CN105874568A - 用于从包含低介电常数介电材料和铜的半导体设备基板选择性移除金属硬遮罩和其它残留物的方法和组合物 - Google Patents
用于从包含低介电常数介电材料和铜的半导体设备基板选择性移除金属硬遮罩和其它残留物的方法和组合物 Download PDFInfo
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- CN105874568A CN105874568A CN201480055154.9A CN201480055154A CN105874568A CN 105874568 A CN105874568 A CN 105874568A CN 201480055154 A CN201480055154 A CN 201480055154A CN 105874568 A CN105874568 A CN 105874568A
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- 239000000203 mixture Substances 0.000 title claims abstract description 200
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000004065 semiconductor Substances 0.000 title claims abstract description 31
- 239000000758 substrate Substances 0.000 title claims abstract description 30
- 239000010949 copper Substances 0.000 title claims description 69
- 229910052802 copper Inorganic materials 0.000 title claims description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 22
- 229910052751 metal Inorganic materials 0.000 title claims description 20
- 239000002184 metal Substances 0.000 title claims description 20
- 239000003989 dielectric material Substances 0.000 title claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000005530 etching Methods 0.000 claims abstract description 41
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 25
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 50
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 230000001590 oxidative effect Effects 0.000 claims description 20
- 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 18
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 12
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 12
- 150000001413 amino acids Chemical class 0.000 claims description 11
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 10
- 239000004251 Ammonium lactate Substances 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 10
- 229940059265 ammonium lactate Drugs 0.000 claims description 10
- 235000019286 ammonium lactate Nutrition 0.000 claims description 10
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 10
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000001393 triammonium citrate Substances 0.000 claims description 9
- 235000011046 triammonium citrate Nutrition 0.000 claims description 9
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 claims description 8
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000005695 Ammonium acetate Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229940043376 ammonium acetate Drugs 0.000 claims description 8
- 235000019257 ammonium acetate Nutrition 0.000 claims description 8
- 229940090948 ammonium benzoate Drugs 0.000 claims description 8
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 claims description 8
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 claims description 7
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 5
- JGDFPHKQQFLDRY-UHFFFAOYSA-N [NH4+].[NH4+].CC(O)=O.CC(O)=O.CC([O-])=O.CC([O-])=O.NCCN Chemical class [NH4+].[NH4+].CC(O)=O.CC(O)=O.CC([O-])=O.CC([O-])=O.NCCN JGDFPHKQQFLDRY-UHFFFAOYSA-N 0.000 claims description 5
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical group [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 5
- 229960003330 pentetic acid Drugs 0.000 claims description 5
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 4
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 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
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 claims description 3
- YUUVAZCKXDQEIS-UHFFFAOYSA-N azanium;chlorite Chemical compound [NH4+].[O-]Cl=O YUUVAZCKXDQEIS-UHFFFAOYSA-N 0.000 claims description 3
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 3
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 3
- TVWHTOUAJSGEKT-UHFFFAOYSA-N chlorine trioxide Chemical compound [O]Cl(=O)=O TVWHTOUAJSGEKT-UHFFFAOYSA-N 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- FDXKBUSUNHRUIZ-UHFFFAOYSA-N chlorous acid tetramethylazanium Chemical compound C[N+](C)(C)C.Cl(=O)O FDXKBUSUNHRUIZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000267 glycino group Chemical group [H]N([*])C([H])([H])C(=O)O[H] 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- HLQAWDQQEJSALG-UHFFFAOYSA-N periodic acid tetramethylazanium Chemical compound C[N+](C)(C)C.I(=O)(=O)(=O)O HLQAWDQQEJSALG-UHFFFAOYSA-N 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002305 electric material Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 claims description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims 2
- LUVHDTDFZLTVFM-UHFFFAOYSA-N chloric acid tetramethylazanium Chemical compound C[N+](C)(C)C.Cl(=O)(=O)O LUVHDTDFZLTVFM-UHFFFAOYSA-N 0.000 claims 2
- ZCWKIFAQRXNZCH-UHFFFAOYSA-N perchloric acid;tetramethylazanium Chemical compound C[N+](C)(C)C.OCl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-N 0.000 claims 2
- 229910001128 Sn alloy Inorganic materials 0.000 claims 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- -1 carboxylate compound Chemical class 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 description 22
- 230000008569 process Effects 0.000 description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 13
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 11
- 239000012634 fragment Substances 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 9
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 9
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 150000007942 carboxylates Chemical class 0.000 description 7
- 239000002738 chelating agent Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000006184 cosolvent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
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- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229960004643 cupric oxide Drugs 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- UUEDINPOVKWVAZ-UHFFFAOYSA-N bis(2-ethylhexyl) 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OCC(CC)CCCC UUEDINPOVKWVAZ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
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- 229910052737 gold Inorganic materials 0.000 description 2
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- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
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- 239000013522 chelant Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 238000001020 plasma etching Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002510 pyrogen Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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Classifications
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts 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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- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
-
- 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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- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- 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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- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/34—Alkaline compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract
本发明公开了具有2至14范围内的pH的含水移除组合物和用于从半导体基板相对于低介电常数材料选择性移除基本上由TiN、TaN、TiNxOy、TiW、W、或者Ti或W的合金组成的蚀刻遮罩的方法,所述半导体基板包含所述低介电常数材料,所述低介电常数材料在其上具有TiN、TaN、TiNxOy、TiW、W、或者Ti或W的合金的蚀刻遮罩,其中所述移除组合物包含至少一种氧化剂和羧酸盐化合物。
Description
相关申请的交叉引用/声明以引用的方式并入
本申请要求2013年10月11日提交的美国临时申请系列号61/889,968的权益,据此将其全部内容以引用方式并入本文。
背景技术
本发明公开的受权利要求书保护的一个或多个发明概念涉及用于从集成电路(IC)设备基板选择性移除金属硬遮罩和其它残留物的组合物和方法,并且更具体地,涉及使用羧酸盐化合物,可用于从包含低介电常数介电材料TEOS、铜、钴、和其它低介电常数介电材料的此类基板选择性移除TiN、TaN、TiNxOy、TiW、和W金属硬遮罩、和包含上述物质的合金的金属硬遮罩、以及其它残留物的组合物和方法。
临界尺寸为约90纳米(nm)的设备已涉及铜导体与低介电常数电介质的整合,并且它们需要交替材料沉积工艺和极化工艺。等离子干蚀刻常用于在铜(Cu)/低介电常数双镶嵌制造工艺中制造垂直侧壁沟槽和各向异性互连通路。随着技术节点发展至45nm及更小,半导体设备尺寸的缩小使得达到通路与沟槽的精准轮廓控制更具挑战性。集成电路设备公司正在研究利用各种金属硬遮罩来改善对低介电常数材料的蚀刻选择性,从而获得更佳的轮廓控制。
为了获得高良率和低阻抗,在进行下一个工艺步骤之前,蚀刻期间产生在侧壁上的聚合物残留物和通路底部处的颗粒/聚合物残留物必须被移除。如果清洁溶液也可有效蚀刻金属硬遮罩以形成中间形态例如拉回/修圆形态,或者完全移除金属硬遮罩,则将非常有利。拉回/修圆形态可避免底切硬遮罩,这继而可使阻隔金属、Cu晶种层和Cu填充能够可靠沉积。另选地,使用相同组合物完全移除金属硬遮罩可通过消除对阻隔化学机械抛光(CMP)的需要而向下游工艺步骤(尤其是CMP)提供许多有益效果。
几乎制造进程中的每一个步骤(例如平面化步骤、光刻步骤或蚀刻步骤)之后,均需要清洁制程,以移除等离子蚀刻、光致抗蚀剂、氧化剂、研磨物、金属和/或其它液体或颗粒的残留物,该其它液体或颗粒残留下来并且如果未将它们有效移除,则它们可能污染设备的表面。制造需要铜导体和低介电常数介电材料(通常为碳掺杂的氧化硅(SiOCH),或多孔低介电常数材料)的近代设备带来了以下问题,即这两种材料可与各种类型的现有技术清洁剂反应并且受其损伤。
低介电常数电介质尤其可能在清洁制程中受损,表现出蚀刻、孔隙率/尺寸变化,以及介电特性的最终变化。移除残留物所需的时间取决于残留物的性质、产生残留物的制程(加热、交联、蚀刻、焙烧和/或灰化)、以及可否使用批量或单一晶片清洁制程。一些残留物可在非常短的时间段内被清除,而一些残留物需要远远更长的清洁制程。在与清洁剂接触的持续期间内,与低介电常数电介质以及铜导体二者的相容性是期望的特性。
在后段(BEOL)IC制程(即双镶嵌制程)期间,在形成通路和沟槽时使用TiN、TaN、TiNxOy、TiW、和/或W(包括Ti和W的合金)作为蚀刻硬遮罩,以在干蚀刻步骤期间获得对低介电常数介电材料的高选择性。需要有效的清洁组合物,所述清洁组合物可选择性移除TiN、TaN、TiNxOy、TiW、或W,与低介电常数材料、铜、钴以及其它介电材料相容,并且还从所得的双镶嵌结构同时移除非期望的蚀刻残留物和Cu氧化物。除了选择性清洁外,还高度期望清洁组合物可实现的移除速率()长时间内保持基本上恒定。
随着设备临界尺寸的持续缩小以及对于高生产效率与可靠设备性能的相应要求,需要此类改善的清洁组合物。
发明内容
本发明公开的并且受权利要求书保护的一个或多个发明概念涉及具有一种或多种羧酸盐化合物的改善的半导体处理组合物即湿式清洁化合物或移除组合物,其提供从双镶嵌结构高选择性移除金属硬遮罩,而不损伤布线冶金和介电材料。此类在双镶嵌后段金属化中制造的半导体基板由多层或多级金属互连组成,所述金属互连由中间层电介质隔离。所述组合物可从通路和沟槽表面移除金属硬遮罩蚀刻残留物、光致抗蚀剂、聚合物材料、和氧化铜,而不会损伤形成结构的下面层。所述基板通常包含铜、钴,一种或多种低介电常数介电材料SiON、SiCN、TEOS,以及选自TiN、TaN、TiNxOy、TiW、和W(包括Ti和W的合金)的金属硬遮罩。所述移除组合物包含0.1重量%至90重量%的至少一种氧化剂、0.0001重量%至50重量%的羧酸盐化合物,以及补足100重量%移除组合物的剩余部分,包括水例如去离子水。
根据本文所述的一个或多个发明概念被发现获得优异结果的羧酸盐化合物是羧酸铵。羧酸铵的示例为草酸铵、乳酸铵、酒石酸铵、柠檬酸三铵、乙酸铵、氨基甲酸铵、碳酸铵、苯甲酸铵、EDTA四铵、乙二胺四乙酸二铵盐、琥珀酸铵、甲酸铵、1-H-吡唑-3-甲酸铵、以及它们的混合物。本发明的移除组合物中存在羧酸铵化合物,不仅如下文实例中所示提高TiN蚀刻速率,而且数据还支持它们的存在也可用于长时间(例如达至少35小时)内使可达到的TiN蚀刻速率稳定的结论。
虽然金属抗蚀剂对于实施本发明而言不是必需的,但在例如所述组合物待用于BEOL应用的半导体处理以及关注铜或其它金属组分的腐蚀的其它应用中时,至少一种抗蚀剂也可存在于所述组合物中。
所述组合物还可包含碱,所述碱选自例如季铵盐诸如四甲基氢氧化铵(TMAH)、四乙基氢氧化铵(TEAH)、和苄基三甲基氢氧化铵(BTAH)、以及它们的混合物。所述碱也可选自伯胺、仲胺或叔胺,诸如例如单乙醇胺(MEA)、二甘醇胺(DGA)、三乙醇胺(TEA)、和四丁基氢氧化(TBPH)、以及它们的混合物。此外,所述组合物可按需要包含一种或多种酸,例如无机酸诸如硫酸、硝酸、磷酸、氢氟酸(HF)、或氢溴酸,或有机酸诸如羧酸、羟基羧酸、多羧酸、氨基酸、或此类酸的混合物,以将工作组合物的pH值调节至2至14,但优选3至13的范围内的值。在一个优选的实施例中,就涉及Cu互连制造的应用而言,移除组合物的pH优选在7至12的范围内。
所述组合物还可包含0.001重量%至20重量%的氨基酸、胺多羧酸(即氨基多羧酸)、和/或羧酸、多羧酸螯合剂、或它们的混合物,已观察到,其与羧酸盐化合物一起使所述组合物稳定。本文使用术语“稳定”意指可达到的硬遮罩蚀刻速率(例如的TiN移除速率)在长时间内维持基本上恒定,例如在选定的操作温度下例如在50℃的操作温度下,二十二(22)小时至三十五(35)小时或更长的时间段。
适于实施本发明概念的氧化剂可选自过氧化氢(H2O2)、过氧化苯甲酰、过氧单硫酸四丁铵、臭氧、n-甲基吗啉氧化物(NMMO,NMO)、氯化铁、高锰酸盐、过硼酸盐、高氯酸盐、过硫酸盐、过氧二硫酸铵、过乙酸、过氧化脲、过碳酸盐、过硼酸盐、以及它们的混合物。当氧化剂为过氧化氢(H2O2)时,已观察到最佳的结果。
在另一个实施例中,本发明包括用于从半导体基板相对于下面的低介电常数Cu、Co、SiON、SlCN和TEOS材料选择性移除基本上由TiN、TaN、TiNxOy、TiW、或W(包括Ti或W的合金)组成的蚀刻遮罩的方法,所述半导体基板在其上具有TiN、TaN、TiNxOy、TiW、或W蚀刻遮罩,包括包含Ti或W的合金的蚀刻遮罩,其中所述方法包括在室温至80℃范围内的温度和2至14范围内的pH下,使所述基板与移除组合物接触,所述移除组合物包含:
(a)0.1重量%至90重量%的至少一种氧化剂;
(b)0.0001重量%至50重量%的羧酸铵,所述羧酸铵选自一种或多种草酸铵、乳酸铵、酒石酸铵、柠檬酸三铵、乙酸铵、氨基甲酸铵、碳酸铵、苯甲酸铵、EDTA四铵、乙二胺四乙酸二铵盐、琥珀酸铵、甲酸铵、和1-H-吡唑-3-甲酸铵;以及
(c)补足100重量%所述移除组合物的剩余部分,包括去离子水,其中所述移除组合物相对于所述低介电常数Cu、Co、TEOS、和其它介电材料,选择性移除所述TiN、TaN、TiNxOy、TiW或W(包括Ti和/或W的合金)蚀刻遮罩。
在另一个实施例中,本发明包括用于从半导体基板相对于下面的低介电常数Cu、Co、SiON、SlCN和TEOS材料选择性移除基本上由TiN、TaN、TiNxOy、TiW、或W(包括Ti和/或W的合金)组成的蚀刻遮罩的方法,所述半导体基板在其上具有TiN、TaN、TiNxOy、TiW、或W蚀刻遮罩,包括包含Ti和/或W的合金的蚀刻遮罩,其中所述方法包括在室温至80℃范围内的温度和2至14范围内的pH下,使所述基板与移除组合物接触,所述移除组合物包含:
(a)0.1重量%至90重量%的至少一种氧化剂;
(b)0.0001重量%至50重量%的羧酸铵,所述羧酸铵选自一种或多种草酸铵、乳酸铵、酒石酸铵、柠檬酸三铵、乙酸铵、氨基甲酸铵、碳酸铵、苯甲酸铵、EDTA四铵、乙二胺四乙酸二铵盐、琥珀酸铵、甲酸铵、和1-H-吡唑-3-甲酸铵;
(c)0.001重量%至20重量%的氨基酸、胺多羧酸(即氨基多羧酸)、和/或羧酸、多羧酸螯合剂、或它们的混合物;以及
(d)补足100重量%的所述移除组合物的剩余部分,包括去离子水,其中所述移除组合物相对于所述低介电常数Cu、Co、TEOS、和其它介电材料,选择性移除所述TiN、TaN、TiNxOy、TiW和W(包括Ti和W的合金)蚀刻遮罩,并且移除所述蚀刻遮罩的速
率在可长达三十五(35)小时或更长的长时间内维持恒定。
在另一个实施例中,本文所述并且受权利要求书保护的一个或多个发明概念涵盖用于从半导体基板相对于下面的低介电常数Cu、Co、SiON、SlCN和TEOS材料选择性移除基本上由TiN、TaN、TiNxOy、TiW、或W(包括Ti或W的合金)组成的蚀刻遮罩的组合物和方法的改进,所述半导体基板在其上具有TiN、TaN、TiNxOy、TiW、或W蚀刻遮罩,包括包含Ti或W的合金的蚀刻遮罩,其中所述改进包括向所述移除组合物中掺入0.0001重量%至50重量%的羧酸铵,所述羧酸铵选自草酸铵、乳酸铵、酒石酸铵、柠檬酸三铵、乙酸铵、氨基甲酸铵、碳酸铵、苯甲酸铵、EDTA四铵、乙二胺四乙酸二铵盐、琥珀酸铵、甲酸铵、和1-H-吡唑-3-甲酸铵,由此所述移除组合物相对于所述低介电常数材料,选择性移除所述TiN、TaN、TiNxOy、TiW、W、或者Ti或W的合金的蚀刻遮罩。
在任何给定工序中待移除的不可取残留物的量和类型将影响所述组合物的操作pH的选择。
根据本文所述的发明概念所述的组合物和方法能够独特地选择性蚀刻TiN、TaN、TiNxOy、TiW和W(包括Ti和W的合金),与Cu、Co、低介电常数和TEOS介电材料相容,并且还可同时从待处理的基板即双镶嵌结构移除氧化铜、聚合物材料和蚀刻残留物。
根据本发明配制的并且本质上对TiN、TaN、TiNxOy、TiW、和W(包括Ti和W的合金)表现出高蚀刻速率的组合物使处理能够在较低温度(例如低于65℃的温度)下进行。较低温度处理表现出降低的氧化剂分解速率,其继而延长可用组合物浸浴寿命和留釜时间。另外,根据本发明所述的对TiN、TaN、TiNxOy、TiW、和W(包括Ti和W的合金)表现出高蚀刻速率和选择性蚀刻速率的组合物是所需的,因为它们可缩短设备处理时间,从而提高产量。通常,对TiN、TaN、TiNxOy、TiW、和W(包括Ti和W的合金)的高蚀刻速率已通过提高工艺温度而达到。然而,对于单晶片工艺应用而言,最高工艺温度为约75℃,其继而可限制TiN蚀刻速率的上限,从而限制从双镶嵌结构完全移除TiN金属硬遮罩的能力。根据本发明所述的组合物可在20℃至60℃范围内的温度下以单晶片工具应用来有效递送对TiN、TaN、TiNxOy、TiW、和W(包括Ti和W的合金)的高蚀刻速率,并且TiN、TaN、TiNxOy、TiW、和W(包括Ti和W的合金)金属硬遮罩可利用单晶片应用工艺设备完全移除(如果需要的话)。
附图说明
图1A和1B为半导体晶片片段的剖视SEM图像,其分别显示双镶嵌设备制造期间,但在与本发明移除组合物接触之前的沟槽和通路。
图2A和2B为在与表1的移除组合物1在50℃下接触90秒钟之后,图1A和1B中所示的此类半导体晶片片段的剖视SEM图像。
图3A和3B为在与表1的移除组合物2在50℃下接触90秒钟之后,图1A和1B中所示的此类半导体晶片片段的剖视SEM图像。
图4A和4B为在与表1的移除组合物3在53℃下接触90秒钟之后,图1A和1B中所示的此类半导体晶片片段的剖视SEM图像。
具体实施方式
已经认识到,本发明组合物的各种组分可能相互作用,因此任何组成被表示为当添加在一起时形成所述组合物的各种组分的量。除非另外特别说明,以百分比形式给出的任何组成均为已加入所述组合物的组分的重量百分比(重量%)。当将该组合物描述为基本上不含特定组分时,一般来讲将提供数值范围以指引本领域的普通技术人员了解何谓“基本上不含”,但在所有情况中,“基本上不含”涵盖其中所述组合物完全不含该特定组分的优选实施例。
如上简述,双镶嵌制程用于在后段金属化中形成金属互连,其接着用于在半导体基板中电互连各种电子部件以形成功能性电路。后段金属化(包括制造多级或多层的金属互连,该金属互连由一个或多个中间层介电层和/或一个或多个阻隔层所隔离)的论述可见于例如美国专利8,080,475,其教导内容以引用方式全文并入本文。将新材料诸如超低介电常数电介质整合到微电子设备中,带来对清洁性能的全新要求。同时,设备尺寸缩小降低了对通路和沟槽的精准尺寸变化的容差。
根据第一实施例,本发明为半导体处理组合物,所述半导体处理组合物包含水、至少一种氧化剂、任选地至少一种碱或酸(取决于工作组合物的期望pH)、和0.0001重量%至50重量%的羧酸铵。羧酸铵可以举例的方式但不限制性地选自草酸铵、乳酸铵、酒石酸铵、柠檬酸三铵、乙酸铵、氨基甲酸铵、碳酸铵、苯甲酸铵、EDTA四铵、乙二胺四乙酸二铵盐、琥珀酸铵、甲酸铵、1-H-吡唑-3-甲酸铵、以及它们的混合物。
在一个优选的实施例中,羧酸铵的浓度为0.001重量%至50重量%。虽然金属抗蚀剂对于实施本发明而言不是必需的,但在所述组合物待用于BEOL半导体处理应用以及关注金属组分例如Cu和Cu合金组分的腐蚀的其它应用中时,至少一种抗蚀剂也可存在于所述组合物中。在一个实施例中,所述制剂优选具有3至13的pH。就BEOL Cu互连制造而言,其优选具有7至12范围内的pH。
本发明的组合物有效地从半导体基板相对于低介电常数材料选择性移除基本上由TiN、TaN、TiNxOy、TiW、或W(包括Ti和/或W的合金)组成的蚀刻遮罩,所述半导体基板包含所述低介电常数介电材料,并且在该基板上具有TiN、TaN、TiNxOy、TiW、和W(包括Ti和/或W的合金)蚀刻遮罩。此外,所述组合物还可用于从基板同时移除光致抗蚀剂、聚合物材料、蚀刻残留物和氧化铜。
本发明的所述组合物还可包含0.001重量%至20重量%,优选0.001重量%至10重量%,更优选0.001重量%至5重量%的氨基酸、胺多羧酸(即氨基多羧酸)、和/或羧酸、多羧酸螯合剂、或它们的混合物。根据本文所述的并且受权利要求书保护的发明概念已经观察到,氨基酸、胺多羧酸(即氨基多羧酸)、和/或羧酸、多羧酸螯合剂、或它们的混合物的存在,稳定了所述组合物。本文使用术语“稳定”意指在选定的操作温度下可达到的硬遮罩蚀刻速率(即移除速率)在长时间内维持基本上恒定。此类螯合剂的示例包括但不限于1,2-环己二胺-N,N,N',N'-四乙酸;乙二胺四乙酸;次氮基三乙酸;二亚乙基三胺五乙酸;1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸;乙二醇四乙酸(EGTA);1,2-双(邻氨基苯氧基)乙烷-N,N,N',N'-四乙酸;N-{2-[双(羧甲基)氨基]乙基}-N-(2-羟乙基)甘氨酸(HEDTA);和乙二胺-N,N'-双(2-羟基苯乙酸)(EDDHA)。。
根据本文描述的发明概念所述的组合物和方法尤其适用于在单晶片设备中处理单晶片。当需要高TiN蚀刻速率时,常用方法为在高工艺温度下处理晶片。然而,已知高温致使氧化剂降解,这缩短浸浴寿命和留釜时间。根据本文描述的发明概念已观察到,令人满意的结果可在20℃至60℃范围内的显著较低温度下获得,以在硬遮罩包含TiN时产生拉回方案或完全移除金属硬遮罩。
共溶剂
在本发明的一些实施例中,所述组合物可包含一或多种可与水混溶的共溶剂。这些共溶剂增强残留物移除效果。适宜的共溶剂包括但不限于环丁砜、N-甲基吡咯烷酮、和二甲基亚砜。
氧化剂
根据一个或多个本发明概念的可用氧化剂选自能够与金属硬遮罩发生化学反应并且实现其移除的任何物质。此类氧化剂包括但不限于基本上由以下项组成的组:过氧化氢(H2O2)、n-甲基吗啉氧化物(NMMO或NMO)、过氧化苯甲酰、过氧单硫酸四丁铵、臭氧、氯化铁、高锰酸盐、过硼酸盐、高氯酸盐、过硫酸盐、过氧二硫酸铵、过乙酸、过氧化脲、硝酸(HNO3)、亚氯酸铵(NH4ClO2)、氯酸铵(NH4ClO3)、碘酸铵(NH4IO3)、过硼酸铵(NH4BO3)、高氯酸铵(NH4ClO4)、高碘酸铵(NH4IO3)、过硫酸铵((NH4)2S2O8)、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)、高氯酸四甲铵((N(CH3)4)ClO4)、高碘酸四甲铵((N(CH3)4)IO4)、过硫酸四甲铵((N(CH3)4)S2O8)、((CO(NH2)2)H2O2)、过氧乙酸(CH3(CO)OOH)、以及它们的混合物。在上述这些物质中,H2O2是最优选的氧化剂,因为其不含金属,并且提供处理简便性和较低的相对成本。
所述氧化剂或其混合物在所述组合物中的含量可为约0.1重量%至约90重量%,优选约5重量%至90重量%,并且为获得最佳效果,优选10重量%至90重量%。
pH调节
所述组合物也可视情况包含碱或酸,以调节工作组合物的pH。所述碱可选自例如季铵盐诸如四甲基氢氧化铵(TMAH)、四乙基氢氧化铵(TEAH)、苄基三甲基氢氧化铵(BTAH)、以及它们的混合物。所述碱也可选自伯胺、仲胺和叔胺,诸如例如单乙醇胺(MEA)、二甘醇胺(DGA)、三乙醇胺(TEA)、四丁基氢氧化(TBPH)、以及它们的混合物。在一些实施例中,所述碱可为季铵盐和胺的组合。适宜的酸包括例如无机酸诸如硫酸、硝酸、磷酸、氢氟酸(HF)、或氢溴酸,或者有机酸诸如羧酸、氨基酸、羟基羧酸、多羧酸、或此类酸的混合物。该工作组合物的pH值应保持在2至14,优选3至12的范围内的值。如上所述,在用于BEOL Cu互连制造应用中时,使用过氧化氢作为氧化剂以达到高TiN蚀刻速率情况下,所述工作组合物的优选pH在7至12的范围内。
金属抗蚀剂
Cu或Co抗蚀剂或者它们的混合物是本发明组合物中的任选组分。当用于其中需要存在抗蚀剂,以保护金属表面免遭蚀刻或以其它方式劣化的BEOL应用时,一种或多种Cu或Co抗蚀剂通常存在于本发明组合物和相关工艺中。对于本发明组合物与相关方法的其它应用,包括FEOL应用,一般不需要一种或多种抗蚀剂,即Cu或Co不曝露于所述清洁化合物,Cu或Co不存在于晶片基板,或者铜或钴表面的轻微蚀刻/劣化通常不造成顾虑。
金属(Cu或Co)抗蚀剂为有机化合物诸如唑、硫醇、和/或吲哚,优选选自包含至少一个氮原子的杂环化合物诸如例如吡咯及其衍生物、吡唑及其衍生物、咪唑及其衍生物、三唑及其衍生物、吲唑及其衍生物以及硫醇-三唑及其衍生物、苯并三唑(BTA)、甲苯三唑、5-苯基-苯并三唑、5-硝基-苯并三唑、3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、羟苯并三唑、2-(5-氨基-戊基)-苯并三唑、1-氨基-1,2,3-三唑、1-氨基-5-甲基-1,2,3-三唑、3-氨基-1,2,4-三唑、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、5-苯硫醇-苯并三唑、卤代-苯并三唑(卤素=F、Cl、Br或I)、萘并三唑、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、5-氨基四唑一水合物、5-氨基-1,3,4-噻二唑-2-硫醇、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-咪唑啉酮、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-1,2,4-三唑-3-硫醇、5-氨基-1,3,4-噻二唑-2-硫醇、苯并噻唑、以及它们的混合物。在上述这些物质中,BTA、吡唑、或BTA与吡唑的混合物、或BTA与甲苯三唑的混合物(可从Wincom,Inc.以商品名“Wintrol A-90”商购获得)是优选的Cu抗蚀剂,以获得更好的清洁性能。
Cu或Co抗蚀剂或它们的混合物在所述组合物中的含量可为约0.0001重量%至约50重量%,并且为获得最佳效果,优选为约0.0001重量%至约20重量%。
其它适宜的Cu或Co抗蚀剂包括但不限于芳族酰肼和席夫碱化合物。
羧酸盐
本文所描述的和受权利要求书保护的一个或多个发明概念来自于发现,即可通过将0.0001重量%至50重量%的有效量羧酸盐化合物(但尤其是羧酸铵)掺入所述移除组合物中,而实现从半导体设备完全移除金属硬遮罩,其中所述金属硬遮罩与低介电常数介电材料形成重叠关系。在一个优选的实施例中,羧酸铵的浓度为0.001重量%至10重量%。
如下文实例中所示,本发明的移除组合物中存在羧酸铵化合物,这不仅提高TiN蚀刻速率,而且数据还支持它们的存在也可用于长时间(例如达至少35小时)内使可达到的TiN蚀刻速率稳定的结论。
本文所用的术语“羧酸盐”是指通式M(RCOO)n,其中M为金属,并且n为1,2,...,是具有通式RCOOR'的化合物中羧酸酯的数目,其中R和R'为有机基团,前提条件是R'≠H。当本文所述的该类化合物用于电子设备制造中时,诸如制造IC设备,优选所述化学组合物中没有任何金属杂质。在此类情形下,M用NH4+替代。羧酸铵是用于所述一种或多种移除组合物中的优选化合物,并且它们可被直接加入所述组合物,或它们可在处理期间通过化学反应,以副产物或中间体形式生成。
实例
现在通过参照本发明概念和后续的实例来详细释明根据本发明所述的移除组合物,但本发明不限于这些实例以及各测试所显示的结果。本发明的组合物可体现为多种特定配方,如下文中更完整描述的。在其中所述组合物的具体组分以重量百分比范围(包括零下限)来论述的所有此类组合物中,应当理解,此类组分可存在或不存在于所述组合物的各种具体实施例中,并且在此类组分存在的情况下,它们的浓度含量以其中使用此类组分的组合物的总重量计可低至0.0001重量%。
在以下实例中,根据本文描述的一个或多个发明概念制备100g移除组合物样品。各样品组合物包含不同表格中所列示的各组分,其遵照对应配方列中所示的重量。例如,表1中示出的标示为“1”的100g量的样品组合物包含2g的10%酒石酸铵水溶液,7.21g的10%DGA水溶液,12.43g的1.5%BTA水溶液,60g的H2O2(30%的水溶液),和18.36g的去离子水(DIW)。
所述移除组合物可在使用时配制,或者它们可方便地预先配制而不含氧化剂,然后在使用时添加氧化剂。各种成分的混合或共混也没有具体的顺序。
TiN、Cu、Co、W和TEOS蚀刻速率
分别在60℃和50℃下化学处理1和2分钟后,实施TiN蚀刻速率评定,而在10分钟后实施Cu、Co、W和TEOS的蚀刻速率评定。使用Four Dimensions Four Point Probe Meter333A测定TiN、Cu、Co和W的厚度,由此膜的阻抗与在接触本发明组合物之后剩余的膜厚度有关。使用得自HORIBA JOBIN YVON的Auto SE Spectroscopic Ellipsometer来测量TEOS厚度。蚀刻速率计算为厚度变化(化学处理之前和之后)除以化学处理时间。化学溶液pH使用Beckman 260pH/Temp/mV计来测量。实验中所用的H2O2来源于J.T.Baker。残留物移除效率和TiN硬遮罩蚀刻由SEM结果(Hitachi S-5500)来评定。
使用作为溶剂的去离子水、作为Cu抗蚀剂的BTA或BTA与吡唑的混合物、作为氧化剂的H2O2、以及作为碱调节pH的二甘醇胺(DGA)或苄基三甲基氢氧化铵(BTAH),制备表1中所示的组合物。如上所述,在50℃的温度和约8的pH下进行TiN和Cu蚀刻速率评定。
表1
组合物1、2和3表现出的TiN移除速率在50℃至53℃范围内的相对较低的温度下为至就商用晶片处理而言,或更低的铜蚀刻速率被视为良好。
现请参照图,图1A和1B为半导体晶片片段在双镶嵌制造步骤之后,但在用移除组合物处理之前所接收的SEM图像,其分别示出沟槽和通路。图2A和2B为在50℃的温度下与移除组合物1接触90秒钟之后的晶片片段的视图,类似于图1A和1B中所示的晶片片段。残留物被移除,但部分TiN硬遮罩仍保留,如图2A中所示。图3A和3B为在50℃的温度下与移除组合物2接触90秒钟之后的晶片片段的视图,类似于图1A和1B中所示的晶片片段,其中TiN硬遮罩和残留物已被完全移除。图4A和4B为在53℃的温度下与移除组合物3接触90秒钟之后的晶片片段的视图,类似于图1A和1B中所示的晶片片段。TiN硬遮罩和残留物已被完全移除。
使用作为溶剂的去离子水、作为Cu抗蚀剂的BTA,作为氧化剂的H2O2,以及作为碱调节pH的四甲基氢氧化铵(TMAH),制备表2中所示的组合物。如上所述,在60℃的温度和约7.8的pH下进行TiN和Cu蚀刻速率评定。
与不包含羧酸铵的相应对照组合物4相比,分别包含所示量的乳酸铵、酒石酸铵、碳酸铵、和柠檬酸三铵化合物的各移除组合物均表现出较高的TiN蚀刻速率。
表2
制备表3中所示的制剂,并且如上所述,在50℃的温度和pH 8下进行TiN和Cu蚀刻速率评定。与不包含羧酸铵的对照组合物9相比,所述移除组合物表现出较高的TiN蚀刻速率和类似的铜蚀刻速率。
表3
使用DGA调节pH,并且使用BTA作为铜抗蚀剂,制备表4中所示的制剂。如上所述,在50℃的温度和pH 8下进行TiN和Cu蚀刻速率评定。与不包含羧酸铵的对照组合物13相比,所述移除组合物表现出较高的TiN蚀刻速率和类似的Cu蚀刻速率。
表4
使用TMAH调节pH,并且使用BTA作为铜抗蚀剂,制备表5中所示的制剂。如上所述,在50℃的温度和pH 8下进行TiN和Cu蚀刻速率评定。与不包含羧酸铵的对照组合物17相比,所述移除组合物表现出较高的TiN蚀刻速率和类似的Cu蚀刻速率。
表5
使用苄基三甲基氢氧化铵(BTAH)调节pH,并且使用BTA作为铜抗蚀剂,制备表6中所示的制剂。如上所述,在50℃的温度和约8的pH下进行TiN和Cu蚀刻速率评定。与不包含羧酸铵的对照组合物21相比,所述移除组合物表现出较高的TiN蚀刻速率和类似的Cu蚀刻速率。
表6
使用四乙基氢氧化铵(TEAH)调节pH,并且使用BTA作为铜抗蚀剂,制备表7中所示的制剂。如上所述,在50℃的温度和pH 8下进行TiN和Cu蚀刻速率评定。与不包含羧酸铵的对照组合物25相比,所述移除组合物表现出较高的TiN蚀刻速率和类似的Cu蚀刻速率。
表7
使用DGA调节pH,但是不使用铜抗蚀剂,制备表8中所示的制剂。如上所述,在50℃的温度和约8的pH下进行TiN和TEOS移除速率评定。与具有的TiN蚀刻速率的对照组合物31相比,所述移除组合物表现出低达至高达范围内的高TiN蚀刻速率。所述化合物碳酸铵、乙酸铵、草酸铵、乳酸铵和酒石酸铵以1.46重量%至低于3重量%的浓度存在,用于向本发明的移除组合物提供在相对低的温度例如50℃下递送非常高的TiN蚀刻速率的能力。值得注意的是,根据描述和受权利要求书保护的本发明概念,与对照组合物31相比,所述化合物碳酸铵、乙酸铵、草酸铵、乳酸铵或酒石酸铵对TEOS移除速率均无显著影响。
表8
不使用pH调节剂,制备表9中所示的制剂。所用的Cu抗蚀剂为Wintrol A-90,其为BTA和甲苯三唑的商业混合物。所期望的TiN和Cu蚀刻速率以及pH通过改变过氧化氢和羧酸铵的浓度来获得。在这些实例中,使用各种浓度的若干羧酸盐。过氧化氢浓度为20重量%或80重量%。所述制剂的pH在低达pH 5至高达pH 8.4的范围内,并且TiN蚀刻速率即移除速率在低达至高达范围内。
表9
制备表10中所示的制剂,使用酒石酸或TMAH,或者不使用任何pH调节剂。使用Wintrol A-90作为Co抗蚀剂。在这些实例中,使用各种浓度的若干羧酸盐。过氧化氢浓度在20重量%至80重量%的范围内。该制剂pH在低达pH 5至高达pH 11的范围内。Co蚀刻速率在所有案例中均不显著(即最高Co蚀刻速率为)。
表10
下表11中所示的结果显示,与不含羧酸铵的对照组合物53相比,移除组合物54中的乳酸铵和酒石酸铵的混合物表现出较高的TiN蚀刻速率。
表11
使用TMAH调节pH,并且使用BTA作为铜抗蚀剂,制备表12中所示的制剂。组合物56、57和58中所用的羧酸盐分别为柠檬酸三钾一水合物、酒石酸钾钠四水合物、和L-乳酸钾。与不含羧酸盐的对照组合物55相比,这些组合物中的每个均表现出较高的TiN蚀刻速率和类似的Cu蚀刻速率。
表12
表13中所示的结果表明,与对照组合物59相比,当羧酸铵浓度低达0.001重量%时,移除组合物60至63均表现出较高的TiN蚀刻速率以及类似的Cu和Co蚀刻速率。
表13
表14中所示的结果显示,与不含羧酸铵的对照组合物64相比,在50重量%的乙酸铵浓度下,移除组合物65表现出较高的TiN蚀刻速率以及类似的Cu和Co蚀刻速率。
表14
钨(W)蚀刻速率
制备表15中所示的制剂,并且如上结合TiN移除所述,在45℃和55℃的温度下进行W(钨)蚀刻速率评定。
表15
羧酸铵以1.46重量%至3重量%的浓度存在并且在约4至稍高于11的pH下,与相同pH下不含对应羧酸铵的对照组合物66、70与72相比,显示W移除速率显著提高。
组合物稳定性
如上所示,观察到氨基酸、胺多羧酸(即氨基多羧酸)、和/或羧酸、多羧酸螯合剂、或它们的混合物的存在,意料不到地稳定了本发明的组合物。本文使用术语“稳定”意指可达到的硬遮罩蚀刻速率(即移除硬遮罩的速率)在长时间内维持基本上恒定,例如在选定的操作温度下,二十二(22)小时至至少三十五(35)小时的时间段。如本文所用,术语“基本上恒定的”旨在表示在选定的操作温度下,移除硬遮罩的可达到的蚀刻速率在所述组合物的使用寿命期间不下降超过根据本文所述并且受权利要求书保护的发明概念,可用的螯合剂的示例包括但不限于1,2-环己二胺-N,N,N',N'-四乙酸(CDTA);乙二胺四乙酸;次氮基三乙酸;二亚乙基三胺五乙酸;1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸;乙二醇四乙酸(EGTA);1,2-双(邻氨基苯氧基)乙烷-N,N,N',N'-四乙酸;N-{2-[双(羧甲基)氨基]乙基}-N-(2-羟乙基)甘氨酸(HEDTA);和乙二胺-N,N'-双(2-羟基苯乙酸)(EDDHA)。
留釜时间为所述移除组合物制剂在一段时间内表现最佳并且功能性不会随时间推移而显著变化的能力的量度。留釜时间为温度的强函数。在高温下处理许多小时之后,混合物中的化合物可分解并且制剂将丧失功能性。
如下实施留釜时间研究(以确认本发明移除组合物的蚀刻速率维持恒定所处的时间段和程度):制备800克原液并且保持在50℃下。将150克样品从热原液中取出,并且在特定时间,在50℃下用于TiN和Cu蚀刻速率以及pH研究。在每次蚀刻速率测量之后丢弃样品。
根据描述和受权利要求书保护的一个或多个发明概念制备移除组合物,其中选择0.3重量%浓度的酒石酸铵作为羧酸铵。选择1,2-环己二胺-N,N,N',N'-四乙酸(CDTA)作为制剂74和75中的氨基多羧酸螯合剂,并且在对照制剂76中未包含螯合剂。组成示于表16中。
在0、2、4、7.5、和22小时的间隔处,从所述移除组合物中取样,以测定TiN和Cu蚀刻速率。结果示于表17中。
表16
表17
表17中示出的数据显示,在移除组合物74和75包含CDTA的情况下,TiN蚀刻速率在22小时期间内维持稳定,即基本上恒定。组合物75的初始TiN蚀刻速率为并且在22小时期间内其维持在就组合物74而言,初始TiN蚀刻速率为并且在22小时期间内维持在在不含CDTA的组合物76中,TiN蚀刻速率从的初始蚀刻速率衰减到22小时后的的蚀刻速率。
根据描述和受权利要求书保护的一个或多个发明概念制备移除组合物,其中选择0.3重量%浓度的酒石酸铵作为羧酸铵。选择1,2-环己二胺-N,N,N',N'-四乙酸(CDTA)作为制剂77和78中的氨基多羧酸螯合剂。组成示于表18中。
在0、2、4、7、和24小时的间隔处,从所述移除组合物中取样,以测定TiN和Cu蚀刻速率。结果示于表19中。
表18
表19
表19中示出的数据显示,在移除组合物77和78中分别包含0.001%和0.005%的CDTA的情况下,TiN蚀刻速率在24小时期间内维持稳定,即基本上恒定。组合物77的初始TiN蚀刻速率为并且在24小时期间内其维持在就组合物78而言,初始TiN蚀刻速率为并且在24小时期间内维持在
使用DGA调节pH,并且使用BTA作为铜抗蚀剂,制备表20中所示的制剂。使用EDTA四铵使TiN蚀刻速率稳定。
根据上述方法实施留釜时间研究。在0、2、4、8、24、28和35小时的间隔处取样,以测定TiN和Cu蚀刻速率以及pH。结果示于表21中。
表20
表21
表21中示出的实验结果显示,在移除组合物79中包含EDTA四铵的情况下,TiN蚀刻速率在三十五(35)小时期间内维持稳定,即维持基本上恒定。初始TiN蚀刻速率为并且在三十五(35)小时期间内其维持在在不含EDTA四铵的组合物80中,TiN蚀刻速率从的初始速率下降至24小时后的速率。
使用DGA调节pH,制备表22中的制剂。使用BTA作为铜抗蚀剂。所选的羧酸铵为EDTA四铵。表22中示出的结果显示,与不含羧酸铵的对照组合物82相比,移除组合物81中的EDTA四铵表现出较高的TiN蚀刻速率。
表22
本发明的移除组合物中存在羧酸铵,不仅如表2至8、11、13至15、以及22中所示提高TiN蚀刻速率,而且数据还支持它们的存在也可用于长时间(例如达至少35小时)内稳定TiN蚀刻速率的结论。
已描述本发明概念的若干实施例。然而,本领域的技术人员认识到,本发明不限于所述的实施例。本发明概念可在所附权利要求书实质和范围内进行变型和更改来实施。
Claims (13)
1.一种具有2至14范围内的pH的移除组合物,所述移除组合物用于从半导体设备基板相对于低介电常数介电材料选择性移除基本上由TiN、TaN、TiNxOy、TiW、W以及Ti和W的合金组成的蚀刻遮罩,所述半导体设备基板包含所述低介电常数介电材料,所述低介电常数介电材料在其上具有TiN、TaN、TiNxOy、TiW、W或者Ti或W的合金的蚀刻遮罩,其中所述移除组合物包含:
(a)0.1重量%至90重量%的氧化剂;
(b)0.0001重量%至50重量%的羧酸铵;以及
(c)补足100重量%的所述移除组合物的剩余部分,包括去离子水。
2.根据权利要求1所述的移除组合物,所述移除组合物还包含可与水混溶的有机共溶剂。
3.根据权利要求1或权利要求2所述的移除组合物,其中(a)所述氧化剂选自基本上由以下项组成的组:过氧化氢(H2O2)、n-甲基吗啉氧化物(NMMO或NMO)、过氧化苯甲酰、过氧单硫酸四丁铵、臭氧、氯化铁、高锰酸盐、过硼酸盐、高氯酸盐、过硫酸盐、过氧二硫酸铵、过乙酸、过氧化脲、硝酸(HNO3)、亚氯酸铵(NH4ClO2)、氯酸铵(NH4ClO3)、碘酸铵(NH4IO3)、过硼酸铵(NH4BO3)、高氯酸铵(NH4ClO4)、高碘酸铵(NH4IO3)、过硫酸铵((NH4)2S2O8)、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)、高氯酸四甲铵((N(CH3)4)ClO4)、高碘酸四甲铵((N(CH3)4)IO4)、过硫酸四甲铵((N(CH3)4)S2O8)、((CO(NH2)2)H2O2)、过氧乙酸(CH3(CO)OOH)、以及它们的混合物;并且
(b)所述羧酸铵选自包含以下各项的组:草酸铵、乳酸铵、酒石酸铵、柠檬酸三铵、乙酸铵、氨基甲酸铵、碳酸铵、苯甲酸铵、EDTA四铵、乙二胺四乙酸二铵盐、琥珀酸铵、甲酸铵、1-H-吡唑-3-甲酸铵、以及它们的混合物。
4.根据权利要求3所述的移除组合物,其中所述氧化剂为过氧化氢。
5.根据权利要求1所述的移除组合物,所述移除组合物还包含0.001重量%至20重量%的氨基酸、氨基多羧酸、羧酸、多羧酸、或它们的混合物,其选自基本上由以下项组成的组:1,2-环己二胺-N,N,N',N'-四乙酸;乙二胺四乙酸;次氮基三乙酸;二亚乙基三胺五乙酸;1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸;乙二醇四乙酸(EGTA);1,2-双(邻氨基苯氧基)乙烷-N,N,N',N'-四乙酸;N-{2-[双(羧甲基)氨基]乙基}-N-(2-羟乙基)甘氨酸(HEDTA);和乙二胺-N,N'-双(2-羟基苯乙酸)(EDDHA)。
6.根据权利要求1所述的移除组合物,所述移除组合物还包含0.0001重量%至50重量%的金属抗蚀剂。
7.根据权利要求1所述的移除组合物,其中所述pH在3至13的范围内,并且所述氧化剂为过氧化氢。
8.根据权利要求7所述的移除组合物,其中所述pH在7至12的范围内。
9.一种用于从半导体基板相对于低介电常数材料选择性移除基本上由TiN、TaN、TiNxOy、TiW、W或者Ti或W的合金组成的蚀刻遮罩的方法,所述半导体基板包含所述低介电常数材料,所述低介电常数材料在其上具有基本上由TiN、TaN、TiNxOy、TiW、W或者Ti或W的合金组成的蚀刻遮罩,其中所述方法包括在室温至80℃的范围内的温度下和在3至13的范围内的pH下,使所述基板与移除组合物接触一段时间,所述移除组合物包含:
(a)0.1重量%至90重量%的至少一种氧化剂;
(b)0.0001重量%至50重量%的羧酸铵;以及
(c)补足100重量%的所述移除组合物的剩余部分,包括去离子水,
其中所述移除组合物相对于所述低介电常数材料选择性移除所述TiN、TaN、TiNxOy、TiW、W或者Ti或W的合金的蚀刻遮罩,并且所述组合物的可达到的蚀刻速率在长时间内维持基本上恒定。
10.根据权利要求9所述的方法,其中:
(a)所述氧化剂选自基本上由以下项组成的组:过氧化氢(H2O2)、n-甲基吗啉氧化物(NMMO或NMO)、过氧化苯甲酰、过氧单硫酸四丁铵、臭氧、氯化铁、高锰酸盐、过硼酸盐、高氯酸盐、过硫酸盐、过氧二硫酸铵、过乙酸、过氧化脲、硝酸(HNO3)、亚氯酸铵(NH4ClO2)、氯酸铵(NH4ClO3)、碘酸铵(NH4IO3)、过硼酸铵(NH4BO3)、高氯酸铵(NH4ClO4)、高碘酸铵(NH4IO3)、过硫酸铵((NH4)2S2O8)、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)、高氯酸四甲铵((N(CH3)4)ClO4)、高碘酸四甲铵((N(CH3)4)IO4)、过硫酸四甲铵((N(CH3)4)S2O8)、((CO(NH2)2)H2O2)、过氧乙酸(CH3(CO)OOH)、以及它们的混合物;并且
(b)所述羧酸铵选自包含以下各项的组:草酸铵、乳酸铵、酒石酸铵、柠檬酸三铵、乙酸铵、氨基甲酸铵、碳酸铵、苯甲酸铵、EDTA四铵、乙二胺四乙酸二铵盐、琥珀酸铵、甲酸铵、1-H-吡唑-3-甲酸铵、以及它们的混合物。
11.根据权利要求10所述的方法,其中所述移除组合物还包含0.0001重量%至20重量%的铜抗蚀剂。
12.根据权利要求10所述的方法,其中所述移除组合物还包含0.001重量%至20重量%的氨基酸、氨基多羧酸、羧酸、多羧酸、或它们的混合物,其选自基本上由以下项组成的组:1,2-环己二胺-N,N,N',N'-四乙酸;乙二胺四乙酸;次氮基三乙酸;二亚乙基三胺五乙酸;1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸;乙二醇四乙酸(EGTA);1,2-双(邻氨基苯氧基)乙烷-N,N,N',N'-四乙酸;N-{2-[双(羧甲基)氨基]乙基}-N-(2-羟乙基)甘氨酸(HEDTA);和乙二胺-N,N'-双(2-羟基苯乙酸)(EDDHA);由此所述蚀刻遮罩的可达到的移除速率在达至少三十五小时的长时间内维持基本上恒定。
13.一种用于从半导体基板相对于低介电常数材料选择性移除基本上由TiN、TaN、TiNxOy、TiW、W或者Ti或W的合金组成的蚀刻遮罩的方法,所述半导体基板包含所述低介电常数材料,所述低介电常数材料在其上具有基本上由TiN、TaN、TiNxOy、TiW、W或者Ti或W的合金组成的蚀刻遮罩,其中所述方法包括在室温至80℃的范围内的温度下和在3至13的范围内的pH下,使所述基板与移除组合物接触一段时间,所述移除组合物包含:
(a)0.1重量%至90重量%的过氧化氢;
(b)0.0001重量%至50重量%的羧酸铵,所述羧酸铵选自包含以下各项的组:草酸铵、乳酸铵、酒石酸铵、柠檬酸三铵、乙酸铵、氨基甲酸铵、碳酸铵、苯甲酸铵、EDTA四铵、乙二胺四乙酸二铵盐、琥珀酸铵、甲酸铵、1-H-吡唑-3-甲酸铵、以及它们的混合物;
(c)0.001重量%至20重量%的氨基酸、氨基多羧酸、羧酸、多羧酸、或它们的混合物,其选自基本上由以下项组成的组:1,2-环己二胺-N,N,N',N'-四乙酸;乙二胺四乙酸;次氮基三乙酸;二亚乙基三胺五乙酸;1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸;乙二醇四乙酸(EGTA);和1,2-双(邻氨基苯氧基)乙烷-N,N,N',N'-四乙酸;以及
(d)补足100重量%的所述移除组合物的剩余部分,包括去离子水,
其中所述移除组合物相对于所述低介电常数材料选择性移除所述TiN、TaN、TiNxOy、TiW、W或者Ti或W的合金的蚀刻遮罩,由此所述蚀刻遮罩被选择性移除,并且所述蚀刻遮罩的可达到的移除速率在长时间内维持基本上恒定。
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CN107148156A (zh) * | 2017-05-08 | 2017-09-08 | 广东光华科技股份有限公司 | 3,6‑二氧杂‑1,8‑辛二胺四乙酸衍生物的应用及osp处理液 |
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CN110272742A (zh) * | 2018-03-16 | 2019-09-24 | 弗萨姆材料美国有限责任公司 | 用于钨字线凹进的蚀刻溶液 |
CN110911278A (zh) * | 2018-09-18 | 2020-03-24 | 三星电子株式会社 | 蚀刻金属阻挡层和金属层的方法和制造半导体器件的方法 |
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CN113430066A (zh) * | 2020-03-23 | 2021-09-24 | 上海新阳半导体材料股份有限公司 | 用于选择性移除硬遮罩的清洗组合物、其制备方法及应用 |
CN113430072A (zh) * | 2020-03-23 | 2021-09-24 | 上海新阳半导体材料股份有限公司 | 移除硬遮罩的钴兼容性半水基清洗液、其制备方法及应用 |
CN113430066B (zh) * | 2020-03-23 | 2024-04-19 | 上海新阳半导体材料股份有限公司 | 用于选择性移除硬遮罩的清洗组合物、其制备方法及应用 |
CN113430072B (zh) * | 2020-03-23 | 2024-05-07 | 上海新阳半导体材料股份有限公司 | 移除硬遮罩的钴兼容性半水基清洗液、其制备方法及应用 |
Also Published As
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TWI650415B (zh) | 2019-02-11 |
US10155921B2 (en) | 2018-12-18 |
JP2017502491A (ja) | 2017-01-19 |
WO2015053800A2 (en) | 2015-04-16 |
US20160254182A1 (en) | 2016-09-01 |
KR102334603B1 (ko) | 2021-12-06 |
CN105874562A (zh) | 2016-08-17 |
KR20160068903A (ko) | 2016-06-15 |
CN105612599A (zh) | 2016-05-25 |
TW201527518A (zh) | 2015-07-16 |
KR102327432B1 (ko) | 2021-11-17 |
KR20160068902A (ko) | 2016-06-15 |
US10005991B2 (en) | 2018-06-26 |
WO2015053800A3 (en) | 2015-06-18 |
TW201522574A (zh) | 2015-06-16 |
CN105874562B (zh) | 2019-05-14 |
JP2016535819A (ja) | 2016-11-17 |
US20150104952A1 (en) | 2015-04-16 |
US20160240368A1 (en) | 2016-08-18 |
TWI650414B (zh) | 2019-02-11 |
TW201527519A (zh) | 2015-07-16 |
JP6523269B2 (ja) | 2019-05-29 |
JP2016536785A (ja) | 2016-11-24 |
US20160312162A1 (en) | 2016-10-27 |
KR20170076616A (ko) | 2017-07-04 |
CN105612599B (zh) | 2019-05-14 |
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