N(CH3)4)BO3)、過氯酸四甲銨((N(CH3)4)ClO4)、過碘酸四甲銨((N(CH3)4)IO4)、過硫酸四甲銨((N(CH3)4)S2O8)、過氧單硫酸四丁銨、過氧單硫酸、硝酸鐵(Fe(NO3)3)、過乙酸(CH3(CO)OOH)、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯苯醌、四氧嘧啶(alloxan)、N-甲基啉N-氧化物、三甲胺N-氧化物、及其組合,較佳為選自由下列所組成之群之物質:V6O13、氧化釩、碘酸銨、過碘酸銨、釩酸銨、過碘酸、碘酸、及其組合。
- 如請求項1或2之組成物,其中,該氧化劑包括選自由V6O13、過碘酸、及其組合所組成之群之物質。
- 如請求項1或2之組成物,其中,該至少一種腐蝕抑制劑包括選自由下列所組成之群之物質: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-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-胺基四唑、伸戊基四唑、5-苯基-1H-四唑、5-苄基-1H-四唑、Ablumine O、2-苄基吡啶、琥珀醯亞胺、順丁烯二醯亞胺、酞二醯亞胺、戊二醯亞胺、2,4-二胺基-6-甲基-1,3,5-三、噻唑、吡唑、三、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、二胺甲基三、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、苯并噻唑、咪唑、吲二唑(indiazole)、腺苷酸、咔唑、糖精、安息香肟、PolyFox PF-159、聚(乙二醇)、聚(丙二醇)、PEG-PPG共聚物、十二烷基苯磺酸、十二烷基苯磺酸鈉、殺藻胺、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、Aliquat 336、氯化苄基二甲基苯基銨、Crodaquat TES、Rewoquat CPEM、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’-聯吡錠、溴化烷基三甲基銨、鹽酸安保寧(amprolium hydrochloride)、氫氧化苯乙基銨(benzethonium hydroxide)、氯化苯乙基銨(benzethonium chloride)、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、膽鹼對甲苯磺酸鹽、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、吉拉德試劑(Girard’s reagent)、十六烷基(2-羥乙基)二甲基磷酸二氫銨、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、氯化甲基苯乙基銨、Hyamine® 1622、LuviquatTM、N,N,,N’-聚氧伸乙基(10)-N-牛脂-1,3-二胺基丙烷液體、溴化羥苯乙胺(oxyphenonium bromide)、溴化四庚基銨、溴化肆(癸基)銨、通佐溴銨(thonzonium bromide)、 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、氯化二甲基二硬脂基銨、氯化六羥季銨(hexamethonium chloride)、及其組合,較佳為選自由吡唑、苯并三唑衍生物、陽離子性四級表面活性劑、及其組合所組成之群之物質。
- 如請求項1或2之組成物,其中,該至少一種有機溶劑包括選自由下列所組成之群之物質: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、1,2-及1,3-丙二醇、1,2-、1,3-、及1,4-丁二醇、四氫呋喃甲醇(THFA)、碳酸丁二酯、碳酸乙二酯、碳酸丙二酯、二丙二醇、二甘醇、二甘醇單甲醚、三甘醇單甲醚、二甘醇單乙醚、三甘醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二甘醇單丁醚、三甘醇單丁醚、乙二醇單己醚、二甘醇單己醚、乙二醇苯基醚、丙二醇甲基醚、二丙二醇甲基醚(DPGME)、三丙二醇甲基醚(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、乙基全氟丁基醚、甲基全氟丁基醚、碳酸烷二酯、4-甲基-2-戊醇、四亞甲二醇二甲基醚、二甲亞碸、四氫噻吩碸、甲磺酸(MSA)、及其組合,較佳為二甘醇單乙醚、二甘醇甲基醚、丙二醇、乙二醇、四甘醇二甲醚、三甘醇甲基醚、三甘醇乙基醚、三丙二醇單甲醚、二丙二醇單甲醚、或其組合,較佳為選自由下列所組成之群之物質:碳酸丁二酯(BC)、碳酸乙二酯、碳酸丙二酯(PC)、乙二醇、1,2-及1,3-丙二醇、二丙二醇、二甘醇 (DEG)、DMSO、二甘醇單丁醚、二甘醇單己醚、及其組合。
- 如請求項1或2之組成物,其中,該組成物進一步包括至少一種選自由下列所組成之群之額外組分:至少一種矽石來源、至少一種低k鈍化劑、至少一種表面活性劑、至少一種碘清除劑、及其組合。
- 如請求項7之組成物,其中,該組成物進一步包括至少一種選自由硼酸、五硼酸銨、四硼酸鈉、3-羥基-2-萘甲酸、丙二酸、亞胺二乙酸、及其組合所組成之群之低k鈍化劑。
- 如請求項1或2之組成物,其中,該組成物實質上不含胺、化學機械拋光研磨材料、金屬鹵化物、及其組合。
- 如請求項1或2之組成物,其中,該組成物在約45℃至約60℃範圍內之溫度下具有大於50:1之TiN對鎢之選擇性及小於約2埃/分鐘之鎢移除速率。
- 如請求項1或2之組成物,其中,該組成物在約45℃至約60℃範圍內之溫度下具有大於50:1之TiN對SiGe之選擇性及小於約3埃/分鐘之SiGe移除速率。
- 如請求項1或2之組成物,其中,該組成物之pH係在約0至約4之範圍內。
- 如請求項1或2之組成物,其中,基於組成物之總重量,該組成物中之水量係在約0.1重量%至約50重量%、較佳約1重量%至約30重量%、及再更佳約5重量%至約20重量%之範圍內。
- 如請求項1或2之組成物,其中,基於組成物之總重量,該組成物中之有機溶劑量係在約0.1重量%至約50重量%、較佳約1重量%至約30重量%、及再更佳約5重量%至約20重量%之範圍內。
- 一種自其上具有氮化鈦材料之微電子裝置之表面蝕刻該材料 之方法,該方法包括使該表面與一組成物接觸,其中該組成物相對於半導體基板、金屬、及絕緣材料自表面選擇性地移除氮化鈦材料,且其中該組成物包含至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、至少一種Ge/SiGe鈍化劑、水、及至少一種有機溶劑,其中該組成物實質上不含過氧化氫,及其中該至少一種Ge/SiGe鈍化劑包括選自由下列所組成之群之物質:丙酮酸、1,2-己二醇、草乙酸、殺藻胺、聚丙烯酸、葡萄糖、乙醯乙酸、乙醯丙酸、2-酮基戊二酸酯、聚乙二醇(如PEG 200)、氯化十二烷基三甲基銨(DTAC)、及其組合。
- 如請求項15之方法,其中,該接觸包括在約20℃至約100℃範圍內之溫度下約0.3分鐘至約30分鐘範圍內之時間。
- 如請求項15或16之方法,其中,該組成物在該期望的蝕刻作用後自該表面沖洗。
- 如請求項15或16之方法,其中,該等金屬包含銅、鎢或兩者。
- 如請求項15或16之方法,其中,該半導體基板包括鍺或鍺化矽。
- 如請求項15或16之方法,其中,該組成物在約45℃至約60℃範圍內之溫度下具有大於50:1之TiN對鎢之選擇性及低於約2埃/分鐘之鎢移除速率。
- 如請求項15或16之方法,其中,該組成物在約45℃至約60℃範圍內之溫度下具有大於50:1之TiN對SiGe之選擇性及低於約3埃/分鐘之SiGe移除速率。
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