CN105304485B - 选择性蚀刻金属氮化物的组合物及方法 - Google Patents
选择性蚀刻金属氮化物的组合物及方法 Download PDFInfo
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- CN105304485B CN105304485B CN201510644253.7A CN201510644253A CN105304485B CN 105304485 B CN105304485 B CN 105304485B CN 201510644253 A CN201510644253 A CN 201510644253A CN 105304485 B CN105304485 B CN 105304485B
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- acid
- composition
- ether
- ammonium
- metal gate
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 175
- 239000002184 metal Substances 0.000 title claims abstract description 175
- 239000000203 mixture Substances 0.000 title claims abstract description 128
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 150
- 239000000758 substrate Substances 0.000 claims abstract description 35
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims abstract description 13
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 methylene phosphonic acid Chemical compound 0.000 claims description 62
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 42
- 239000003112 inhibitor Substances 0.000 claims description 40
- 239000007800 oxidant agent Substances 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 34
- 230000001590 oxidative effect Effects 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 28
- 239000004094 surface-active agent Substances 0.000 claims description 26
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 23
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 239000000908 ammonium hydroxide Substances 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
- 239000011668 ascorbic acid Substances 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 230000031709 bromination Effects 0.000 claims description 10
- 238000005893 bromination reaction Methods 0.000 claims description 10
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 claims description 10
- FTMKAMVLFVRZQX-UHFFFAOYSA-N octadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCP(O)(O)=O FTMKAMVLFVRZQX-UHFFFAOYSA-N 0.000 claims description 10
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- 150000003009 phosphonic acids Chemical class 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 7
- 239000012964 benzotriazole Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-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
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 claims description 6
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003851 azoles Chemical class 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- LUVHDTDFZLTVFM-UHFFFAOYSA-N chloric acid tetramethylazanium Chemical compound C[N+](C)(C)C.Cl(=O)(=O)O LUVHDTDFZLTVFM-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 6
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 claims description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 claims description 5
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical class CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 5
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 5
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- JDPSFRXPDJVJMV-UHFFFAOYSA-N hexadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCP(O)(O)=O JDPSFRXPDJVJMV-UHFFFAOYSA-N 0.000 claims description 5
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- 229910052914 metal silicate Inorganic materials 0.000 claims description 4
- 229940049964 oleate Drugs 0.000 claims description 4
- 239000011236 particulate material Substances 0.000 claims description 4
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- 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
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-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
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- OMAFFHIGWTVZOH-UHFFFAOYSA-O 1-methyl-2h-tetrazol-1-ium Chemical compound C[N+]1=CN=NN1 OMAFFHIGWTVZOH-UHFFFAOYSA-O 0.000 claims description 3
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 3
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 3
- UGAGPNKCDRTDHP-UHFFFAOYSA-N 16-hydroxyhexadecanoic acid Chemical compound OCCCCCCCCCCCCCCCC(O)=O UGAGPNKCDRTDHP-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
- MTVLEKBQSDTQGO-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol Chemical compound CCOC(C)COC(C)CO MTVLEKBQSDTQGO-UHFFFAOYSA-N 0.000 claims description 3
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 claims description 3
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 claims description 3
- CIWBSHSKHKDKBQ-SZSCBOSDSA-N 2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one Chemical compound OC[C@H](O)C1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-SZSCBOSDSA-N 0.000 claims description 3
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- FYYLCPPEQLPTIQ-UHFFFAOYSA-N 2-[2-(2-propoxypropoxy)propoxy]propan-1-ol Chemical compound CCCOC(C)COC(C)COC(C)CO FYYLCPPEQLPTIQ-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 3
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 claims description 3
- PDBMKOUAWURVBE-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-yloxy)pentane Chemical compound CCCC(C)(C)OC(C)(C)CCC PDBMKOUAWURVBE-UHFFFAOYSA-N 0.000 claims description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-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
- XILPCSMEKCBYFO-UHFFFAOYSA-N 4-methyl-1,2,4-triazole Chemical compound CN1C=NN=C1 XILPCSMEKCBYFO-UHFFFAOYSA-N 0.000 claims description 3
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-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
- 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 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
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- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
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- 150000003863 ammonium salts Chemical class 0.000 description 1
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- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 229960000800 cetrimonium bromide Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
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- 230000003628 erosive effect Effects 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- 238000003754 machining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 description 1
- LGAWFGCTQRLGQE-UHFFFAOYSA-N octan-3-ylphosphonic acid Chemical class CCCCCC(CC)P(O)(O)=O LGAWFGCTQRLGQE-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical group O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920000053 polysorbate 80 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
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910021324 titanium aluminide Inorganic materials 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28088—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being a composite, e.g. TiN
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
- H01L21/82—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices to produce devices, e.g. integrated circuits, each consisting of a plurality of components
- H01L21/822—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices to produce devices, e.g. integrated circuits, each consisting of a plurality of components the substrate being a semiconductor, using silicon technology
- H01L21/8232—Field-effect technology
- H01L21/8234—MIS technology, i.e. integration processes of field effect transistors of the conductor-insulator-semiconductor type
- H01L21/8238—Complementary field-effect transistors, e.g. CMOS
- H01L21/823828—Complementary field-effect transistors, e.g. CMOS with a particular manufacturing method of the gate conductors, e.g. particular materials, shapes
- H01L21/823842—Complementary field-effect transistors, e.g. CMOS with a particular manufacturing method of the gate conductors, e.g. particular materials, shapes gate conductors with different gate conductor materials or different gate conductor implants, e.g. dual gate structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/00523—Etching material
- B81C1/00539—Wet etching
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28079—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being a single metal, e.g. Ta, W, Mo, Al
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
- Drying Of Semiconductors (AREA)
Abstract
本发明涉及选择性蚀刻金属氮化物的组合物及方法。具体地,本发明涉及用于自其上具有第一金属栅极材料(例如,氮化钛)及第二金属栅极材料(例如,氮化钽)的微电子装置,将第一金属栅极材料相对于第二金属栅极材料选择性地移除的移除组合物及方法。该移除组合物可包含氟化物或者实质上不含氟化物。该基板优选包括高k/金属栅极集成配置。
Description
本申请为国际申请PCT/US2011/055049于2013年4月8日进入中国国家阶段、申请号为201180048783.5、发明名称为“选择性蚀刻金属氮化物的组合物及方法”的分案申请。
技术领域
本发明涉及用于自包含一种金属栅极材料及第二金属栅极材料的基板,将该一种金属栅极材料相对于第二金属栅极材料选择性地移除的组合物及方法。该基板优选包括高k/金属栅极集成配置。
背景技术
大部分目前的集成电路(IC)通过使用多个互连场效晶体管(FET)(亦称为金属氧化物半导体场效晶体管(MOSFET或MOS晶体管))来实施。MOS晶体管包括栅电极作为覆盖在半导体基板上的控制电极及位于基板中的隔开的源区及漏区,电流可于其间流动。栅极绝缘体设置于栅电极与半导体基板之间,以使栅电极与基板电隔离。施加至栅电极的控制电压控制电流通过基板中的通道在栅电极下方的源极与漏区之间流动。存在将愈来愈多的电路并入至单一IC芯片上的持续趋势。为并入增加量的电路,必需减小电路中各单独装置的尺寸及装置组件间的尺寸及间隔(特征尺寸)。
为实现半导体装置的缩放,考虑各种非公知的、敏感性的、和/或奇特的材料。考虑将高介电常数材料(亦称为“高k介电质”,诸如二氧化铪(HfO2)、氧氮化硅铪(HfSiON)、或二氧化锆(ZrO2))用于45纳米节点及超越的技术,以容许栅极绝缘体的缩放。为防止费米能阶钉扎(Fermi-level pinning),使用具有适当功函数的金属栅极作为高k栅极介电质上的栅电极。此等金属栅电极通常由金属栅极形成材料诸如镧(La)、铝(Al)、镁(Mg)、钌(Ru)、钛基材料诸如钛(Ti)及氮化钛(TiNx)、钽基材料诸如钽(Ta)及氮化钽(TaNx)、碳化钛(Ti2C)或碳化钽(Ta2C)等形成。
金属栅电极的最优选功函数将根据其是否用于形成NMOS晶体管或PMOS晶体管而异。因此,当使用相同材料来制造NMOS及PMOS晶体管的金属栅电极时,该等栅电极无法展现针对两种类型装置的期望功函数。已证实此问题可藉由自第一材料形成NMOS晶体管的金属栅电极及自第二材料形成PMOS晶体管的金属栅电极来消除。第一材料可确保针对NMOS栅电极的可接受的功函数,而第二材料可确保针对PMOS栅电极的可接受的功函数。然而,形成此等双金属栅极装置的制程可能复杂且昂贵。举例来说,在高k/金属栅极集成配置中选择性蚀刻诸如TiNx及TaNx的功函数金属由于此等金属氮化物的相似物理及化学性质而极具挑战性。
为此,本发明的目的为提供用于自其上具有一种金属栅极材料及第二金属栅极材料的微电子装置,将该一种金属栅极材料相对于第二金属栅极材料选择性地移除的改良组合物及方法,该组合物可与存在于基板上的其它栅极堆栈材料兼容。
发明内容
本发明大体上涉及用于自包含一种金属栅极材料及第二金属栅极材料的基板,将该一种金属栅极材料相对于第二金属栅极材料选择性地移除的组合物及方法。该基板优选包括高k/金属栅极集成配置。
在一方面中,描述一种相对于至少第二金属栅极材料选择性地移除第一金属栅极材料的方法,该方法包括使包含第一金属栅极材料及第二金属栅极材料的基板与移除组合物接触,其中该移除组合物相对于该第二金属栅极材料选择性地移除该第一金属栅极材料。
在另一方面中,描述一种相对于至少第二金属栅极材料选择性地移除第一金属栅极材料的方法,该方法包括使包含第一金属栅极材料及第二金属栅极材料的基板与移除组合物接触,其中该移除组合物相对于该第二金属栅极材料选择性地移除该第一金属栅极材料,以及其中该移除组合物包含至少一种氧化剂及至少一种金属氮化物抑制剂。
本发明的其它方面、特征及优点可由下文内容及权利要求书更加明白。
具体实施方案
本发明大体上涉及用于自包含一种金属栅极材料及第二金属栅极材料的基板,将该一种金属栅极材料相对于第二金属栅极材料选择性地移除的组合物及方法。更具体而言,本发明大体上涉及用于自包含一种金属栅极材料及第二金属栅极材料的基板,将该一种金属栅极材料相对于第二金属栅极材料选择性地移除的组合物及湿式方法,其中该组合物及方法实质上未移除存在于基板上的其它栅极堆栈材料。该基板优选包括高k/金属栅极集成配置。
为容易参考起见,“微电子装置”相当于经制造用于微电子、集成电路、能量收集、或计算机芯片应用中是半导体基板、平板显示器、相变记忆装置、太阳能面板及包括太阳能电池装置、光伏打组件、及微机电***(MEMS)的其它产品。应明了术语“微电子装置”、“微电子基板”及“微电子装置结构”并不具任何限制意味,且其包括任何最终将成为微电子装置或微电子组件的基板或结构。微电子装置可为图案化、毯覆式、控制和/或测试装置。
如本文所定义的“金属栅极材料”相当于具有对应于半导体基板的中间间隙(mid-gap)的费米能阶的材料,诸如Ti、Ta、W、Mo、Ru、Al、La、氮化钛、氮化钽、碳化钽、碳化钛、氮化钼、氮化钨、氧化钌(IV)、氮化钽硅、氮化钛硅、氮化钽碳、氮化钛碳、铝化钛、铝化钽、氮化钛铝、氮化钽铝、氧化镧、或其组合。应明了被公开为金属栅极材料的化合物可具有不同的化学计量。因此,氮化钛在文中将表示为TiNx,氮化钽在文中将表示为TaNx,等等。
如本文所定义的“高k介电质”材料相当于:氧化铪(例如,HfO2);氧化锆(例如,ZrO2);氧硅酸铪;硅酸铪;硅酸锆;硅酸钛;氧化铝;它的掺镧类似物(例如,LaAlO3);硅酸铝;钛酸盐(例如,Ta2O5);铪及硅的氧化物及氮化物(例如,HfSiON);它的掺镧类似物(例如,HFSiON(La));钛酸钡锶(BST);铪及铝的氧化物(例如,HfxAlyOz);钛酸锶(SrTiO3);钛酸钡(BaTiO3);及其组合。
如本文所定义的“栅极堆栈材料”相当于:钽、氮化钽、氮化钛、钛、镍、钴、钨、氮化钨、及前述金属的硅化物;低k介电质;多晶硅;聚-SiGe;氧化硅;氮化硅;BEOL层;高k置换栅极;氧化铪;氧硅酸铪;氧化锆;氧化镧;钛酸盐;它的掺氮类似物;钌;铱;镉;铅;硒;银;MoTa;及其于微电子装置上的组合及盐。
如本文所使用的“约”意在相当于所述值的±5%。
“实质上不含”在本文被定义为小于2重量%,优选小于1重量%,更优选小于0.5重量%,甚至更优选小于0.1重量%,及最优选0重量%。
如本文所使用的“相对于第二金属栅极材料选择性地移除第一金属栅极材料”相当于约2:1至约1000:1,优选约2:1至约100:1,及最优选约3:1至约50:1的蚀刻速率选择性。换句话说,当第一金属栅极材料的蚀刻速率为2埃/分钟(或至多1000埃/分钟)时,第二金属栅极材料的蚀刻速率为1埃/分钟。
如本文所使用的术语“移除”相当于将第一金属栅极材料自基板选择性地移除至组合物中。应明了第一金属栅极材料被溶解或以其它方式增溶于组合物中,以溶解为优选方式。此外,本领域技术人员应明了组合物可包括可忽略量的溶解或以其它方式增溶于其中的来自基板的第二金属栅极材料。
如本文所定义的“胺”物质包括至少一种伯胺、仲胺、叔胺及胺-N-氧化物,其前提条件为(i)同时包括羧酸基及胺基的物质,(ii)包括胺基的表面活性剂,及(iii)其中的胺基为取代基(例如,连接至芳基或杂环部分)的物质不被视为根据此定义的「胺」。胺的化学式可由NR1R2R3表示,其中R1、R2及R3可彼此相同或不同且选自由氢、直链或支链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)、直链或支链C1-C6烷醇(例如,甲醇、乙醇、丙醇、丁醇、戊醇、己醇)、及其组合所组成的组,其前提条件为R1、R2及R3不可皆为氢。
如本文所使用的“氟化物”物质相当于包括离子氟化物(F-)或共价键合的氟的物质。应明了可包括氟化物物质作为氟化物物质或于原位产生。
如本文所使用的“氯化物”物质相当于包括离子氯化物(Cl-)的物质,其前提条件为包括氯阴离子的表面活性剂不被视为根据此定义的“氯化物”。
本发明的组合物可以如更完整说明于下文的相当多样的特定调配物具体实施。
在所有此等组合物中,当参照包括零下限的重量百分比范围论述组合物的特定组分时,当明了在组合物的各种特定实施方案中可存在或不存在此等组分,且在存在此等组分的情况中,其可以基于其中使用此等组分的组合物的总重量计低至0.001重量百分比的浓度存在。
在一方面中,描述一种相对于至少第二金属栅极材料选择性地移除第一金属栅极材料的方法,该方法包括使包含第一金属栅极材料及第二金属栅极材料的基板与移除组合物接触,其中该移除组合物相对于该第二金属栅极材料选择性地移除该第一金属栅极材料。优选地,该组合物实质上不移除存在于基板上的其它栅极堆栈材料。在一实施方案中,该第一金属栅极材料包含钛及该第二金属栅极材料包含钽。在另一实施方案中,该第一金属栅极材料是第一金属氮化物及该第二金属栅极材料是第二金属氮化物。在另一实施方案中,该第一金属栅极材料是氮化钛及该第二金属栅极材料是氮化钽。在另一实施方案中,该第一金属栅极材料是氮化钽及该第二金属栅极材料是氮化钛。该基板优选包括高k/金属栅极集成配置。应明了第一金属栅极材料不一定是最先沉积的金属栅极材料(例如,当将至少两种金属栅极材料沉积于基板上时),而是被优先选择性移除的金属栅极材料。
该方法在约室温至约100℃,优选约40℃至约80℃范围内的温度下相对于第二金属栅极材料选择性地移除第一金属栅极材料。本领域技术人员应明了移除时间应根据移除是否在单一晶圆工具或多个晶圆工具中进行而异,其中对于前者时间优选在约1分钟至约10分钟的范围内及对于后者为约1分钟至约60分钟。此等接触时间及温度是说明性的,可采用任何其它可有效地自基板将第一金属栅极材料相对于第二金属栅极材料选择性地移除的适当时间及温度条件。
第一金属栅极材料的移除速率优选在约20埃/分钟至约200埃/分钟的范围内,更优选为约30埃/分钟至约100埃/分钟。第一金属栅极材料的移除优选是各向同性的。如文中所述,第二金属栅极材料的移除速率低于第一金属栅极材料的移除速率。
在第二方面中,描述一种含氟化物的移除组合物,该含氟化物的移除组合物包含至少一种氟化物、至少一种金属氮化物抑制剂、任选的至少一种氧化剂、任选的至少一种表面活性剂、及至少一种溶剂,其用于相对于第二金属栅极材料选择性地移除第一金属栅极材料。优选地,该组合物实质上不移除存在于基板上的其它栅极堆栈材料。在一实施方案中,本发明的移除组合物包含下列成分,由其所组成,或基本上由其所组成:至少一种氟化物、至少一种金属氮化物抑制剂、及至少一种溶剂。在另一实施方案中,本发明的移除组合物包含下列成分,由其所组成,或基本上由其所组成:至少一种氟化物、至少一种金属氮化物抑制剂、至少一种氧化剂、及至少一种溶剂。在另一实施方案中,本发明的移除组合物包含下列成分,由其所组成,或基本上由其所组成:至少一种氟化物、至少一种金属氮化物抑制剂、至少一种表面活性剂、及至少一种溶剂。在另一实施方案中,本发明的移除组合物包含下列成分,由其所组成,或基本上由其所组成:至少一种氟化物、至少一种金属氮化物抑制剂、至少一种氧化剂、至少一种表面活性剂、及至少一种溶剂。
在本发明的一优选实施方案中,含氟化物的移除组合物实质上不含研磨剂或其它无机颗粒材料、胺、氯化物(Cl-)、金属卤化物、硅酸盐、及其组合。第二方面的含氟化物的移除组合物的pH优选在约3至约7的范围内。
该至少一种溶剂可包含水及至少一种选自由式R1R2R3C(OH)化合物所组成的组的可与水相混溶的有机溶剂,其中R1、R2及R3彼此独立且选自由氢、C2-C30烷基、C2-C30烯基、环烷基、C2-C30烷氧基、及其组合所组成的组。举例来说,该至少一种溶剂可包含至少一种选自由下列所组成的组的物质:水、甲醇、乙醇、异丙醇、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、二甘醇单甲醚、三甘醇单甲醚、二甘醇单***、三甘醇单***、乙二醇单丙醚、乙二醇单丁醚、二甘醇单丁醚、三甘醇单丁醚、乙二醇单己醚、二甘醇单己醚、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、2,3-二氢十氟戊烷、乙基全氟丁基醚、甲基全氟丁基醚、碳酸烷基酯、碳酸亚烷基酯、4-甲基-2-戊醇、致密流体、及其组合。该至少一种溶剂优选包含水,最优选为去离子水。
该至少一种氟化物源包括,但不限于,氢氟酸、氟化铵、氟化氢铵、六氟硅酸、四氟硼酸、四氟硼酸四丁铵(TBA-BF4)、六氟钽酸、六氟钽酸铵、及其组合。该氟化物源优选包括氟化氢铵、TBA-BF4、或其组合。
此处涵盖的氧化剂包括,但不限于,臭氧、过氧化氢(H2O2)、过硫酸氢钾制剂(oxone)、过硫酸氢钾制剂四丁基铵盐、硝酸铁(Fe(NO3)3)、碘酸钾(KIO3)、碘酸(HIO3)、过碘酸(H5IO6)、过锰酸钾(KMnO4)、过锰酸(HMnO4)、氧化铬(III)、硝酸铵铈((NH4)2Ce(NO3)6)、硝酸(HNO3)、亚氯酸铵(NH4ClO2)、氯酸铵(NH4ClO3)、碘酸铵(NH4IO3)、过硼酸铵(NH4BO3)、过氯酸铵(NH4ClO4)、过碘酸铵(NH4IO3)、过硫酸铵((NH4)2S2O8)、过硫酸钠(Na2S2O8)、过硫酸钾(K2S2O8)、亚氯酸四甲铵((N(CH3)4)ClO2)、氯酸四甲铵((N(CH3)4)ClO3)、碘酸四甲铵((N(CH3)4)IO3)、过硼酸四甲铵((N(CH3)4)BO3)、过氯酸四甲铵((N(CH3)4)ClO4)、过碘酸四甲铵((N(CH3)4)IO4)、过硫酸四甲铵((N(CH3)4)S2O8)、尿素过氧化氢((CO(NH2)2)H2O2)、过乙酸(CH3(CO)OOH)、及其组合。该氧化剂优选包括过氧化氢。该氧化剂可于工厂处或工厂前引入至组合物。当存在氧化剂时,该移除组合物可被进一步补充至少一种酸,包括,但不限于,硫酸、硝酸、乙酸、三氟乙酸、及氢氯酸。
金属氮化物抑制剂优选地抑制第二金属栅极材料相对于第一金属栅极材料的移除,且其包括,但不限于,硼酸、硼酸铵、抗坏血酸、L(+)-抗坏血酸、异抗坏血酸、抗坏血酸衍生物、五倍子酸、二膦酸诸如1-羟亚乙基-1,1-二膦酸(HEDP)、1-羟乙烷-1,1-二膦酸、次氮基三(亚甲基膦酸)(NTMPA)、N,N,N’,N’-乙二胺四(亚甲基膦酸)(EDTMP)、1,5,9-三氮杂环十二烷-N,N’,N”-三(亚甲基膦酸)(DOTRP)、1,4,7,10-四氮杂环十二烷-N,N’,N”,N’”-四(亚甲基膦酸)(DOTP)、二亚乙三胺五(亚甲基膦酸)(DETAP)、氨基三(亚甲基膦酸)、双(六亚甲基)三胺膦酸、1,4,7-三氮杂环壬烷-N,N’,N”-三(亚甲基膦酸)(NOTP)、磷酸的酯;5-氨基-1,3,4-噻二唑-2-硫醇(ATDT)、苯并***(BTA)、柠檬酸、草酸、鞣酸、乙二胺四乙酸(EDTA)、尿酸、1,2,4-***(TAZ)、甲苯***、5-苯基苯并***、5-硝基苯并***、3-氨基-5-巯基-1,2,4-***、1-氨基-1,2,4-***、羟基苯并***、2-(5-氨基戊基)-苯并***、1-氨基-1,2,3-***、1-氨基-5-甲基-1,2,3-***、3-氨基-1,2,4-***、3-巯基-1,2,4-***、3-异丙基-1,2,4-***、5-苯基硫醇-苯并***、卤基苯并***(卤基=F、Cl、Br或I)、萘并***、2-巯基苯并咪唑(MBI)、2-巯基苯并噻唑、4-甲基-2-苯基咪唑、2-巯基噻唑啉、5-氨基四唑、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑烷酮、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、二氨基甲基三嗪、咪唑啉硫酮、巯基苯并咪唑、4-甲基-4H-1,2,4-***-3-硫醇、苯并噻唑、磷酸三甲苯酯、咪唑、吲二唑(indiazole)、苯甲酸、丙二酸、苯甲酸铵、儿茶酚、五倍子酚、间苯二酚、氢醌、氰尿酸、巴比妥酸及衍生物诸如1,2-二甲基巴比妥酸、α-酮酸诸如丙酮酸、腺嘌呤、嘌呤、甘氨酸/抗坏血酸、Dequest 2000、Dequest7000、对甲苯基硫脲、琥珀酸、膦酰基丁烷三羧酸(PBTCA)、
在另一实施方案中,金属氮化物抑制剂包含式(R1)(R2)P(=O)(R3)的化合物,其中R1、R2及R3彼此独立且选自由氢、羟基、C1-C30烷基、C2-C30烯基、环烷基、C2-C30烷氧基、或其任何组合所组成的组。在另一实施方案中,金属氮化物抑制剂包含式(R1R2R3R4)NX的化合物,其中R1、R2、R3及R4彼此独立且选自由氢、C1-C30烷基、C2-C30烯基、环烷基、C1-C30烷氧基、C1-C30羧酸酯、或其任何组合所组成的组,且其中X是任何具有-1电荷的阴离子。在另一实施方案中,金属氮化物抑制剂包含式[(R1)(R2)N]C(=O)(CR3R4)nC(=O)[N(R5)(R6)]的化合物,其中R1、R2、R3、R4、R5、及R6彼此独立且选自由氢、C2-C30烷基、C2-C30烯基、环烷基、C2-C30烷氧基、C2-C30羧酸酯、或其任何组合所组成的组,且其中n=1-12的任何整数。在另一实施方案中,金属氮化物抑制剂包含式R1C(=O)(OH)或R1C(=O)(OH)(CH2)n(O=)(HO)CR2的羧酸,其中R1或R2选自C1-C30烷基链或C2-C30烯基链,优选为C1-C20烷基链或C2-C20烯基链,n是介于0与20之间的整数。优选的抑制剂包括下列中的至少之一:癸基膦酸、十二烷基膦酸(DDPA)、十四烷基膦酸、十六烷基膦酸、双(2-乙基己基)磷酸酯、十八烷基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、磷酰基乙酸、十二烷基苯磺酸、十二烯基琥珀酸、二-十八烷基磷酸氢酯、十八烷基磷酸二氢酯、十二烷基胺、十二烯基琥珀酸单二乙醇酰胺、月桂酸、棕榈酸、油酸、桧酸、羟基硬脂酸、十八烷基膦酸(ODPA)、及其组合。金属氮化物抑制剂最优选包含HEDP、十二烷基膦酸、十八烷基膦酸、或其任何组合。
应明了金属氮化物抑制剂优选地抑制第二金属栅极材料相对于第一金属栅极材料的移除。甚至更优选地,金属氮化物抑制剂同时加速第一金属栅极材料的移除。可能存在金属氮化物抑制剂抑制第一及第二金属栅极材料两者的移除的情况,在此情况中,假设第二金属栅极材料实质上受抑制和/或包含用于移除第一金属栅极材料的加速剂,则该金属氮化物抑制剂仍可接受。
涵盖的表面活性剂包括,但不限于,酸及碱、非离子性表面活性剂、阴离子性表面活性剂、阳离子性表面活性剂、两性离子表面活性剂、及其组合。优选的酸性或碱性表面活性剂包括,但不限于,具有酸或碱官能性(“头”)及直链或支链烃基(“尾”)的表面活性剂和/或具有酸官能性(“头”)及全氟化烃基(“尾”)的表面活性剂。优选的酸或碱官能度包括磷酸、膦酸、膦酸单酯、磷酸单酯及二酯、羧酸、二羧酸单酯、三羧酸单酯及二酯、硫酸单酯、磺酸、胺、及其盐。该等烃基优选具有至少10个(例如,10-24个)碳原子(例如,癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基),仅除了当分子包含两个烷基链(诸如在磷酸二酯及膦酸单酯中)时,6-20个碳的稍短的烃基(例如,己基、2-乙基己基、十二烷基)为优选。全氟化烃基优选具有7-14个碳原子(例如,庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基)。优选的表面活性剂包括癸基膦酸、十二烷基膦酸、十四烷基膦酸、十六烷基膦酸、双(2-乙基己基)磷酸酯、十八烷基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、磷酰基乙酸、十二烷基苯磺酸、及十二烷基胺。
涵盖的非离子性表面活性剂包括,但不限于,聚氧亚乙基月桂基醚(Emalmin NL-100(Sanyo)、Brij 30、Brij 98)、十二烯基琥珀酸单二乙醇酰胺(DSDA,Sanyo)、乙二胺四(乙氧化物-嵌段-丙氧化物)四醇(Tetronic 90R4)、聚氧亚乙基聚氧亚丙基二醇(NewpolePE-68(Sanyo)、Pluronic L31、Pluronic 31R1)、聚氧亚丙基蔗糖醚(SN008S,Sanyo)、叔-辛基苯氧基聚乙氧乙醇(Triton X100)、支链的聚氧亚乙基(9)壬苯基醚(IGEPAL CO-250)、聚氧亚乙基山梨糖醇六油酸酯、聚氧亚乙基山梨糖醇四油酸酯、聚乙二醇脱水山梨糖醇单油酸酯(Tween 80)、脱水山梨糖醇单油酸酯(Span 80)、烷基-多葡萄糖苷、全氟丁酸乙酯、1,1,3,3,5,5-六甲基-1,5-双[2-(5-降冰片烯-2-基)乙基]三硅氧烷、单体十八烷基硅烷衍生物诸如SIS6952.0(Siliclad,Gelest)、经硅氧烷改性的聚硅氮烷诸如PP1-SG10 SilicladGlide 10(Gelest)、有机硅-聚醚共聚物诸如Silwet L-77(Setre Chemical Company)、及Silwet ECO Spreader(Momentive)、及醇乙氧化物(NatsurfTM265,Croda)。
涵盖的阳离子性表面活性剂包括,但不限于,十七烷氟辛烷磺酸四乙铵、氯化硬脂基三甲铵(Econol TMS-28,Sanyo)、溴化4-(4-二乙氨基苯基偶氮)-1-(4-硝基苄基)吡啶鎓、氯化鲸蜡基吡啶鎓单水合物、苯扎氯铵、苄索氯铵(benzethonium chloride)、氯化苄基二甲基十二烷基铵、氯化苄基二甲基十六烷基铵、溴化十六烷基三甲基铵、氯化二甲基二-十八烷基铵、氯化十二烷基三甲基铵、对甲苯磺酸十六烷基三甲基铵、溴化二-十二烷基二甲基铵、氯化二(氢化牛脂)二甲基铵、溴化四庚基铵、溴化四癸基铵、 336及奥芬溴铵(oxyphenonium bromide)。该等烃基优选具有至少10个(例如,10-24个)碳原子(例如,癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基),仅除了当分子包含两个官能化烷基链诸如在氯化二甲基二-十八烷基铵、溴化二甲基二-十六烷基铵及氯化二(氢化牛脂)二甲基铵时,6-20个碳的稍短的烃基(例如,己基、2-乙基己基、十二烷基)为优选。
涵盖的阴离子性表面活性剂包括,但不限于,聚氧亚乙基月桂基醚钠、二己基磺基琥珀酸钠、二环己基磺基琥珀酸钠盐、7-乙基-2-甲基-4-十一烷基硫酸钠(Tergitol 4)、SODOSIL RM02、及磷酸酯含氟表面活性剂诸如Zonyl FSJ。
两性离子表面活性剂包括,但不限于,环氧乙烷烷基胺(AOA-8,Sanyo)、N,N-二甲基十二烷基胺N-氧化物、椰子胺基丙酸钠(sodium cocaminpropinate)(LebonApl-D,Sanyo)、3-(N,N-二甲基肉豆蔻基铵基)丙磺酸盐、及(3-(4-庚基)苯基-3-羟丙基)二甲铵基丙磺酸盐。
在一优选实施方案中,第二方面的移除组合物包含下列成分,由其所组成,或基本上由其所组成:
在第三方面中,描述一种实质上不含氟化物的第二移除组合物,该移除组合物包含至少一种氧化剂、至少一种金属氮化物抑制剂、至少一种蚀刻剂化合物、任选的至少一种表面活性剂、及至少一种溶剂,用于相对于第二金属栅极材料选择性地移除第一金属栅极材料,其中该第二移除组合物实质上不含氟化物。该第二移除组合物优选实质上不移除存在于基板上的其它栅极堆栈材料。在一实施方案中,本发明的第二移除组合物包含下列成分,由其所组成,或基本上由其所组成:至少一种氧化剂、至少一种金属氮化物抑制剂、至少一种蚀刻剂化合物、及至少一种溶剂,其中该第二移除组合物实质上不含氟化物。在另一实施方案中,本发明的移除组合物包含下列成分,由其所组成,或基本上由其所组成:至少一种氧化剂、至少一种金属氮化物抑制剂、至少一种蚀刻剂化合物、至少一种表面活性剂、及至少一种溶剂,其中该第二移除组合物实质上不含氟化物。
该至少一种溶剂可包含水及至少一种选自由式R1R2R3C(OH)化合物所组成的组的可与水相混溶的有机溶剂,其中R1、R2及R3彼此独立且选自由氢、C2-C30烷基、C2-C30烯基、环烷基、C2-C30烷氧基、及其组合所组成的组。举例来说,该至少一种溶剂可包含至少一种选自由下列所组成的组的物质:水、甲醇、乙醇、异丙醇、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、二甘醇单甲醚、三甘醇单甲醚、二甘醇单***、三甘醇单***、乙二醇单丙醚、乙二醇单丁醚、二甘醇单丁醚、三甘醇单丁醚、乙二醇单己醚、二甘醇单己醚、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、2,3-二氢十氟戊烷、乙基全氟丁基醚、甲基全氟丁基醚、碳酸烷基酯、碳酸亚烷基酯、4-甲基-2-戊醇、致密流体、及其组合。该至少一种溶剂优选包含水,最优选为去离子水。
此处涵盖的氧化剂包括,但不限于,臭氧、过氧化氢(H2O2)、过硫酸氢钾制剂、过硫酸氢钾制剂四丁基铵盐、硝酸铁(Fe(NO3)3)、碘酸钾(KIO3)、碘酸(HIO3)、过碘酸(H5IO6)、过锰酸钾(KMnO4)、过锰酸(HMnO4)、氧化铬(III)、硝酸铵铈((NH4)2Ce(NO3)6)、硝酸(HNO3)、亚氯酸铵(NH4ClO2)、氯酸铵(NH4ClO3)、碘酸铵(NH4IO3)、过硼酸铵(NH4BO3)、过氯酸铵(NH4ClO4)、过碘酸铵(NH4IO3)、过硫酸铵((NH4)2S2O8)、过硫酸钠(Na2S2O8)、过硫酸钾(K2S2O8)、亚氯酸四甲铵((N(CH3)4)ClO2)、氯酸四甲铵((N(CH3)4)ClO3)、碘酸四甲铵((N(CH3)4)IO3)、过硼酸四甲铵((N(CH3)4)BO3)、过氯酸四甲铵((N(CH3)4)ClO4)、过碘酸四甲铵((N(CH3)4)IO4)、过硫酸四甲铵((N(CH3)4)S2O8)、尿素过氧化氢((CO(NH2)2)H2O2)、过乙酸(CH3(CO)OOH)、及其组合。该氧化剂优选包括过氧化氢。该氧化剂可于制造处或制造前引入至组合物。当存在氧化剂时,该移除组合物可被进一步补充至少一种酸,包括,但不限于,硫酸、硝酸、乙酸、三氟乙酸、及氢氯酸。
金属氮化物抑制剂优选地抑制第二金属栅极材料相对于第一金属栅极材料的移除,且其包括,但不限于,硼酸、硼酸铵、抗坏血酸、L(+)-抗坏血酸、异抗坏血酸、抗坏血酸衍生物、五倍子酸、二膦酸诸如1-羟亚乙基-1,1-二膦酸(HEDP)、1-羟乙烷-1,1-二膦酸、次氮基三(亚甲基膦酸)(NTMPA)、N,N,N’,N’-乙二胺四(亚甲基膦酸)(EDTMP)、1,5,9-三氮杂环十二烷-N,N’,N”-三(亚甲基膦酸)(DOTRP)、1,4,7,10-四氮杂环十二烷-N,N’,N”,N’”-四(亚甲基膦酸)(DOTP)、二亚乙三胺五(亚甲基膦酸)(DETAP)、氨基三(亚甲基膦酸)、双(六亚甲基)三胺膦酸、1,4,7-三氮杂环壬烷-N,N’,N”-三(亚甲基膦酸)(NOTP)、磷酸的酯;5-氨基-1,3,4-噻二唑-2-硫醇(ATDT)、苯并***(BTA)、柠檬酸、草酸、鞣酸、乙二胺四乙酸(EDTA)、尿酸、1,2,4-***(TAZ)、甲苯***、5-苯基苯并***、5-硝基苯并***、3-氨基-5-巯基-1,2,4-***、1-氨基-1,2,4-***、羟基苯并***、2-(5-氨基戊基)-苯并***、1-氨基-1,2,3-***、1-氨基-5-甲基-1,2,3-***、3-氨基-1,2,4-***、3-巯基-1,2,4-***、3-异丙基-1,2,4-***、5-苯基硫醇-苯并***、卤基苯并***(卤基=F、Cl、Br或I)、萘并***、2-巯基苯并咪唑(MBI)、2-巯基苯并噻唑、4-甲基-2-苯基咪唑、2-巯基噻唑啉、5-氨基四唑、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑烷酮、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、二氨基甲基三嗪、咪唑啉硫酮、巯基苯并咪唑、4-甲基-4H-1,2,4-***-3-硫醇、苯并噻唑、磷酸三甲苯酯、咪唑、吲二唑、苯甲酸、丙二酸、苯甲酸铵、儿茶酚、五倍子酚、间苯二酚、氢醌、氰尿酸、巴比妥酸及衍生物诸如1,2-二甲基巴比妥酸、α-酮酸诸如丙酮酸、腺嘌呤、嘌呤、甘氨酸/抗坏血酸、Dequest 2000、Dequest 7000、对甲苯基硫脲、琥珀酸、膦酰基丁烷三羧酸(PBTCA)、及其组合。其它涵盖的二膦酸包括式I的衍生物,其中R1、R2、R3、R4、R5、R6、R7独立地选自,但不限于,氢、烷基、环烷基、烷氧基,及n是0至20的整数。
在另一实施方案中,金属氮化物抑制剂包含式(R1)(R2)P(=O)(R3)的化合物,其中R1、R2及R3彼此独立且选自由氢、羟基、C1-C30烷基、C2-C30烯基、环烷基、C2-C30烷氧基、或其任何组合所组成的组。在另一实施方案中,金属氮化物抑制剂包含式(R1R2R3R4)NX的化合物,其中R1、R2、R3及R4彼此独立且选自由氢、C1-C30烷基、C2-C30烯基、环烷基、C1-C30烷氧基、C1-C30羧酸酯、或其任何组合所组成的组,且其中X是任何具有-1电荷的阴离子。在另一实施方案中,金属氮化物抑制剂包含式[(R1)(R2)N]C(=O)(CR3R4)nC(=O)[N(R5)(R6)]的化合物,其中R1、R2、R3、R4、R5、及R6彼此独立且选自由氢、C2-C30烷基、C2-C30烯基、环烷基、C2-C30烷氧基、C2-C30羧酸酯、或其任何组合所组成的组,且其中n=1-12的任何整数。在另一实施方案中,金属氮化物抑制剂包含式R1C(=O)(OH)或R1C(=O)(OH)(CH2)n(O=)(HO)CR2的羧酸,其中R1或R2选自C1-C30烷基链或C2-C30烯基链,优选为C1-C20烷基链或C2-C20烯基链,n是介于0与20之间的整数。优选的抑制剂包括下列中的至少之一:癸基膦酸、十二烷基膦酸(DDPA)、十四烷基膦酸、十六烷基膦酸、双(2-乙基己基)磷酸酯、十八烷基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、磷酰基乙酸、十二烷基苯磺酸、十二烯基琥珀酸、二-十八烷基磷酸氢酯、十八烷基磷酸二氢酯、十二烷基胺、十二烯基琥珀酸单二乙醇酰胺、月桂酸、棕榈酸、油酸、桧酸、羟基硬脂酸、十八烷基膦酸(ODPA)、及其组合。金属氮化物抑制剂最优选包含HEDP、十二烷基膦酸、十八烷基膦酸、或其任何组合。
蚀刻剂化合物可包括,但不限于下列的铵盐或四烷基铵盐:氢氧化物、氯化物、硝酸盐、溴化物、碘化物、亚硝酸盐、硫酸盐、亚硫酸盐、乙酸盐、及磷酸盐,其中该四烷基铵阳离子由式[NR1R2R3R4]+表示,其中R1、R2、R3及R4彼此相同或不同且选自由C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)及C6-C10芳基(例如,苄基)所组成的组;氢氧化钾;氢氧化钠;氢氧化锂;氢氧化钙;氢氧化镁;及其组合。蚀刻剂化合物优选包括氢氧化铵。
第二移除组合物所涵盖的表面活性剂包括在本文关于第二方面的移除组合物所揭示的那些。
在本发明的一优选实施方案中,第三方面的第二移除组合物实质上不含研磨剂或其它无机颗粒材料、氟化物、胺、氯化物、金属卤化物、硅酸盐、及其组合。第三方面的第二移除组合物的pH优选在约7至约11的范围内。
在一优选方面中,第三方面的第二移除组合物包含下列成分,由其所组成,或基本上由其所组成:
在一实施方案中,第三方面的第二移除组合物包含氢氧化铵、过氧化氢、硼酸及水,由其所组成,或基本上由其所组成。在另一实施方案中,第三方面的第二移除组合物包含氢氧化铵、过氧化氢、HEDP及水,由其所组成,或基本上由其所组成。
在本发明的另一方面中,文中所述的任何移除组合物可进一步包含溶解的第一金属栅极材料,例如,包含诸如TiN的材料。举例来说,含氟化物的移除组合物可包含下列成分,基本上由其所组成,或由其所组成:至少一种氟化物、至少一种金属氮化物抑制剂、任选的至少一种氧化剂、任选的至少一种表面活性剂、第一金属栅极材料及至少一种溶剂。在另一实施方案中,实质上不含氟化物的第二移除组合物包含下列成分,基本上由其所组成,或由其所组成:至少一种氧化剂、至少一种金属氮化物抑制剂、至少一种蚀刻剂化合物、第一金属栅极材料、任选的至少一种表面活性剂、及至少一种溶剂,其中该第二移除组合物实质上不含氟化物。
当明了一般实践是制造浓缩形式的移除组合物以于使用前稀释。举例来说,可制造呈更浓缩形式的包含至少一种氟化物、至少一种金属氮化物抑制剂、任选的至少一种氧化剂、任选的至少一种表面活性剂的移除组合物,其后再在制造商处、在使用前、和/或在工厂在使用期间用溶剂和/或任选的至少一种氧化剂稀释。在另一实施方案中,移除组合物可包含至少一种氧化剂、至少一种金属氮化物抑制剂、至少一种蚀刻剂化合物、任选的至少一种表面活性剂,及其后在制造商处、在使用前、和/或在工厂在使用期间用溶剂和/或至少一种氧化剂稀释。在另一实施方案中,移除组合物可包含至少一种金属氮化物抑制剂、至少一种蚀刻剂化合物、任选的至少一种表面活性剂,及其后在制造商处、在使用前、和/或在工厂在使用期间用溶剂及至少一种氧化剂稀释。稀释比可在约0.1份稀释剂:1份移除组合物浓缩物至约100份稀释剂:1份移除组合物浓缩物的范围内。
本发明的移除组合物通过简单地添加个别成分及混合至均匀状态而容易地调配得。此外,可轻易地将移除组合物调配为单包装调配物或在使用点处或使用点前混合的多份调配物,优选为多份调配物。可将多份调配物的单独部分于工具处或于混合区域/范围诸如在线混合器或于工具上游的储槽中混合。涵盖多份调配物的各个部分可包含当混合在一起时形成期望移除组合物的成分/组分的任何组合。在本发明的广泛实践中,个别成分的浓度可在移除组合物的特定倍数内广泛地改变,即更稀或更浓,且当明了本发明的移除组合物可变化及替代地包含与本文所公开内容一致的成分的任何组合,由其所组成,或基本上由其所组成。
因此,本发明的另一方面涉及一种套组(kit),其包括存于一个或多个容器中的一种或多种适于形成本发明的组合物的组分。套组优选包括用于在工厂或使用点处与溶剂和/或氧化剂结合的存于一个或多个容器中的至少一种氟化物、至少一种金属氮化物抑制剂、任选的至少一种氧化剂、任选的至少一种表面活性剂。套组的容器视需要可包括用于在工厂或使用点处与溶剂和/或氧化剂结合的至少一种氧化剂、至少一种金属氮化物抑制剂、至少一种蚀刻剂化合物、任选的至少一种表面活性剂。在另一实施方案中,套组的容器可包括用于在工厂或使用点处与溶剂及氧化剂结合的至少一种金属氮化物抑制剂、至少一种蚀刻剂化合物、任选的至少一种表面活性剂。套组的容器必需适于储存及运送该移除组合物,例如,容器(Advanced Technology Materials,Inc.,Danbury,Conn.,USA)。容纳移除组合物的组分的一个或多个容器优选包括用于使该一个或多个容器中的组分流体相通,以进行掺混及配送的构件。举例来说,参照容器,可对该一个或多个容器中的衬里的外侧施加气体压力,以导致衬里的至少一部分的内容物排出,且因此可流体相通而进行掺混及配送。或者,可对公知的可加压容器的顶部空间施加气体压力,或可使用泵以达成流体相通。此外,***优选包括用于将经掺混的清洁组合物配送至加工工具的配送口。
优选使用实质上化学惰性、不含杂质、挠性及回弹性的聚合薄膜材料,诸如高密度聚乙烯,以制造该一个或多个容器的衬里。理想的衬里材料不需要共挤出或障壁层以进行加工,且不含任何会不利影响待置于衬里中的组分的纯度需求的颜料、UV抑制剂、或加工剂。理想衬里材料的清单包括含纯粹(无添加剂)聚乙烯、纯粹聚四氟乙烯(PTFE)、聚丙烯、聚氨基甲酸酯、聚偏二氯乙烯、聚氯乙烯、聚缩醛、聚苯乙烯、聚丙烯腈、聚丁烯等等的薄膜。此等衬里材料的优选厚度在约5密尔(mil)(0.005英寸)至约30密尔(0.030英寸)的范围内,例如,20密尔(0.020英寸)的厚度。
关于套组的容器,将以下专利及专利申请案的揭示内容的各别全体并入本文为参考数据:美国专利第7,188,644号,标题“使超纯液体中的颗粒产生减至最小的装置及方法(APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURELIQUIDS)”;美国专利第6,698,619号,标题“可回收及再利用的桶中袋流体储存及配送容器***(RETURNABLE AND REUSABLE,BAG-IN-DRUM FLUID STORAGE AND DISPENSINGCONTAINER SYSTEM)”;及2007年5月9日以John E.Q.Hughes的名义提出申请的美国专利申请案第60/916,966号,标题“材料掺混及分布用的***及方法(SYSTEMS AND METHODS FORMATERIAL BLENDING AND DISTRIBUTION)”,及2008年5月9日提出申请的PCT/US08/63276,标题“材料掺混及分布用的***及方法(SYSTEMS AND METHODS FOR MATERIAL BLENDINGAND DISTRIBUTION)”。
当应用至微电子制造操作时,文中所述的移除组合物可有效用于自微电子装置的表面相对于第二金属栅极材料选择性地移除第一金属栅极材料,及可在施用经调配用于自装置表面移除另类材料的其它组合物之前或之后应用于该表面。文中所述的移除组合物应相对于第二金属栅极材料选择性地移除第一金属栅极材料,同时不会实质上地移除存在于基板上的其它金属堆栈材料。
在移除应用中,移除组合物以任何适当方式被施加至装置,例如,经由将移除组合物喷涂于装置的表面上,经由将装置浸泡于静态或动态体积的移除组合物中,经由使装置与其上吸收有移除组合物的另一材料(例如,垫、或纤维吸收性涂布器组件)接触,或藉由任何其它藉以使移除组合物与具有第一及第二金属栅极材料的装置进行移除接触的适当手段、方式或技术。此外,此处涵盖批式或单一晶圆加工。
在实现期望的移除作用后,可轻易地将移除组合物自其先前经施用的装置移除(例如,经由冲洗、洗涤、或其它移除步骤),此可能是所需的且有效的。举例来说,装置可用包含去离子水的冲洗溶液冲洗和/或经干燥(例如,旋转干燥、N2、溶剂(诸如IPA)蒸气干燥等)。
本发明的另一方面涉及根据本发明的方法制得的改良的微电子装置,及含有该等微电子装置的产品。
本发明的另一方面涉及制造包含微电子装置的制品的方法,该方法包括使微电子装置与移除组合物接触足够的时间,以自其上具有第一金属栅极材料及第二金属栅极材料的微电子装置相对于第二金属栅极材料选择性地移除第一金属栅极材料,及将该微电子装置并入至该制品中。该移除组合物可包含下列成分,由其所组成,或基本上由其所组成:至少一种氟化物、至少一种金属氮化物抑制剂、任选的至少一种氧化剂、任选的至少一种表面活性剂、及至少一种溶剂。或者,该移除组合物可包含下列成分,由其所组成,或基本上由其所组成:至少一种金属氮化物抑制剂、至少一种蚀刻剂化合物、至少一种氧化剂、任选的至少一种表面活性剂、及至少一种溶剂。
本发明的另一方面涉及一种制造制品,该制品包括微电子装置基板及移除组合物,其中该微电子装置基板包括第一金属栅极材料及第二金属栅极材料,以及其中该移除组合物可为文中所述的任何移除组合物。举例来说,该移除组合物可包含至少一种氟化物、至少一种金属氮化物抑制剂、任选的至少一种氧化剂、任选的至少一种表面活性剂、及至少一种溶剂。或者,该移除组合物可包含至少一种氧化剂、至少一种金属氮化物抑制剂、至少一种蚀刻剂化合物、任选的至少一种表面活性剂、及至少一种溶剂。
本发明的特征及优点由非限制性实施例作更完整说明,其中除非另外明确陈述,否则所有份数及百分比是以重量计的。
实施例1
制备以下组合物。
组合物A:0.6重量%硼酸、25.0重量%三丙二醇甲基醚、29.25重量%四氢呋喃醇、0.1重量%TBA-BF4、0.56重量%氢氟化铵、0.015重量%ATDT、0.3重量%TAZ、44.175重量%水
组合物B:4重量%氢氧化铵、4重量%H2O2(30%)、15重量%HEDP、77重量%水
组合物C:4重量%氢氧化铵、4重量%H2O2(30%)、1重量%硼酸、91重量%水
组合物D:4重量%氢氧化铵、4重量%H2O2(30%)、1重量%HEDP、91重量%水
组合物E:4重量%氢氧化铵、4重量%H2O2(30%)、0.1重量%硼酸、91.9重量%水
组合物F:4重量%氢氧化铵、4重量%H2O2(30%)、8重量%HEDP、84重量%水
组合物G:4重量%氢氧化铵、4重量%H2O2(30%)、10重量%HEDP、82重量%水
组合物H:4重量%氢氧化铵、4重量%H2O2(30%)、2重量%HEDP、90重量%水
组合物I:4重量%氢氧化铵、4重量%H2O2(30%)、4重量%HEDP、88重量%水
组合物J:4重量%氢氧化铵、4重量%H2O2(30%)、6重量%HEDP、86重量%水
组合物K:4重量%氢氧化铵、4重量%H2O2(30%)、0.01重量%硼酸、91.99重量%水
组合物L:0.6重量%硼酸、0.56重量%氢氟化铵、98.84重量%水
组合物M:4重量%氢氧化铵、4重量%H2O2(30%)、5重量%HEDP、87重量%水
组合物N:4重量%氢氧化铵、4重量%H2O2(30%)、92重量%水
将具有氮化钛层的毯覆式晶圆及具有氮化钽层的毯覆式晶圆单独于80℃下的调配物D、H及I、以及对照调配物N中浸泡1分钟。使用光谱椭圆偏振(SE)测定各氮化物的蚀刻速率及结果列表于表1。
表1:TiNx及TaNx在移除组合物中的蚀刻速率
可见当添加至调配物的HEDP的量增加时(例如,自调配物D至H至I),TaNx的蚀刻速率减小而TiNx的蚀刻速率维持不受影响。可见调配物I对于抑制TaNx的蚀刻速率最为有效。虽然不希望受理论所限制,但据认为当HEDP的存在量增加及pH减小时,氧化剂的活性减小且因此TaNx的蚀刻速率减小。
将具有氮化钛层的毯覆式晶圆及具有氮化钽层的毯覆式晶圆单独于40℃下的调配物M、以及对照调配物N中浸泡3分钟。使用SE测定各氮化物的蚀刻速率及结果列表于表2。
表2:TiNx及TaNx在移除组合物中的蚀刻速率
可见HEDP的存在适当地抑制TaNx的蚀刻速率。
虽然本发明已参照说明实施方案及特征以不同方式公开于文中,但当明了前文所述的实施方案及特征并非要限制本发明,且本领域技术人员当可基于本文中的公开内容明白其它的变化、修改及其它实施方案。因此,本发明应被广泛解释为涵盖在权利要求书的精神及范畴内的所有此等变化、修改及另类实施方案。
Claims (24)
1.一种组合物,所述组合物包含:
至少一种蚀刻剂,所述至少一种蚀刻剂含有氢氧化铵或氢氧化物的四烷基铵盐;
至少一种金属氮化物抑制剂,所述至少一种金属氮化物抑制剂选自由下列所组成的组的物质:硼酸、硼酸铵、抗坏血酸、五倍子酸、1-羟亚乙基-1,1-二膦酸、次氮基三(亚甲基膦酸)、1,5,9-三氮杂环十二烷-N,N’,N”-三(亚甲基膦酸)、1,4,7,10-四氮杂环十二烷-N,N’,N”,N’”-四(亚甲基膦酸)、二亚乙三胺五(亚甲基膦酸)、氨基三(亚甲基膦酸)、双(六亚甲基)三胺膦酸、1,4,7-三氮杂环壬烷-N,N’,N”-三(亚甲基膦酸)、磷酸的酯;5-氨基-1,3,4-噻二唑-2-硫醇、苯并***、鞣酸、乙二胺四乙酸、尿酸、1,2,4-***、甲苯***、5-苯基苯并***、5-硝基苯并***、3-氨基-5-巯基-1,2,4-***、1-氨基-1,2,4-***、羟基苯并***、2-(5-氨基戊基)-苯并***、1-氨基-1,2,3-***、1-氨基-5-甲基-1,2,3-***、3-氨基-1,2,4-***、3-巯基-1,2,4-***、3-异丙基-1,2,4-***、5-苯基硫醇-苯并***、卤基苯并***、萘并***、2-巯基苯并噻唑、4-甲基-2-苯基咪唑、2-巯基噻唑啉、5-氨基四唑、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑烷酮、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、二氨基甲基三嗪、咪唑啉硫酮、巯基苯并咪唑、4-甲基-4H-1,2,4-***-3-硫醇、苯并噻唑、咪唑、吲二唑、儿茶酚、五倍子酚、间苯二酚、氢醌、氰尿酸、巴比妥酸、1,2-二甲基巴比妥酸、丙酮酸、嘌呤、甘氨酸/抗坏血酸、对甲苯基硫脲、膦酰基丁烷三羧酸、癸基膦酸、十二烷基膦酸、十四烷基膦酸、十六烷基膦酸、十八烷基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、磷酰基乙酸、十二烷基苯磺酸、十二烯基琥珀酸、十二烷基胺、十二烯基琥珀酸单二乙醇酰胺、月桂酸、棕榈酸、油酸、桧酸、12-羟基硬脂酸、及其组合;
至少一种溶剂;和
至少一种氧化剂,所述至少一种氧化剂以从0.01wt.%至小于10wt.%的量存在,
其中该组合物用于相对于第二金属栅极材料选择性地移除第一金属栅极材料。
2.权利要求1的组合物,其中,该至少一种氧化剂包含选自由下列所组成的组的物质:臭氧、过氧化氢、过硫酸氢钾制剂、过硫酸氢钾制剂四丁基铵盐、硝酸铁、碘酸钾、碘酸、过碘酸、过锰酸钾、过锰酸、氧化铬(III)、硝酸铵铈、硝酸、亚氯酸铵、氯酸铵、碘酸铵、过硼酸铵、过氯酸铵、过碘酸铵、过硫酸铵、过硫酸钠、过硫酸钾、亚氯酸四甲铵、氯酸四甲铵、碘酸四甲铵、过硼酸四甲铵、过氯酸四甲铵、过碘酸四甲铵、过硫酸四甲铵、尿素过氧化氢、过乙酸、及其组合。
3.权利要求1的组合物,其中,该至少一种氧化剂包含过氧化氢。
4.权利要求2或3的组合物,其中,该组合物进一步包含至少一种选自由硫酸、硝酸、乙酸、三氟乙酸及氢氯酸所组成的组的酸。
5.权利要求1的组合物,其中,该至少一种金属氮化物抑制剂包含1-羟亚乙基-1,1-二膦酸。
6.权利要求1的组合物,其中,该至少一种溶剂包含选自由下列所组成的组的物质:水、甲醇、乙醇、异丙醇、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、二甘醇单甲醚、三甘醇单甲醚、二甘醇单***、三甘醇单***、乙二醇单丙醚、乙二醇单丁醚、二甘醇单丁醚、三甘醇单丁醚、乙二醇单己醚、二甘醇单己醚、乙二醇苯基醚、丙二醇甲基醚、二丙二醇甲基醚、三丙二醇甲基醚、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、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、2,3-二氢十氟戊烷、乙基全氟丁基醚、甲基全氟丁基醚、碳酸烷基酯、碳酸亚烷基酯、4-甲基-2-戊醇、及其组合。
7.权利要求1的组合物,其中,该至少一种溶剂包含水。
8.权利要求1的组合物,其中pH在3-7的范围内。
9.权利要求1的组合物,其中pH在7-11的范围内。
10.权利要求1的组合物,其中,该组合物还包含至少一种表面活性剂。
11.权利要求10的组合物,其中,该至少一种表面活性剂选自:癸基膦酸、十二烷基膦酸、十四烷基膦酸、十六烷基膦酸、双(2-乙基己基)磷酸酯、十八烷基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、磷酰基乙酸、十二烷基苯磺酸、十二烷基胺、聚氧亚乙基月桂基醚、十二烯基琥珀酸单二乙醇酰胺、乙二胺四(乙氧化物-嵌段-丙氧化物)四醇、聚氧亚乙基聚氧亚丙基二醇、聚氧亚丙基蔗糖醚、叔-辛基苯氧基聚乙氧乙醇、支链的聚氧亚乙基(9)壬苯基醚、聚氧亚乙基山梨糖醇六油酸酯、聚氧亚乙基山梨糖醇四油酸酯、聚乙二醇脱水山梨糖醇单油酸酯、脱水山梨糖醇单油酸酯、烷基-多葡萄糖苷、全氟丁酸乙酯、1,1,3,3,5,5-六甲基-1,5-双[2-(5-降冰片烯-2-基)乙基]三硅氧烷、Siliclad SIS6952.0、经硅氧烷改性的聚硅氮烷、有机硅-聚醚共聚物、及醇乙氧化物、十七烷氟辛烷磺酸四乙铵、氯化硬脂基三甲铵、溴化4-(4-二乙氨基苯基偶氮)-1-(4-硝基苄基)吡啶鎓、氯化鲸蜡基吡啶鎓单水合物、苯扎氯铵、苄索氯铵、氯化苄基二甲基十二烷基铵、氯化苄基二甲基十六烷基铵、溴化十六烷基三甲基铵、氯化二甲基二-十八烷基铵、氯化十二烷基三甲基铵、对甲苯磺酸十六烷基三甲基铵、溴化二-十二烷基二甲基铵、氯化二(氢化牛脂)二甲基铵、溴化四庚基铵、溴化四癸基铵、奥芬溴铵、聚氧亚乙基月桂基醚钠、二己基磺基琥珀酸钠、二环己基磺基琥珀酸钠盐、7-乙基-2-甲基-4-十一烷基硫酸钠、磷酸酯含氟表面活性剂、环氧乙烷烷基胺、N,N-二甲基十二烷基胺N-氧化物、椰子胺基丙酸钠、3-(N,N-二甲基肉豆蔻基铵基)丙磺酸盐、及(3-(4-庚基)苯基-3-羟丙基)二甲铵基丙磺酸盐。
12.权利要求1-3和5-11中任一项的组合物,其中,该组合物实质上不含研磨剂或其它无机颗粒材料、胺、氯化物、金属卤化物、硅酸盐、及其组合。
13.权利要求4的组合物,其中,该组合物实质上不含研磨剂或其它无机颗粒材料、胺、氯化物、金属卤化物、硅酸盐、及其组合。
14.权利要求1的组合物,其中所述嘌呤是腺嘌呤。
15.权利要求1的组合物,其中所述抗坏血酸是L(+)-抗坏血酸。
16.权利要求1的组合物,其中所述抗坏血酸是异抗坏血酸。
17.权利要求1的组合物,其中所述巯基苯并咪唑是2-巯基苯并咪唑。
18.权利要求1的组合物,其中所述磷酸的酯选自磷酸三甲苯酯、双(2-乙基己基)磷酸酯、二-十八烷基磷酸氢酯和十八烷基磷酸二氢酯。
19.相对于至少第二金属栅极材料选择性地移除第一金属栅极材料的方法,该方法包括使包含该第一金属栅极材料及该第二金属栅极材料的基板与权利要求1-11任一项的组合物接触,其中该组合物相对于该第二金属栅极材料选择性地移除该第一金属栅极材料。
20.权利要求19的方法,其中,该组合物实质上不移除存在于该基板上的其它栅极堆栈材料。
21.权利要求20的方法,其中,该第一金属栅极材料包含钛及该第二金属栅极材料包含钽。
22.权利要求20或21的方法,其中,该第一金属栅极材料是第一金属氮化物及该第二金属栅极材料是第二金属氮化物。
23.权利要求20或21的方法,其中,该第一金属栅极材料是氮化钛及该第二金属栅极材料是氮化钽。
24.权利要求20或21的方法,其中,利用冲洗溶液自该基板冲洗该组合物。
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US9831088B2 (en) | 2017-11-28 |
WO2012048079A2 (en) | 2012-04-12 |
WO2012048079A3 (en) | 2012-06-28 |
KR20130139278A (ko) | 2013-12-20 |
TW201221627A (en) | 2012-06-01 |
KR20180016619A (ko) | 2018-02-14 |
KR101827031B1 (ko) | 2018-02-07 |
CN103154321A (zh) | 2013-06-12 |
SG10201508015RA (en) | 2015-10-29 |
KR101868319B1 (ko) | 2018-06-15 |
TWI619800B (zh) | 2018-04-01 |
CN103154321B (zh) | 2015-11-25 |
US20140038420A1 (en) | 2014-02-06 |
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