JP6503102B2 - 窒化チタンハードマスク及びエッチ残留物除去 - Google Patents
窒化チタンハードマスク及びエッチ残留物除去 Download PDFInfo
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- JP6503102B2 JP6503102B2 JP2018036368A JP2018036368A JP6503102B2 JP 6503102 B2 JP6503102 B2 JP 6503102B2 JP 2018036368 A JP2018036368 A JP 2018036368A JP 2018036368 A JP2018036368 A JP 2018036368A JP 6503102 B2 JP6503102 B2 JP 6503102B2
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- acid
- ammonium
- titanium nitride
- tin
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims description 38
- 239000000203 mixture Substances 0.000 claims description 200
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- 239000003112 inhibitor Substances 0.000 claims description 36
- 230000007797 corrosion Effects 0.000 claims description 34
- 238000005260 corrosion Methods 0.000 claims description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 150000002978 peroxides Chemical class 0.000 claims description 31
- 150000001412 amines Chemical class 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 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 17
- 239000003989 dielectric material Substances 0.000 claims description 16
- 150000007524 organic acids Chemical class 0.000 claims description 14
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 14
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 14
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 14
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 claims description 14
- 239000002738 chelating agent Substances 0.000 claims description 13
- 150000003863 ammonium salts Chemical class 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000012964 benzotriazole Substances 0.000 claims description 10
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- LBOQZDCAYYCJBU-UHFFFAOYSA-N 4-methyl-2h-benzotriazole;5-methyl-2h-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21.CC1=CC=CC2=NNN=C12 LBOQZDCAYYCJBU-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002516 radical scavenger Substances 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 229940075419 choline hydroxide Drugs 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004377 microelectronic Methods 0.000 claims description 6
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-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
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 3
- CWIYBOJLSWJGKV-UHFFFAOYSA-N 5-methyl-1,3-dihydrobenzimidazole-2-thione Chemical compound CC1=CC=C2NC(S)=NC2=C1 CWIYBOJLSWJGKV-UHFFFAOYSA-N 0.000 claims description 3
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 239000001741 Ammonium adipate Substances 0.000 claims description 3
- 239000004251 Ammonium lactate Substances 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019293 ammonium adipate Nutrition 0.000 claims description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229940059265 ammonium lactate Drugs 0.000 claims description 3
- 235000019286 ammonium lactate Nutrition 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- FRRMMWJCHSFNSG-UHFFFAOYSA-N diazanium;propanedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC([O-])=O FRRMMWJCHSFNSG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229960003540 oxyquinoline Drugs 0.000 claims description 3
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 3
- 229940081066 picolinic acid Drugs 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 3
- 229940035024 thioglycerol Drugs 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003796 beauty Effects 0.000 claims 2
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 claims 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- DORQJWCVGBHIGB-UHFFFAOYSA-N azane;2-(carboxymethylamino)acetic acid Chemical compound [NH4+].OC(=O)CNCC([O-])=O DORQJWCVGBHIGB-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 34
- 239000002184 metal Substances 0.000 description 33
- 239000010949 copper Substances 0.000 description 32
- 238000005229 chemical vapour deposition Methods 0.000 description 25
- 239000004094 surface-active agent Substances 0.000 description 25
- 150000003839 salts Chemical class 0.000 description 24
- 238000004140 cleaning Methods 0.000 description 19
- 239000000654 additive Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- -1 organic acid salt Chemical class 0.000 description 16
- 238000005530 etching Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical class CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical class CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 12
- 235000012431 wafers Nutrition 0.000 description 12
- 229920002873 Polyethylenimine Polymers 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 229940093915 gynecological organic acid Drugs 0.000 description 10
- 235000005985 organic acids Nutrition 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 10
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical class CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 9
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 9
- 239000001393 triammonium citrate Substances 0.000 description 9
- 235000011046 triammonium citrate Nutrition 0.000 description 9
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical class CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 8
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 7
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 7
- 125000005210 alkyl ammonium group Chemical group 0.000 description 7
- 239000003125 aqueous solvent Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 238000001039 wet etching Methods 0.000 description 5
- 239000000337 buffer salt Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000007979 citrate buffer Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 3
- 229910021654 trace metal Inorganic materials 0.000 description 3
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 2
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- OEDPMSDASHAOCT-UHFFFAOYSA-N diazanium;2-(carboxylatomethylamino)acetate Chemical compound [NH4+].[NH4+].[O-]C(=O)CNCC([O-])=O OEDPMSDASHAOCT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- OTRUYRHKOCXYTI-UHFFFAOYSA-N C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CCCCCCC)[NH3+].C(CCCCCCC)[NH3+].C(CCCCCCC)[NH3+] Chemical compound C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CCCCCCC)[NH3+].C(CCCCCCC)[NH3+].C(CCCCCCC)[NH3+] OTRUYRHKOCXYTI-UHFFFAOYSA-N 0.000 description 1
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 244000208734 Pisonia aculeata Species 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000005380 borophosphosilicate glass Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
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- GQZXNSPRSGFJLY-UHFFFAOYSA-M dioxidophosphate(1-) Chemical compound [O-]P=O GQZXNSPRSGFJLY-UHFFFAOYSA-M 0.000 description 1
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- 238000007323 disproportionation reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical class [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 239000005360 phosphosilicate glass Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/16—Organic compounds
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- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/30—Amines; Substituted amines ; Quaternized amines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/3947—Liquid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
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- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their composition, e.g. multilayer masks, materials
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- 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
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- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
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- 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
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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Description
本出願は、合衆国法典第35巻119条(e)項の下で、2015年5月1日に出願された先の出願である米国特許出願第62/155794号、2015年5月20日に出願された先の出願である米国特許出願第62/164293号、及び2016年1月21日に出願された先の出願である米国特許出願第62/281658号の優先権の利益を主張し、これらの出願の開示は参照することにより、本明細書に含まれる。
本発明では、ハードマスク層並びに、エッチ残留物を、存在する金属導体層及び低−k誘電体層に対して選択的に除去/エッチングするための組成物、システム及びプロセスを提供する。より具体的には、本発明は、PVD窒化チタンハードマスク並びに/又はエッチ残留物を、銅(Cu)、コバルト(Co)、金属ライナー層若しくは接着層に使用されるCVD窒化チタン、TEOS、PETEOSのような誘電体材料、及び低−k誘電体層に対して、選択的に除去/エッチングするための組成物、システム及びプロセスに関連する。
1〜20wt%の過酸化物、
1〜5wt%の塩基、
0.1〜1wt%の弱酸、
0.5〜2wt%のアンモニウム塩、
25〜5000ppmの腐食防止剤又は1〜15wt%の長鎖若しくは混合水酸化アルキルアンモニウム、
10〜5000ppmの長鎖有機アミン又はポリアルキルアミン、及び
残部は溶媒
を含み、7〜11.5、好ましくは8〜10.5、より好ましくは8.5〜9.5のpHを有し、かつ、第2の材料がCVD窒化チタンである場合に、2より大きいCVD窒化チタンに対するPVD窒化チタンの除去/エッチ選択性を示す。
PVD窒化チタンと、Cu、Co、CVD窒化チタン、誘電体材料、低−k誘電体材料及びそれらの組み合わせをから選択される第2の材料とを含む半導体デバイスと、
窒化チタンを半導体デバイスから選択的に除去するための組成物であって、
1〜20wt%の過酸化物、
1〜5wt%の塩基、
0.1〜1wt%の弱酸、
0.5〜2wt%のアンモニウム塩、
25〜5000ppmの腐食防止剤又は1〜15wt%の長鎖若しくは混合水酸化アルキルアンモニウム、
10〜5000ppmの長鎖有機アミン又はポリアルキルアミン、及び
残部は溶媒
を含む組成物とを含み、その組成物が、7〜11.5、好ましくは8〜10.5、より好ましくは8.5〜9.5のpHを有し、かつ、PVD窒化チタン及び第2の材料がその組成物と直接接触しているシステムである。
PVD窒化チタンと、Cu、Co、CVD窒化チタン、誘電体材料、低−k誘電体材料から選択される第2の材料とを含む半導体デバイスを提供する工程、
その半導体デバイスを組成物に接触させる工程であって、その組成物が
1〜20wt%の過酸化物、
1〜5wt%の塩基、
0.1〜1wt%の弱酸、
0.5〜2wt%のアンモニウム塩、
25〜5000ppmの腐食防止剤又は1〜15wt%の長鎖若しくは混合水酸化アルキルアンモニウム、
10〜5000ppmの長鎖有機アミン若しくはポリアルキルアミン及び/又は長鎖有機酸、並びに
残部は溶媒
を含み、7〜11.5、好ましくは8〜10.5、より好ましくは8.5〜9.5のpHを有する、半導体デバイスを組成物に接触させる工程、及び
PVD窒化チタンを選択的に除去する工程を含み、
PVD窒化チタン及び第2の材料が組成物と直接接触しており、かつ、第2の材料がCVD窒化チタンである場合に、CVD窒化チタンに対するPVD窒化チタンの除去選択性が2より大きいプロセスである。
1.高速のPVD TiNエッチが、35〜55℃の範囲の適温で測定される。プラズマエッチ残留物は、パターンウエハから容易に除去される。
2.Cuエッチ速度は、新規の腐食防止剤、例えば、メチルベンゾトリアゾール/TTLを加えることで抑制される。あるいはまた、Cuエッチ速度は、新規の非腐食防止剤タイプの化学添加剤、例えば、嵩高水酸化トリメチルフェニルアンモニウムを使用することで抑制することができる。
3.ライナー層又は接着層に使用されるCVD TiNに対してのハードマスクに使用されるPVD TiNのエッチ選択性は、嵩高有機アミン、例えば、オクチルアミン又はポリエチレンイミンを使用して有意に改善することができる。
4.Coエッチ速度は、長鎖有機酸又はアミン、例えば、デカン酸を加えることでさらに抑制することができる。
特定量のクエン酸及びクエン酸三アンモニウムを秤量し、ビーカー中のDI水に溶解してクエン酸緩衝溶液を得た。TEAH(35%)をそのクエン酸緩衝溶液中にゆっくり加えた。次いで、メチル−1H−ベンゾトリアゾールを、EDTA及びPEI溶液と一緒にその溶液中に加えた。もしスルホランを加える場合は、この時点で加えることができた。その溶液を撹拌して、メチル−1H−ベンゾトリアゾール及びEDTAを溶解した。オクチルアミンをこの時点で原液のまま加えることができ、又は水に溶解したクエン酸オクチルアンモニウム塩として加えることができた。H2O2をその溶液に加えた。その溶液を均一に混合した。全ての工程は室温で実施した。
組成物E21334−136I、E61412−106Q、E61412−106R、E61412−107C、及びE61412−107Kを調製して、それらを表1に示した。
組成物E61412−106U、及びE61412−106U2を調製して、それらを表2に示した。両組成物は、同量の水酸化アンモニウム、クエン酸三アンモニウム、TTL、H2O2、EDTA、TEAH、分子量10000を持つPEI、及びDI水を含有していた。2つの組成物の唯一の相違点は、E61412−106U2に0.1wt%のデカン酸を使用したことであった。表2のデータは、必要なグラム数で示した。
組成物E21334−193I、E21334−193K、E21334−193L、E21334−193M、E21334−193Nを調製して、それらを表3に示した。表3のデータを必要なグラム数で示した。
表5に示される組成物e21334−111及びe21334−111Sを、以下の工程にしたがって調製した。
組成物e21334−111SのTiN除去能力及び洗浄性能を表6に示した。
図2は、60℃での時間に対する過酸化水素濃度及びpHのプロットを示している。そのプロットは、e21334−111S組成物の安定性を示した。
Cu腐食防止剤を使用した組成物及び使用しない組成物を、表7に示した。組成物e21334−106Rとe21334−106Sの間の相違点は、e21334−106Sがチオグリセロールを有することであった。組成物e21334−107Aとe21334−107Xの間の相違点は、e21334−107Xがメチル−1H−ベンゾトリアゾール(TTL)を有することであった。
表8(a−c)のデータは、TiN及びCuエッチ速度に対しての、組成物のpHを7〜10.4に変更したことによる影響を示している。表8(a−c)の組成物はまた、異なる濃度のH2O2を有していた。
緩衝剤としてクエン酸三アンモニウムを含有する組成物及び含有しない組成物の両方を表9に示した。
e21334−111S組成物が、これらの組成物による遅い(<1Å/分)銅のエッチングからでさえ生じた金属不純物、例えば、微量濃度の銅イオンに曝露すると、組成物中の過酸化水素はすぐに酸素ガスと水に分解した。過酸化物の分解により、洗浄性能及びTiNエッチ速度が害される。
ベンゾトリアゾール(BAT)及びその誘導体は、Cu腐食防止剤として使用することができる。それらの腐食防止剤は、更なる腐食から金属を保護するCu−BATの靱性被膜を形成することができる。しかしながら、そのCu−BATの靱性被膜は、電気試験測定中に高い抵抗を生み出す可能性が高い。
本発明の1つの実施形態では、組成物を排水モードで使用する場合があり、すなわち、化学成分をシングルウエハツールのウエハ上に分配し、次いで処分する。この運転モードでは、再利用モード運転よりも極めて希薄な濃度のキレート剤の使用が可能となる。
本発明の別の実施形態では、組成物を再利用モードで使用する場合があり、その場合、化学成分をウエハ上に供給し、次いで、再循環下で貯蔵タンクに戻す。このモードにおいては、化学成分を多くのウエハを洗浄するために効果的に再利用することができる。
様々なアンモニウム緩衝塩を含有する組成物を開発して、それらを表13に示した。組成物のエッチ速度(Å/分)性能をまた、表13に示した。このデータは、組成物中にアンモニウムのカチオンが存在することが、高いTiNエッチ速度及び良好なTiNハードマスク除去を達成するために重要であることを示した。表13によると、過酸化物は水に30%で溶解している。
クエン酸三アンモニウム(TAC)以外に、ECP Cleanを含有する組成物を調製して、それらを表14及び表15に示した。
有機溶媒のスルホラン及びジプロピレングリコールメチルエーテルを含有する組成物を調製して、それらを表16に示した。
Claims (22)
- PVD窒化チタンと、Cu、Co、CVD窒化チタン、誘電体材料、低−k誘電体材料、及びそれらの組み合わせからなる群より選択される第2の材料とを含む半導体デバイスから、PVD窒化チタン(TiN又はTiNxOy、x=0〜1.3かつy=0〜2)を選択的に除去するための組成物であって、
1〜20wt%の過酸化物、
1〜5wt%の塩基、
0.1〜1wt%の弱酸、
0.5〜2wt%のアンモニウム塩、
25〜5000ppmの腐食防止剤又は1〜15wt%の、水酸化トリメチルフェニルアンモニウム(TMPAH)、水酸化コリン、水酸化テトラブチルアンモニウム及びそれらの組み合わせからなる群より選択される長鎖若しくは混合水酸化アルキルアンモニウム、並びに
溶媒
を含み、7〜11.5のpHを有する組成物。 - 前記過酸化物が、過酸化水素、過硫酸アンモニウム、過酢酸、ペルオキシ安息香酸、及びそれらの組み合わせからなる群より選択される、請求項1に記載の組成物。
- 前記塩基が、水酸化テトラエチルアンモニウム(TEAH)、水酸化トリメチルフェニルアンモニウム、水酸化テトラメチルアンモニウム、水酸化テトラブチルアンモニウム、水酸化コリン、水酸化アンモニウム、及びそれらの組み合わせからなる群より選択される、請求項1に記載の組成物。
- 前記弱酸が、クエン酸、シュウ酸、マロン酸、乳酸、アジピン酸、酢酸、イミノ二酢酸、及びそれらの組み合わせからなる群より選択されるカルボン酸である、請求項1に記載の組成物。
- 前記アンモニウム塩が、クエン酸アンモニウム、酢酸アンモニウム、マロン酸アンモニウム、アジピン酸アンモニウム、乳酸アンモニウム、イミノ二酢酸アンモニウム、塩化アンモニウム、臭化アンモニウム、フッ化アンモニウム、二フッ化アンモニウム、硫酸アンモニウム、及びそれらの組み合わせからなる群より選択される、請求項1に記載の組成物。
- 前記腐食防止剤が、1,2,4−トリアゾール、ベンゾトリアゾール、メチル−1H−ベンゾトリアゾール、2−アミノベンゾチアゾール、ベンズイミダゾール、2−メルカプト−5−メチルベンズイミダゾール、8−ヒドロキシキノリン、1−チオグリセロール、アスコルビン酸、ピラゾール、及びそれらの組み合わせからなる群より選択される、請求項1に記載の組成物。
- 前記溶媒が、脱イオン水(DI水)、精製水、蒸留水、ジメチルスルホキシド(DMSO)、ジメチルスルホン(DMSO2)、スルホラン((CH2)4SO2)、n−メチルピロリドン、ジプロピレングリコールメチルエーテル、トリプロピレングリコールメチルエーテル、及びそれらの組み合わせからなる群より選択される、請求項1に記載の組成物。
- グリシン、イミノ二酢酸、ニトリロ三酢酸、グルタミン酸、ピコリン酸、エチレンジアミン四酢酸(EDTA)、及びそれらの組み合わせからなる群より選択される0.01〜1wt%のキレート剤、
マンニトール、ポリアルキルアミン、(2,2,6,6−テトラメチルピペリジン−1−イル)オキシル(TEMPO)、ジフェニルアミン、及びそれらの組み合わせからなる群より選択される100〜1000ppmのラジカル消去剤、並びに
10〜5000ppmの有機酸又はアミン
からなる群より選択される少なくとも1つをさらに含む、請求項1に記載の組成物。 - 前記有機酸が、デカン酸、ドデカン酸、ダイマー酸、及びそれらの組み合わせからなる群より選択される、請求項8に記載の組成物。
- 前記組成物が、過酸化水素、水酸化テトラエチルアンモニウム、クエン酸、クエン酸アンモニウム、メチル−1H−ベンゾトリアゾール、及び水を含む、請求項1に記載の組成物。
- 前記組成物が、エチレンジアミン四酢酸(EDTA)をさらに含む、請求項10に記載の組成物。
- 前記組成物が、過酸化水素、水酸化テトラエチルアンモニウム、クエン酸、クエン酸アンモニウム、水酸化トリメチルフェニルアンモニウム(TMPAH)、及び水を含む、請求項1に記載の組成物。
- 前記組成物が、エチレンジアミン四酢酸(EDTA)をさらに含む、請求項12に記載の組成物。
- 前記組成物が、過酸化水素、水酸化テトラエチルアンモニウム、クエン酸、クエン酸アンモニウム、ベンゾトリアゾール、及び水を含む、請求項1に記載の組成物。
- 前記組成物が、エチレンジアミン四酢酸(EDTA)をさらに含む、請求項14に記載の組成物。
- 前記過酸化物が約3〜約15wt%で存在する、請求項1に記載の組成物。
- 前記pHが8〜10.5である、請求項1に記載の組成物。
- 2より大きい前記第2の材料に対するPVD窒化チタンの除去選択性を示す、請求項1に記載の組成物。
- 前記過酸化物が1〜9wt%で存在する、請求項1に記載の組成物。
- 前記過酸化物が約15wt%で存在する、請求項1に記載の組成物。
- マイクロ電子デバイスの表面からPVD窒化チタン(TiN又はTiNxOy、x=0〜1.3かつy=0〜2)を選択的に除去するためのシステムであって、
前記PVD窒化チタンと、Cu、Co、CVD窒化チタン、誘電体材料、低−k誘電体材料及びそれらの組み合わせから選択される第2の材料とを含む半導体デバイスと、
請求項1〜20のいずれか1項に記載の組成物と
を含み、前記PVD窒化チタン及び前記第2の材料が前記組成物と直接接触しているシステム。 - PVD窒化チタン(TiN又はTiNxOy、x=0〜1.3かつy=0〜2)を選択的に除去するプロセスであって、
前記PVD窒化チタンと、Cu、Co、CVD窒化チタン、誘電体材料、低−k誘電体材料から選択される第2の材料とを含む半導体デバイスを提供する工程、
前記半導体デバイスを請求項1〜20のいずれか1項に記載の組成物に接触させる工程、並びに
前記PVD窒化チタンを選択的に除去する工程を含み、
前記PVD窒化チタン及び前記第2の材料が前記組成物と直接接触しており、かつ、前記第2の材料がCVD窒化チタンである場合に、前記組成物が、2より大きいCVD窒化チタンに対するPVD窒化チタンの除去選択性を示すプロセス。
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CN108121149B (zh) | 2021-11-30 |
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US9976111B2 (en) | 2018-05-22 |
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