WO2015054460A1 - Removal composition for selectively removing hard mask - Google Patents
Removal composition for selectively removing hard mask Download PDFInfo
- Publication number
- WO2015054460A1 WO2015054460A1 PCT/US2014/059840 US2014059840W WO2015054460A1 WO 2015054460 A1 WO2015054460 A1 WO 2015054460A1 US 2014059840 W US2014059840 W US 2014059840W WO 2015054460 A1 WO2015054460 A1 WO 2015054460A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- ammonium
- removal composition
- mixture
- tin
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 404
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 154
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 116
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 108
- 229910008599 TiW Inorganic materials 0.000 claims abstract description 58
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 57
- 239000000956 alloy Substances 0.000 claims abstract description 57
- 239000003989 dielectric material Substances 0.000 claims abstract description 56
- 239000004065 semiconductor Substances 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 45
- 239000007800 oxidant agent Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 34
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims description 105
- 238000005260 corrosion Methods 0.000 claims description 62
- 230000007797 corrosion Effects 0.000 claims description 62
- 239000003112 inhibitor Substances 0.000 claims description 61
- -1 ammonium carboxylate Chemical class 0.000 claims description 55
- 229910052751 metal Inorganic materials 0.000 claims description 50
- 239000002184 metal Substances 0.000 claims description 50
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 33
- 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 claims description 28
- 150000001413 amino acids Chemical class 0.000 claims description 28
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 28
- 239000012964 benzotriazole Substances 0.000 claims description 24
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 22
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 19
- 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 19
- PZZHMLOHNYWKIK-UHFFFAOYSA-N eddha Chemical compound C=1C=CC=C(O)C=1C(C(=O)O)NCCNC(C(O)=O)C1=CC=CC=C1O PZZHMLOHNYWKIK-UHFFFAOYSA-N 0.000 claims description 18
- 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 18
- 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 17
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 16
- FVCHPLIQTBSXKX-UHFFFAOYSA-N azanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O FVCHPLIQTBSXKX-UHFFFAOYSA-N 0.000 claims description 15
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 15
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 15
- LESFYQKBUCDEQP-UHFFFAOYSA-N tetraazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound N.N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LESFYQKBUCDEQP-UHFFFAOYSA-N 0.000 claims description 14
- 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 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 claims description 9
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 claims description 9
- FTEDXVNDVHYDQW-UHFFFAOYSA-N BAPTA Chemical compound OC(=O)CN(CC(O)=O)C1=CC=CC=C1OCCOC1=CC=CC=C1N(CC(O)=O)CC(O)=O FTEDXVNDVHYDQW-UHFFFAOYSA-N 0.000 claims description 9
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 9
- WDLRUFUQRNWCPK-UHFFFAOYSA-N Tetraxetan Chemical compound OC(=O)CN1CCN(CC(O)=O)CCN(CC(O)=O)CCN(CC(O)=O)CC1 WDLRUFUQRNWCPK-UHFFFAOYSA-N 0.000 claims description 9
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 239000004251 Ammonium lactate Substances 0.000 claims description 8
- 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 8
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 8
- 229940059265 ammonium lactate Drugs 0.000 claims description 8
- 235000019286 ammonium lactate Nutrition 0.000 claims description 8
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 8
- 229960003330 pentetic acid Drugs 0.000 claims description 8
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 7
- 239000005695 Ammonium acetate Substances 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229940043376 ammonium acetate Drugs 0.000 claims description 7
- 235000019257 ammonium acetate Nutrition 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- XKWFRVVFRZYIFP-UHFFFAOYSA-N triazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O XKWFRVVFRZYIFP-UHFFFAOYSA-N 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 6
- 150000003141 primary amines Chemical class 0.000 claims description 6
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 6
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 150000003335 secondary amines Chemical class 0.000 claims description 5
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- 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 5
- 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 4
- 229940090948 ammonium benzoate Drugs 0.000 claims description 4
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 4
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- 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 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-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
- 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
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- AENSXLNDMRQIEX-UHFFFAOYSA-L oxido sulfate;tetrabutylazanium Chemical compound [O-]OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC AENSXLNDMRQIEX-UHFFFAOYSA-L 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-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
- PJAHUDTUZRZBKM-UHFFFAOYSA-K potassium citrate monohydrate Chemical compound O.[K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PJAHUDTUZRZBKM-UHFFFAOYSA-K 0.000 claims description 3
- PHZLMBHDXVLRIX-DKWTVANSSA-M potassium;(2s)-2-hydroxypropanoate Chemical compound [K+].C[C@H](O)C([O-])=O PHZLMBHDXVLRIX-DKWTVANSSA-M 0.000 claims description 3
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 3
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 claims description 3
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 claims description 3
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 claims description 3
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 claims description 3
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000010949 copper Substances 0.000 description 67
- 229910052802 copper Inorganic materials 0.000 description 40
- 238000000034 method Methods 0.000 description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 31
- 239000002585 base Substances 0.000 description 31
- 235000012431 wafers Nutrition 0.000 description 26
- 239000002738 chelating agent Substances 0.000 description 25
- 238000009472 formulation Methods 0.000 description 23
- 150000001412 amines Chemical class 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 230000009977 dual effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000005530 etching Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- 239000006184 cosolvent Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000004377 microelectronic Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 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
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 239000000523 sample Substances 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
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011550 stock solution Substances 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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- NHAZGSRLKBTDBF-UHFFFAOYSA-N 1,2,4-triazol-1-amine Chemical compound NN1C=NC=N1 NHAZGSRLKBTDBF-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- NXRIDTLKJCKPOG-UHFFFAOYSA-N 1,4-dihydroimidazole-5-thione Chemical compound S=C1CN=CN1 NXRIDTLKJCKPOG-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- JVSMPWHQUPKRNV-UHFFFAOYSA-N 2h-tetrazol-5-amine;hydrate Chemical compound O.NC=1N=NNN=1 JVSMPWHQUPKRNV-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- AGWWTUWTOBEQFE-UHFFFAOYSA-N 4-methyl-1h-1,2,4-triazole-5-thione Chemical compound CN1C=NN=C1S AGWWTUWTOBEQFE-UHFFFAOYSA-N 0.000 description 1
- YZTYEGCWRPJWEE-UHFFFAOYSA-N 5-(benzotriazol-2-yl)pentan-1-amine Chemical compound C1=CC=CC2=NN(CCCCCN)N=C21 YZTYEGCWRPJWEE-UHFFFAOYSA-N 0.000 description 1
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 1
- HCEKEODXLSQFDV-UHFFFAOYSA-N 5-methyltriazol-1-amine Chemical compound CC1=CN=NN1N HCEKEODXLSQFDV-UHFFFAOYSA-N 0.000 description 1
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 description 1
- WXSBVEKBZGNSDY-UHFFFAOYSA-N 5-phenyl-2h-benzotriazole Chemical compound C1=CC=CC=C1C1=CC2=NNN=C2C=C1 WXSBVEKBZGNSDY-UHFFFAOYSA-N 0.000 description 1
- AJNQPSCMOSUVKK-UHFFFAOYSA-N 5-propan-2-yl-1h-1,2,4-triazole Chemical compound CC(C)C=1N=CNN=1 AJNQPSCMOSUVKK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CWRVKFFCRWGWCS-UHFFFAOYSA-N Pentrazole Chemical compound C1CCCCC2=NN=NN21 CWRVKFFCRWGWCS-UHFFFAOYSA-N 0.000 description 1
- 244000208734 Pisonia aculeata Species 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005441 electronic device fabrication Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229960005152 pentetrazol Drugs 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- LDGFRUUNCRYSQK-UHFFFAOYSA-N triazin-4-ylmethanediamine Chemical compound NC(N)C1=CC=NN=N1 LDGFRUUNCRYSQK-UHFFFAOYSA-N 0.000 description 1
- MPSUGQWRVNRJEE-UHFFFAOYSA-N triazol-1-amine Chemical compound NN1C=CN=N1 MPSUGQWRVNRJEE-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- 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
-
- 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
- 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
- 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
- C23F1/40—Alkaline compositions for etching other metallic material
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- C11D2111/22—
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31144—Etching the insulating layers by chemical or physical means using masks
Definitions
- compositions and methods for selectively removing hard mask and other residues from integrated circuit (IC) device substrates relate to compositions and methods for selectively removing hard mask and other residues from integrated circuit (IC) device substrates, and, more particularly, to compositions and methods useful for selectively removing TiN, TaN, TiNxOy, TiW,Ti and W hard mask, and hard masks comprising alloys of the foregoing, as well as other residues from such substrates comprising low-k dielectric materials, TEOS, copper, cobalt and other low-k dielectric materials, using a carboxylate compound.
- IC integrated circuit
- Plasma dry etching is commonly used to fabricate vertical sidewall trenches and anisotropic interconnecting vias in copper (Cu)/low-k dual damascene fabrication processes.
- Cu copper
- Low-k dual damascene fabrication processes As the technology nodes advance to 45 nm and smaller, the decreasing size of the semiconductor devices makes achieving critical profile control of vias and trenches more challenging.
- Integrated circuit device companies are investigating the use of a variety of hard masks to improve etch selectivity to low-k materials and thereby gain better profile control.
- the removal composition can also effectively etch the hard mask to form an intermediate morphology, e.g., a pulled-back/rounded morphology, or completely remove the hard mask.
- a pulled-back/rounded morphology could prevent undercutting the hard mask, which, in turn, could enable reliable deposition of barrier metal, Cu seed layer and Cu filling.
- fully removing the hard mask using the same composition could offer numerous benefits to
- CMP chemical mechanical polishing
- removal (cleaning) processes are required to remove residues of the plasma etch, photoresist, oxidizer, abrasive, metal and/or other liquids or particles that remain and which can contaminate the surface of the device if they are not effectively removed.
- Fabrication of advanced generation devices that require copper conductors and low-k dielectric materials typically carbon-doped silicon oxide (SiOCH), or porous low-k materials) give rise to the problem that both materials can react with and be damaged by various classes of prior art cleaners.
- Low-k dielectrics may be damaged in the removal process as evidenced by etching, changes in porosity/size, and ultimately changes in dielectric properties.
- Time required to remove residues depends on the nature of the residue, the process (heating, crosslinking, etching, baking, and/or ashing) by which it was created, and whether batch or single wafer removal processes can be used. Some residues may be cleaned in a very short period of time, while some residues require much longer removal procedures. Compatibility with both the low-k dielectric and with the copper conductor over the duration of contact with the removal composition is a desired characteristic.
- TiN, TaN, TiNxOy, TiW, Ti, and/or W are used as an hard mask in the formation of vias and trenches to gain high selectivity to low-k dielectric materials during dry etching steps.
- Effective removal compositions are required that can selectively remove the TiN, TaN, TiNxOy, TiW, Ti or W, be compatible with low-k materials, copper, cobalt and other dielectric materials, and also simultaneously remove unwanted etching residues and Cu oxide from the resulting dual damascene structure. Beyond selective removal, it is also highly desirable that the achievable removal rate of a hard mask (A min) for the removal composition be maintained substantially constant for an extended period of time.
- the present disclosure relates to an improved semiconductor processing composition, i.e., a wet cleaning chemistry or removal composition, with one or more carboxylates which provides highly selective removal of hard mask from a dual damascene structure without damaging wiring metallurgy and dielectric materials.
- the removal composition can remove hard mask etch residues, photoresist, polymeric materials, and copper oxide from via and trench surfaces without damaging underlying layers that form the structure.
- the semiconductor substrates typically comprise copper, cobalt , a Low-k dielectric material(s), SiON, SiCN, TEOS and a hard mask selected from TiN, TaN, TiNxOy, TiW, W, Ti, including alloys of Ti and W.
- the removal composition comprises 0.1 wt% to 90 wt% at least one oxidizing agent, 0.0001 wt% to 50 wt% of a carboxylate, with the balance up to 100 wt% of the removal composition comprising water, e.g., deionized water.
- Figs. 1A and 1 B are cross-sectional SEM images of semiconductor wafer segments which show trenches and vias, respectively, during dual damascene device fabrication, but prior to contact with the removal composition of the invention.
- Figs. 2A and 2B are cross-sectional SEM images of semiconductor wafer segments of the type shown in Figs. 1 A and 1 B after contact with removal compositon 1 from Table 1 at 50°C for 90 sec.
- Figs. 3A and 3B are cross-sectional SEM images of semiconductor wafer segments of the type shown in Figs. 1 A and 1 B after contact with removal compositon 2 from Table 1 at 50°C for 90 sec.
- Figs. 4A and 4B are cross-sectional SEM images of semiconductor wafer segments of the type shown in Figs. 1 A and 1 B after contact with removal compositon 3 from Table 1 at 53° Detailed C for 90 sec.
- any composition is expressed as the amount of various components which, when added together, form the composition. Unless specifically stated otherwise, any composition given in percent is percent by weight (wt%) of that component that has been added to the composition.
- wt% percent by weight
- the dual damascene process is used to form metal interconnects in the backend metallization, which are then used to electrically
- interconnect various electrical components in a semiconductor substrate into functional circuits are interconnect various electrical components in a semiconductor substrate into functional circuits.
- backend metallization which comprises fabrication of multiple levels, or layers, of metal interconnects isolated by an interlayer dielectric layer(s) and/or barrier layer(s) can be found, for example, in U.S. Patent No. 8,080,475, the teachings of which are incorporated herein in their entirety by reference.
- the described and claimed inventive concept(s) reside in the discovery that selective removal of hard mask from semiconductor substrate wherein said hard mask is in overlapping relationship with a low-k dielectric material can be accomplished by incorporating into the removal composition an effective amount of from 0.0001 wt% up to 50 wt% of a carboxylate. In a preferred embodiment, the concentration of
- carboxylate is from 0.001 wt% up to 10 wt%. Another advantage is the addition of a carboxylate increases the etch rate of a hard mask selected from TiN, TaN, TiNxOy, TiW, W, Ti, including alloys of Ti and W.
- Yet another advantage resides in the discovery that ammonium carboxylates in combination with CDTA in removal composition of the present disclosure increase etch rate as well as stabilize the etch rate. And yet another advantage resides in the discovery that ammonium ethylenediaminetetraacetic acids not only increase the etch rate but also stabilize the etch rate.
- the chemicals in a removal composition for removing a metal hard mask can decompose over time.
- the term "stabilize” or “stabilized” is used herein to mean that the achievable etch rate for a hard mask remains substantially constant over an extended period of time, e.g., a time period of from twenty two (22) hours and up to thirty five (35) hours or longer at the selected operating temperature.
- the etch rate of the removal composition after for 2, 4, or 8 hrs of use is substantially the same after 20, 24 or 35 hrs of use.
- substantially constant is intended to mean that decomposition over time is minimized or less than if ammonium ethylenediaminetetraacetic acids or a combination of ammonium carboxylate(s) and amino acid, amine polycarboxylic acid, carboxylic acid or polycarboxylic acid chelating agent were not used in the removal composition.
- the etch rate does not decrease as much as when ammonium ethylenediaminetetraacetic acids or a combination of ammonium carboxylate(s) and amino acid, amine polycarboxylic acid, carboxylic acid or polycarboxylic acid chelating agent were not used.
- Low-k dielectric material is any material used as a dielectric material in a semiconductor substrate or any microelectrinic device where in the dielectric constant is less than 3.5.
- useful Low-k dielectric materials include but are not limited to: silicon dioxide (Si0 2 ), carbon-doped silicon oxide (SiOCH), low-polarity materials such as organic polymers, hybrid organic, inorganic materials, organosilicate glass (OSG), and carbon-doped oxide (CDO) glass.
- Si0 2 silicon dioxide
- SiOCH carbon-doped silicon oxide
- low-polarity materials such as organic polymers
- hybrid organic, inorganic materials hybrid organic, inorganic materials, organosilicate glass (OSG), and carbon-doped oxide (CDO) glass.
- OSG organosilicate glass
- CDO carbon-doped oxide
- carboxylate is used herein to mean the general formula M(RCOO)n, where M is a metal and n is 1 ,2,... is the number of carboxylate esters within the compound having the general formula RCOOR', wherein R and R' are organic groups with the proviso that R' ⁇ H.
- M is replaced with NH4+.
- the removal composition of the present disclosure selectively removes a hard mask from a semiconductor substrate.
- the hard mask consists essentially of TiN, TaN, TiNxOy, TiW, W, Ti and alloys of Ti and W.
- the removal composition selectively removes the hard mask relative to the low-k dielectric material of a semiconductor substrate.
- the removal composition comprises:
- the presence of a carboxylate in the removal composition increases the etch rate of a metal hard mark at least 8% when compared to the same removal composition with out a carboxylate and in some embodiments, at least 39% or 43% or 50% or 60% or 75 or 80%.
- the carboxylate is selected from the group consisting of potassium citrate tribasic monohydrate, potassium sodium tartrate tetrahydrate, potassium L-Lactate and mixtures thereof.
- the carboxylate is an ammonium carboxylate.
- the ammonium carboxylate is selected from the group consisting of ammonium oxalate, ammonium lactate, ammonium tartrate, ammonium citrate tribasic, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, ammonium ethylenediaminetetraacetic acid, diammonium
- ethylenediaminetetraacetic acid triammonium ethylenediaminetetraacetic acid, tetraammonium ethylenediaminetetraacetic acid, ammonium succinate, ammonium formate, ammonium 1 -H-pyrazole-3-carboxylate and mixtures thereof.
- the carboxylate is present in an amount from 0.0001 wt% to 50wt% based on the total weight of the removal composition. In some embodiments, the carboxylate is present in an amount from 0.0001 wt% to 25wt% based on the total weight of the removal composition. In some embodiments, the carboxylate is present in an amount from 0.0001 wt% to 10wt% based on the total weight of the removal composition. In another embodiment, the carboxylate is present in an amount from 0.0001 wt% to 0.6 wt% based on the total weight of the removal composition. In another embodiment, the carboxylate is present in an amount from 0.001 wt% to 50wt% based on the total weight of the removal composition.
- the carboxylate is present in an amount from 0.001 wt% to 10wt% based on the total weight of the removal composition. In yet another embodiment, the carboxylate is present in an amount from 0.2 to 0.5 wt% based on the total weight of the removal composition
- the ammonium carboxylate is present in an amount from 0.0001 wt% to 50wt% based on the total weight of the removal composition. In some embodiments, the ammonium carboxylate is present in an amount from
- the ammonium carboxylate is present in an amount from 0.0001 wt% to 10wt% based on the total weight of the removal composition. In another embodiment, the ammonium carboxylate is present in an amount from 0.0001 to 0.6 wt% based on the total weight of the removal composition. In yet another embodiment, the ammonium carboxylate is present in an amount from 0.001 wt% to 50wt% based on the total weight of the removal composition. In another embodiment, the ammonium carboxylate is present in an amount from 0.001 wt% to 10wt% based on the total weight of the removal composition. In yet another embodiment, the ammonium carboxylate is present in an amount from 0.2 to 0.5 wt% based on the total weight of the removal composition
- the ammonium carboxylate is an ammonium
- ethylenediaminetetraacetic acid or mixture thereof ethylenediaminetetraacetic acid or mixture thereof.
- ammonium ethylenediaminetetraacetic acids in the removal compositions of this disclosure not only increased the etch rate of the hard mask but also operates to stabilize the achievable etch rate over an extended period of time (up to at least 22 hours and in some embodiments up to at least 35 hours).
- the ammonium ethylenediaminetetraacetic acids are selected from the group consisting of ammonium ethylenediaminetetraacetic acid, diammonium ethylenediaminetetraacetic acid, triammonium ethylenediaminetetraacetic acid, tetraammonium ethylenediaminetetraacetic acid and mixtures thereof.
- ammonium ethylenediaminetetraacetic acids stabilize etch rate. In some embodiments, ammonium ethylenediaminetetraacetic acids stabilize TiN etch rate. In some embodiments, ammonium ethylenediaminetetraacetic acids stabilize TiN etch rate such that TiN etch rate at 50 °C does not drop more than 20% or 45
- the ammonium carboxylate is tetraammonium
- ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid.
- tetraammonium ethylenediaminetetraacetic acid.
- ethylenediaminetetraacetic acid stabilizes the TiN etch rate such that TiN etch rate at 50 °C which does not drop more than 20% or 45 A/min at 35 hours.
- TiN etch rate at 50 °C drops 60% or 86 A/min at 35 hours.
- Oxidizing agents useful according to the inventive concept(s) are selected from any substance which has the capability to chemically react with the hard mask and effect its removal.
- the removal composition oxidizing agent is selected from the group consisting of hydrogen peroxide (H2O2), n-methylmorpholine oxide (NMMO or NMO), benzoyl peroxide, tetrabutylammonium peroxymonosulfate, ozone, ferric chloride, permanganate peroxoborate, perchlorate, persulfate, ammonium peroxydisulfate, per acetic acid, urea hydroperoxide, nitric acid (HNO3), ammonium chlorite (NH4CIO2), ammonium chlorate (NH4CIO3), ammonium iodate (NH4IO3), ammonium perborate (NH4BO3), ammonium perchlorate (NH4CIO4), ammonium periodate (NH4IO3), ammonium persulf
- H2O2 is a most preferred oxidizing agent being low concentration of metals and providing ease of handling and lower relative cost.
- the removal composition comprises from 0.1 wt% to 90 wt% of an oxidizing agent. In another embodiment, the removal composition comprises from 0.1 wt% to 24 wt% of an oxidizing agent. In another embodiment, the removal composition comprises from 3 wt% to 24 wt% of an oxidizing agent.
- the removal composition may also include an amino acid, amine polycarboxylic acid (i.e., aminopolycarboxylic acid), and/or carboxylic acid, polycarboxylic acid chelating agent, or a mixture thereof.
- an amino acid, amine polycarboxylic acid i.e., aminopolycarboxylic acid
- carboxylic acid i.e., aminopolycarboxylic acid
- polycarboxylic acid chelating agent i.e., aminopolylic acid
- polycarboxylic acid i.e., aminopolycarboxylic acid
- carboxylic acid i.e., aminopolycarboxylic acid
- the removal composition includes 0.0005 wt% to 20 wt% of an amino acid, amine polycarboxylic acid (i.e., aminopolycarboxylic acid), and/or carboxylic acid, polycarboxylic acid chelating agent, or a mixture thereof.
- the removal composition includes 0.001 wt% to 20 wt% of an amino acid, amine polycarboxylic acid (i.e., aminopolycarboxylic acid), and/or carboxylic acid, polycarboxylic acid chelating agent, or a mixture thereof. In another embodiment, the removal composition includes 0.001 wt% to 10 wt% of an amino acid, amine polycarboxylic acid (i.e., aminopolycarboxylic acid), and/or carboxylic acid, polycarboxylic acid chelating agent, or a mixture thereof. In another embodiment, the removal composition includes 0.001 wt% to 10 wt% of an amino acid, amine
- polycarboxylic acid i.e., aminopolycarboxylic acid
- carboxylic acid i.e., aminopolycarboxylic acid
- the removal composition includes 0.001 wt% to 5 wt% of an amino acid, amine
- polycarboxylic acid i.e., aminopolycarboxylic acid
- carboxylic acid i.e., aminopolycarboxylic acid
- the removal composition includes 0.001 wt% to 1 wt% of an amino acid, amine
- polycarboxylic acid i.e., aminopolycarboxylic acid
- carboxylic acid i.e., aminopolycarboxylic acid
- the removal composition includes 0.001 wt% to 0.607 wt% of an amino acid, amine polycarboxylic acid (i.e., aminopolycarboxylic acid), and/or carboxylic acid,
- polycarboxylic acid chelating agent or a mixture thereof.
- chelating agents include, but are not limited to, 1 ,2- cyclohexanediamine-N, N, N', N'-tetraacetic acid (CDTA); ethylenediaminetetraacetic acid; nitrilotriacetic acid; diethylene triamine pentaacetic acid; 1 ,4,7,10- tetraazacyclododecane-1 ,4,7,10-tetraacetic acid; ethylene glycol tetraacetic acid
- CDTA 1 ,2- cyclohexanediamine-N, N, N', N'-tetraacetic acid
- CDTA ethylenediaminetetraacetic acid
- nitrilotriacetic acid diethylene triamine pentaacetic acid
- 1 ,4,7,10- tetraazacyclododecane-1 ,4,7,10-tetraacetic acid ethylene glycol tetraacetic acid
- EGTA 1 ,2-bis(o-aminophenoxy)ethane-N,N,N', N'-tetraacetic acid
- HEDTA ethylenediamine- N,N'-bis(2-hydroxyphenylacetic acid)
- DOCTA dioxaoctamethylene dinitrilo tetraacetic acid
- TTHA triethylenetetraamine hexaacetic acid
- the addition of 1 ,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid to a removal composition having an ammonium carboxylate stabilizes the TiN etch rate up to at least 35hrs.
- the etch rate at 50°C of a removal composition having ammonium carboxylate without 1 ,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid may decrease 48% or even 54% after 35 hours.
- the ammonium carboxylate removal composition TiN etch rate at 50°C decreases 8% or less and in one embodiment decreases 0.4 %.
- 1 ,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid can be added to the removal composition.
- the amount of 1 ,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid can be tailored to achieve the desired stability.
- 1 ,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid is present in an amount from 0.0005 to 20 wt% based on the total weight percent of the removal composition. In one embodiment, 1 ,2-cyclohexanediamine-N, N, N', N'- tetraacetic acid is present in an amount from 0.0005 to 10 wt% based on the total weight percent of the removal composition. In one embodiment, 1 ,2- cyclohexanediamine-N, N, N', N'-tetraacetic acid is present in an amount from 0.001 to 10 wt% based on the total weight percent of the removal composition.
- 1 ,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid is present in an amount from 0.001 to 5 wt%. In another embodiment, 1 ,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid is present in an amount from 0.001 to 1 wt%. In another embodiment, 1 ,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid is present in an amount from 0.001 wt% to 0.607 wt%.
- a removal composition comprising
- the balance up to 100 wt% of the removal composition comprising deionized water stabilize the etch rate up to at least 35 hours.
- stabilize TiN etch rate up to at least 35 hours.
- stabilize TiN etch rateup to at least 35 hours at a selected operating temperature is from 20 to 60°C. In another embodiment, the selected operating temperature is between and including any two of the following temperature: 20, 30, 45, 50, 53 and 60°C.
- the addition of a chelating agent stabilizes the TiN etch rate such that TiN etch rate at 50 °C does not drop more than 23 A min at 24 hours. In some embodiemnts, the addition of a chelating agent stabilizes the TiN etch rate such that TiN hard mask etch rate at 50 °C does not drop more than 22.5 A min at 24 hours. In some embodiemnts, the addition of a chelating agent stabilizes the TiN etch rate such that TiN etch rate at 50 °C does not drop more than 20.5 A min at 24 hours. In some embodiemnts, the addition of a chelating agent stabilizes the TiN etch rate such that TiN etch rate at 50 °C does not drop more than 1 1 A/min at 24 hours.
- At least one corrosion inhibitor may also be present in the removal composition, for example, where the removal composition is to be deployed in semiconductor processing at BEOL applications and other applications where corrosion of copper or other metal components is a concern.
- the presence of a corrosion inhibitor is needed to protect metal surfaces from being etched or otherwise degraded.
- a corrosion inhibitor(s) is not generally needed, i.e., copper or colbalt, is not exposed to the removal chemistry, copper or colbalt is absent from the wafer substrate, or slight etching/degradation of copper or cobalt surfaces is not usually a concern.
- the metal (copper or colbalt) corrosion inhibitor is an organic compound, such as an azole, thiol, and/or indole preferably selected from the group consisting of a heterocyclic compound containing at least one nitrogen atom, such as, for example, a pyrrole and derivatives thereof, pyrazole and derivatives thereof, imidazole and derivatives thereof, triazole and derivatives thereof, indazole and derivatives thereof, and thiol-triazole and derivatives thereof, benzotriazole (BTA), tolyltriazole, 5-phenyl- benzotriazole, 5-nitro-benzotriazole, 3-amino-5 -mercapto-1 ,2,4-triazole, 1 -amino-1 ,2,4- triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1 -amino-1 ,2,3-triazole, 1 -amino-5-methyl-1 ,
- benzotriazole, pyrazole, or a mixture of benzotriazole and pyrazole, or a mixture of benzotriazole and tolyltriazole are preferred copper corrosion inhibitors for better removal performance.
- the copper or cobalt corrosion inhibitor or mixture thereof may be present in the composition at from 0.0001 wt% to 50 wt%. In another embodiments, the copper or cobalt corrosion inhibitor or mixture thereof is present in an amount from 0.0001 wt% to 10 wt%. In some embodiments, the copper or cobalt corrosion inhibitor or mixture thereof is present in an amount from 0.5 to 0.9 wt%. I In some embodiments, the copper or cobalt corrosion inhibitor or mixture thereof is present in an amount from 0.18 to 0.8 wt%. In another embodiment, the copper or cobalt corrosion inhibitor or mixture thereof is present in an amount from 0.18 to 0.65 wt%. Other suitable copper or cobalt corrosion inhibitors include, but are not limited to aromatic hydrazides and Schiff base compounds.
- the composition can contain one or more cosolvents that are miscible with water.
- Cosolvents enhance residue removal.
- Suitable cosolvents include, but are not limited to, sulfolane, N-methylpyrrolidone, and dimethylsulfoxide. pH adjustment
- the composition may also include a base or an acid, as appropriate, to adjust the pH of the working composition.
- the base can, for example, be selected from the group consisting of quaternary ammonium salts, such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide (BTAH) and mixtures thereof.
- the base can also be selected from the group consisting of primary, secondary and tertiary amines, such as, for example, monoethanol amine (MEA), diglycol amine (DGA), triethanolamine (TEA), tetrabutyphosphonium hydroxide (TBPH), and mixtures thereof.
- the base can be a combination of quaternary ammounium salts and amines.
- Suitable acids include, for example, are selected from the group consisting of inorganic acids, such as sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid (HF), or hydrobromic acid; organic acids, such as a carboxylic acid, an amino acid, a hydroxy carboxylic acid, a polycarboxylic acid, or a mixture of such acids.
- the pH of the working composition should be maintained at a value of from 2 to 14, but preferably in the range of from 3 to 12. As noted above, when used in BEOL Cu interconnect fabrication applications, the preferred pH of the working composition is in the range of from 5 to 1 1 when hydrogen peroxide is used as oxidizer in order to achieve high etch rates.
- aminopolycarboxylic acid and/or carboxylic acid, polycarboxylic acid chelating agent, or a mixture thereof;
- aminopolycarboxylic acid and/or carboxylic acid, polycarboxylic acid chelating agent, or a mixture thereof;
- aminopolycarboxylic acid and/or carboxylic acid, polycarboxylic acid chelating agent, or a mixture thereof;
- the carboxylate is an ammonium carboxylate.
- the ammonium carboxylate is selected from the group consisting of ammonium oxalate, ammonium lactate, ammonium tartrate, ammonium citrate tribasic, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, ammonium
- ethylenediaminetetraacetic acid diammonium ethylenediaminetetraacetic acid, triammonium ethylenediaminetetraacetic acid, tetraammonium
- kits including one or more containers comprising one or more components adapted to form the removal composition.
- the kit includes in one or more containers, comprising at least one carboxylate and deionized water for combining with an oxidizing agent at the point or fabrication or the point of use.
- the kit includes in one or more containers, comprising at least one carboxylate; deionized water; at least one copper corrosion inhibitor; and optionally comprising a base, a acid or mixture thereof for adjusting the pH; and optionally comprising at least one cosolvent for combining with an oxidizing agent at the point or fabrication or the point of use.
- the kit includes in one or more containers, comprising at least one carboxylate; deionized water; at least one amino acid, amine polycarboxylic acid (i.e., aminopolycarboxylic acid), and/or carboxylic acid, polycarboxylic acid chelating agent; and optionally comprising a base, a acid or mixture thereof for adjusting the pH; and optionally comprising at least one cosolvent for combining with an oxidizing agent at the point or fabrication or the point of use.
- amine polycarboxylic acid i.e., aminopolycarboxylic acid
- carboxylic acid polycarboxylic acid chelating agent
- optionally comprising a base, a acid or mixture thereof for adjusting the pH and optionally comprising at least one cosolvent for combining with an oxidizing agent at the point or fabrication or the point of use.
- the kit includes in one or more containers, comprising at least one carboxylate; deionized water; at least one copper corrosion inhibitor; at least one amino acid, amine polycarboxylic acid (i.e., aminopolycarboxylic acid), and/or carboxylic acid, polycarboxylic acid chelating agent; optionally comprising a base, a acid or mixture thereof for adjusting the pH; and optionally comprising at least one cosolvent for combining with an oxidizing agent at the point or fabrication or the point of use.
- amine polycarboxylic acid i.e., aminopolycarboxylic acid
- carboxylic acid polycarboxylic acid chelating agent
- optionally comprising a base, a acid or mixture thereof for adjusting the pH optionally comprising at least one cosolvent for combining with an oxidizing agent at the point or fabrication or the point of use.
- Removal composition is applied in any suitable manner to the semiconductor substrate.
- Contact or contacting the semiconductor substrate is intended to include spraying, dipping, using a pad or applicator that has the removal composition absorbed thereon or any other suitable manner of contacting the semiconductor substrate with a removal composition.
- the method for selectively removing an hard mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, Ti, including alloys of Ti or W, relative to underlying Low-k, Cu, Co, SiON, SICN, and TEOS materials from a
- the method comprises contacting the semiconductor substrate with a removal composition comprising:
- ammonium carboxylate selected from the group consisting of ammonium oxalate, ammonium lactate, ammonium tartrate, ammonium citrate tribasic, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, ammonium ethylenediaminetetraacetic acid, diammonium ethylenediaminetetraacetic acid, triammonium ethylenediaminetetraacetic acid, tetraammonium ethylenediaminetetraacetic acid, ammonium succinate,
- an ammonium carboxylate selected from the group consisting of ammonium oxalate, ammonium lactate, ammonium tartrate, ammonium citrate tribasic, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, ammonium ethylenediaminetetraacetic acid, diammonium ethylenediaminetetraacetic acid, triammonium ethylenedi
- ammonium formate ammonium 1 -H-pyrazole-3-carboxylate and mixtures thereof;
- the removal composition may additionally comprise at least one metal corrosion inhibitor. In some embodiments in accordance with any of the above methods, the removal composition may additionally comprise from 0.001 wt% to 20 wt% of an amino acid, an
- aminopolycarboxylic acid a carboxylic acid, a polycarboxylic acid, or a mixture thereof selected from the group consisting of 1 ,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid; ethylenediaminetetraacetic acid; nitrilotriacetic acid; diethylene triamine
- the removal composition may additionally comprise at least one base, at least one acid or mixture thereof; wherein the base is selected from the group consisting of quaternary
- ammonium salts primary amines, secondary amines, tertiary amines; and wherein the acid is selected from the group consisting of inorganic acids, organic acids or mixtures thereof.
- the removal composition may additionally comprise at least one base at least one acid or mixture thereof, wherein the base is selected from tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide (BTAH), monoethanol amine (MEA), diglycol amine (DGA), triethanolamine (TEA),
- TMAH tetramethylammonium hydroxide
- TEAH tetraethylammonium hydroxide
- BTAH benzyltrimethylammonium hydroxide
- MEA monoethanol amine
- DGA diglycol amine
- TAA triethanolamine
- TBPH tetrabutyphosphonium hydroxide
- the acid is selected from the group consisting of inorganic acids, organic acids or mixtures thereof.
- the method for removing a hard mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, Ti and alloys of Ti and W from a
- the method comprising contacting the semiconductor substrate with a removal composition comprising:
- the method additionally comprises the heating the removal composition up to 60°C. Heating the remoaval composition can occur prior to contacting the semiconductor substrate or after. In some embodiments, the method comprises contacting the semiconductor substrate with a removal composition for at least 2 minutes at a temperature from 20 to 45, 50, 53 or 60°C. In some embodiments, the method comprises contacting the semiconductor substrate with a removal compositionfor at least 2 minutes at a temperature up to 60°C.
- a composition formulated according to the present disclosure and exhibiting an inherently high etch rate for TiN, TaN, TiNxOy, TiW, W, Ti, including alloys of Ti and W, enables processing at relatively low temperature, e.g., temperatures less than 65°C.
- a relatively low temperature process exhibits a reduced oxidizer decomposition rate, which, in turn, extends the useful composition bath life and pot life.
- compositions according to the invention which exhibit high and selective etch rates for TiN, TaN, TiNxOy, TiW, W, Ti, including alloys of Ti and W are desirable because they can reduce device processing time and thereby increase throughput.
- Compositions according to the invention can effectively deliver high etch rates for TiN, TaN, TiNxOy, TiW, W, Ti, including alloys of Ti and W, with single wafer tool applications at a temperature range of from 20°C to 60°C, and the TiN, TaN, TiNxOy, TiW, W, Ti, including alloys of Ti and W, hard mask can be fully removed with single wafer application process equipment if so desired.
- the removal composition is at a temperature from 20 to 45, 50, 53 or 60°C and at a pH from 2 to 14. In some embodiments, the removal composition is at a temperature from 20 to 45, 50, 53 or 60°C and at a pH from 5 to 12. In some embodiments, the removal composition is at a temperature from 20, 30 or 45 to 50, 53 or 60°C and at a pH from 2 to 14.
- the removal composition is at a temperature from 20, 30 or 45 to 50, 53 or 60°C and at a pH from 5 to 12.
- the removal composition has an etch rate that is stabilized up to at least 35 hours at a selected operating temperature.
- the selected operating temperature is from 20 to 45, 50, 53 or 60°C.
- the concentration of ammonium carboxylate is from 0.001 wt% up to 50 wt%.
- compositions of the invention are effective in selectively removing an hard mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, Ti, including alloys of Ti and/or W, relative to Low-k, Cu, Co, SiON, SICN, and TEOS materials from a semiconductor substrate comprising said low-k dielectric material and having a TiN, TaN, TiNxOy, TiW, W, Ti, including alloys of Ti and/or W, hard mask thereon.
- the composition is also functional in simultaneously removing photoresist, polymeric materials, etching residues and copper oxide from the substrate.
- compositions and method according to the inventive concepts described herein are particularly applicable for processing single wafers in single wafer equipment.
- a high TiN etch rate is required, a common approach is to process wafers at high process temperatures.
- higher temperatures are known to contribute to degradation of the oxidizing agent which shortens bath life and pot life. It has been observed according to the inventive concepts described herein that satisfactory results can be achieved at substantially lower temperatures in the range of from 20°C to 60°C to generate a pullback scheme or to completely remove the hard mask when the hard mask comprises TiN.
- compositions of the invention may be embodied in a wide variety of specific
- composition and that in instances where such components are present, they may be present at concentrations as low as 0.0001 wt %, based on the total weight of the composition in which such components are employed.
- 100 g. samples of removal compositions were prepared according to the inventive concept(s) described herein. Each sample composition comprised each of the components listed in the various tables which follow at the weights shown in the corresponding formulation row.
- a 100 g. quantity of sample composition designated "1 " shown in Table 1 contained 2 g. of 10% aqueous ammonium tartrate, 7.21 g. of 10% aqueous DGA, 12.43 g. of 1 .5% aqueous BTA, 60 g. H2O2 (30% aqueous), and 18.36 g. deionized water (DIW).
- DIW deionized water
- the removal compositions can be formulated at the point of use, or they can be conveniently formulated beforehand without an oxidizer and then taken to the point of use where the oxidizer is added. There is also no particular sequence for mixing or blending the various ingredients.
- Blank wafers for determining etch rate were purchased as follows:
- Etch rate evaluations were carried out after 1 and 2 minutes of chemical treatment for TiN and 10 minutes for Cu, Co, W, and TEOS at the temperature noted in each example.
- TiN, Cu, Co, and W thicknesses were measured using a Four
- compositions shown in Table 1 were prepared using deionized water as the solvent, BTA or a mixture of BTA and pyrazole as Cu corrosion inhibitor, H 2 O2 as the oxidizing agent, and diglycolamine (DGA) or benzyltrimethylammonium hydroxide (BTAH) as the base to adjust pH.
- DGA diglycolamine
- BTAH benzyltrimethylammonium hydroxide
- Compositions 1 , 2 and 3 demonstrated a removal rate for TiN in the range of from 178 A min up to 340 A/min at a relatively low temperature in the range of from 50°C to 53°C. A copper etch rate of less than 3 A/min is considered good for commercial wafer processing.
- Figs. 1 A and 1 B are SEM images of semiconductor wafer segments which show trenches and vias, respectively, as received following a dual damascene fabrication step, but before treatment with a removal compositon.
- Figs. 2A and 2B are views of the wafer segments, similar to the wafer segments shown in Figs. 1A and 1 B, after contact with removal composition 1 for 90 sec. at a
- Figs. 3A and 3B are views of wafer segments, similar to the wafer segments shown in Figs. 1 A and 1 B, after contact with removal composition 2 for 90 sec. at a temperature of 50°C wherein TiN hard mask and residue have been
- FIGs. 4a and 4B are views of wafer segments, similar to the wafer segments shown in Figs. 1 A and 1 B, after contact with removal composition 3 for 90 sec. at a temperature of 53°C. TiN hard mask and residue have been completely removed.
- compositions shown in Table 2 were prepared using deionized water as the solvent, BTA as Cu corrosion inhibitor, H2O2 as the oxidizing agent, and
- TMAH tetramethylammonium hydroxide
- composition 4 that did not contain an ammonium carboxylate.
- the formulations shown in Table 4 were prepared using DGA to adjust the pH, and BTA was used as the copper corrosion inhibitor.
- TiN and Cu etch rate evaluations were carried out as described above at a temperature of 50°C and pH of 8. The removal compositions demonstrated a higher TiN etch rate and a similar Cu etch rate when compared to the control, composition 13, that did not contain an ammonium carboxylate.
- Table 5 The formulations shown in Table 5 were prepared using TMAH to adjust the pH, and BTA was used as the copper corrosion inhibitor. TiN and Cu etch rate evaluations were carried out as described above at a temperature of 50°C and pH of 8. The removal compositions demonstrated a higher TiN etch rate and a similar Cu etch rate when compared to the control, composition 17, that did not contain an ammonium carboxylate. Table 5
- BTAH benzyltrimethylammonium hydroxide
- compositions demonstrated a higher TiN etch rate and a similar Cu etch rate when compared to the control, composition 21 , that did not contain an ammonium
- the formulations shown in Table 7 were prepared using tetraethylammonium hydroxide (TEAH) to adjust the pH, and BTA was used as the copper corrosion inhibitor.
- TEAH tetraethylammonium hydroxide
- TiN and Cu etch rate evaluations were carried out as described above at a temperature of 50°C and pH of 8. The removal compositions demonstrated a higher TiN etch rate and a similar Cu etch rate when compared to the control, composition 25, that did not contain an ammonium carboxylate.
- ammonium carbonate, ammonium acetate, ammonium oxalate, ammonium lactate and ammonium tartrate at concentrations of from 1 .46 wt % to less than 3 wt% operate to provide the removal compositions of the invention with the capability to deliver very high TiN etch rates at relatively low temperature, e.g., 50°C. It is noteworthy according to the described and claimed inventive concepts that none of the ammonium carbonate, ammonium acetate, ammonium oxalate, ammonium lactate or ammonium tartrate had significant effect on TEOS removal rate when compared to the control, composition 31 . Table 8
- the formulations shown in Table 9 were prepared without the use of a pH adjustment agent.
- the Cu corrosion inhibitor used was Wintrol A-90, a commercial mixture of BTA and tolyltriazole.
- the desired TiN and Cu etch rates and pH were obtained by varying hydrogen peroxide and ammonium carboxylate concentrations. In these examples, several carboxylates in various concentrations were used. Hydrogen peroxide concentration was either 20 wt% or 80 wt%.
- the formulation pH's ranged from a low of pH 4.3 up to pH 8.3, and the TiN etch rate, i.e., the removal rate, ranged from a low of 1 1 A min up to 228 A min.
- Table 10 The formulations shown in Table 10 were prepared with tartaric acid, or TMAH, or without any pH adjustment agent. Wintrol A-90 was used as a Co corrosion inhibitor In these examples, several carboxylates in various concentrations were used.
- Hydrogen peroxide concentration ranged from 10 wt% to 80 wt%.
- the formulation pH ranged from a low of pH 5 up to pH 10.
- the Co etch rate was insignificant in all cases (i.e., the highest Co etch rate was 1 .48 A min ).
- the formulations shown in Table 12 were prepared using TMAH to adjust the pH, and BTA was used as copper corrosion inhibitor.
- Carboxylates used were potassium citrate tribasic monohydrate, potassium sodium tartrate tetrahydrate, and
- compositions 56, 57 and 58 were prepared in compositions 56, 57 and 58, respectively. Each of these compositions demonstrated a higher TiN etch rate and a similar Cu etch rate when compared to the control, composition 55, that did not contain a carboxylate.
- Table 15 The formulations shown in Table 15 were prepared, and W (tungsten) etch rate evaluations were carried out at temperatures of 45°C and 55°C as described above in connection with TiN removal. Table 15
- Table 15 demonstrates the presence of ammonium carboxylate at a
- concentration of 1 .172 wt% to 3 wt% and at a pH ranging from about 4 to slightly higher than 1 1 was shown to significantly increase the W removal rate when compared to the corresponding ammonium carboxy late-free control compositions 66, 70 and 72 at the same pH.
- Pot life is a measure of the ability of the removal composition formula to perform optimally over time and without significant variation in functionality over time. Pot life is a strong function of temperature. After many hours of treatment at high temperature, the chemicals in the mixture can decompose and the formula will lose functionality.
- CDTA 1,2-cyclohexanediamine-N, N, ⁇ ', N'- tetraacetic acid
- the data presented in Table 17 demonstrates that with CDTA in removal compositions 74 and 75, the TiN etch rate remained stable, i.e., substantialy constant, over a period of 22 hours.
- the initial TiN etch rate was 157 A min, and it remained at 156 .4 A/min for composition 75 over a 22 hour period.
- the initial TiN etch rate was 168.1 A/min and remained at 156.6 A/min over a 22 hour period.
- the TiN etch rate declined from an initial etch rate of 219 A/min to an etch rate of 99.9 A/min at 22 hours.
- the data presented in Table 19 demonstrates that with CDTA in removal compositions 77, the TiN etch rate remained stable, i.e., substantialy constant, over a period of 35 hour.
- the initial TiN etch rate was 174 A min, and it is at 160 A/min for composition 77 at 35 hour period.
- the TiN etch rate declined from an initial etch rate of 212 A/min to an etch rate of 1 10 A/min at 35 hours.
- ethylenediaminetetraacetic acid was selected as the ammonium carboxylate at a concentration of specified in Table 20.
- 1 ,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid (CDTA) was selected as the aminopolycarboxylic acid chelating agent in
- the data presented in Table 21 demonstrates that with CDTA in removal compositions 79, 80 and 81 , the TiN etch rate remained stable, i.e., substantialy constant, over a period of 35 hours.
- the initial TiN etch rate was 192 A min, and it is at 176 A/min for composition 79 over a 35 hour period.
- the initial TiN etch rate was 181 A/min and is at 171 A/min over a 35 hour period.
- the initial TiN etch rate was 167 A/min and is at 160 A/min over a 35 hour period.
- Removal compositions were prepared according to the described and claimed inventive concept(s) wherein ammonium tartrate was selected as the ammonium carboxylate at a concentration of 0.3 wt%.
- 1 ,2-cyclohexanediamine-N, N, ⁇ ', N'- tetraacetic acid (CDTA) was selected as the aminopolycarboxylic acid chelating agent in formulation 82 and 83.
- the compositions are shown in Table 22. Samples were taken from the removal compositions at intervals of 0, 4, 8, 24, 28, 32 and 35 hours to measure TiN and Cu etch rates. Results are shown in Table 23.
- the data presented in Table 23 demonstrates that with 0.001 % and 0.005% of CDTA in removal compositions 82 and 83, respectively, the TiN etch rate remained stable, i.e., substantialy constant, over a period of 35 hours.
- the initial TiN etch rate was 42 A/min, and it remained at 36 A/min for composition 82 over a 35 hour period(16.67% reduced TiN etch rate).
- the initial TiN etch rate was 48 A/min and remained at 45 A/min over a 35 hour period(6.3% reduced TiN etch rate).
- control formulation 84 without CDTA the initial TiN etch rate was 47 A/min, and it is at 30 A/min for over a 35 hour period which shows a 36% reduced TiN etch rate.
- CDTA stabilizes TiN etch rate.
- the formulations shown in Table 24 were prepared using TEAH to adjust the pH, and BTA was used as copper corrosion inhibitor. CDTA was used to stabilize TiN etch rate.
- the data presented in Table 25 demonstrate that with 1 %, 2% and 3% CDTA in removal compositions 85, 86 and 87, respectively, the TiN etch rate remained stable, i.e., substantialy constant, over a period of 35 hours.
- the initial TiN etch rate was 170 A min, and it remained at 159 A/min for composition 85 at a 35 hour period.
- the initial TiN etch rate was 170 A/min and remained at 158 A/min at 35 hour period.
- the initial TiN etch rate was 178A/min and remained at 166 A/min at 35 hour period.
- control formulation 88 without CDTA the initial TiN etch rate was 233 A/min, and it is at 136 A/min for over a 35 hour period.
- ethylenediaminetetraacetic acid was used to stabilize the TiN etch rate.
- Table 27 demonstrates that with tetraammoniunn ethylenediaminetetraacetate in removal composition 89, the TiN etch rate remained stable, i.e., remained
- composition 90 without Tetraammonium
- the etch rate dropped from an initial rate of 143 A/min to a rate of 57 A/min after 35 hours (60% TiN etch rate drop after 35 hours).
- Tetraammonium ethylenediaminetetraacetate stabilizes TiN etch rate.
- the formulations in Table 28 were prepared using DGA to adjust pH . BTA was used as copper corrosion inhibitor. The ammonium carboxylate selected was tetraammonium EDTA. The results shown in Table 28 indicate that Tetraammonium ethylenediaminetetraacetate in removal composition 81 exhibited a higher TiN etch rate when compared to the control, composition 82, which contained no ammonium carboxylate.
- the initial TiN etch rate was 233 A/min, and it is 198 A/min at twenty eight (28) hour period.
- the TiN etch rate dropped from an initial rate of 134 A min to a rate of 61 A min at 28 hours.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/028,501 US10155921B2 (en) | 2013-10-11 | 2014-10-09 | Removal composition for selectively removing hard mask and methods thereof |
JP2016522060A JP6523269B2 (en) | 2013-10-11 | 2014-10-09 | Removal composition for selectively removing hard masks |
CN201480055151.5A CN105612599B (en) | 2013-10-11 | 2014-10-09 | The removal composition of hard mask is removed for selectivity |
KR1020167012242A KR102327432B1 (en) | 2013-10-11 | 2014-10-09 | Removal composition for selectively removing hard mask |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361889968P | 2013-10-11 | 2013-10-11 | |
US61/889,968 | 2013-10-11 | ||
US14/103,303 | 2013-12-11 | ||
USPCT/US2013/074356 | 2013-12-11 | ||
US14/103,303 US20150104952A1 (en) | 2013-10-11 | 2013-12-11 | Method and composition for selectively removing metal hardmask and other residues from semiconductor device substrates comprising low-k dielectric material and copper |
PCT/US2013/074356 WO2015053800A2 (en) | 2013-10-11 | 2014-11-14 | Method and composition for selectively removing metal hardmask and other residues from semiconductor device substrates comprising low-k dielectric material and copper |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015054460A1 true WO2015054460A1 (en) | 2015-04-16 |
Family
ID=52813633
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2014/059840 WO2015054460A1 (en) | 2013-10-11 | 2014-10-09 | Removal composition for selectively removing hard mask |
PCT/US2014/059848 WO2015054464A1 (en) | 2013-10-11 | 2014-10-09 | Removal composition for selectively removing hard mask and methods thereof |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2014/059848 WO2015054464A1 (en) | 2013-10-11 | 2014-10-09 | Removal composition for selectively removing hard mask and methods thereof |
Country Status (1)
Country | Link |
---|---|
WO (2) | WO2015054460A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016213461A (en) * | 2015-05-01 | 2016-12-15 | エア プロダクツ アンド ケミカルズ インコーポレイテッドAir Products And Chemicals Incorporated | Titanium nitride hard mask and etch residue removal |
JP2017162967A (en) * | 2016-03-09 | 2017-09-14 | 株式会社Adeka | Etchant composition for tantalum-containing layer, and etching method |
EP4029050A4 (en) * | 2019-09-10 | 2022-10-12 | FUJIFILM Electronic Materials U.S.A, Inc. | Etching composition |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113430072B (en) * | 2020-03-23 | 2024-05-07 | 上海新阳半导体材料股份有限公司 | Cobalt-compatible semi-aqueous cleaning solution for removing hard mask, preparation method and application thereof |
CN115725369B (en) * | 2022-11-03 | 2024-03-08 | 上海新阳半导体材料股份有限公司 | Application of cleaning fluid composition |
CN116042331B (en) * | 2022-11-11 | 2024-03-08 | 上海新阳半导体材料股份有限公司 | Application of cleaning liquid |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0292057A1 (en) * | 1987-05-18 | 1988-11-23 | Koninklijke Philips Electronics N.V. | Method of manufacturing a semiconductor comprising a titanium-tungsten layer |
US20010003061A1 (en) * | 1999-08-30 | 2001-06-07 | Gary Chen | Manufacture and cleaning of a semiconductor |
JP2006339509A (en) * | 2005-06-03 | 2006-12-14 | Tosoh Corp | Composition for etching metal titanium and etching method using it |
EP2234145A1 (en) * | 2007-12-21 | 2010-09-29 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
EP2322692A1 (en) * | 2008-09-09 | 2011-05-18 | Showa Denko K.K. | Etchant for titanium-based metal, tungsten-based metal, titanium-tungsten-based metal or nitrides thereof |
US8080475B2 (en) | 2009-01-23 | 2011-12-20 | Intel Corporation | Removal chemistry for selectively etching metal hard mask |
KR20120051488A (en) * | 2010-11-12 | 2012-05-22 | 오씨아이 주식회사 | Composition for etching metal layer |
US20120153287A1 (en) * | 2010-12-15 | 2012-06-21 | Dongwoo Fine-Chem Co., Ltd. | Etchant, display device and method for manufacturing display device using the same |
WO2013101907A1 (en) * | 2011-12-28 | 2013-07-04 | Advanced Technology Materials, Inc. | Compositions and methods for selectively etching titanium nitride |
-
2014
- 2014-10-09 WO PCT/US2014/059840 patent/WO2015054460A1/en active Application Filing
- 2014-10-09 WO PCT/US2014/059848 patent/WO2015054464A1/en active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0292057A1 (en) * | 1987-05-18 | 1988-11-23 | Koninklijke Philips Electronics N.V. | Method of manufacturing a semiconductor comprising a titanium-tungsten layer |
US20010003061A1 (en) * | 1999-08-30 | 2001-06-07 | Gary Chen | Manufacture and cleaning of a semiconductor |
JP2006339509A (en) * | 2005-06-03 | 2006-12-14 | Tosoh Corp | Composition for etching metal titanium and etching method using it |
EP2234145A1 (en) * | 2007-12-21 | 2010-09-29 | Wako Pure Chemical Industries, Ltd. | Etching agent, etching method and liquid for preparing etching agent |
EP2322692A1 (en) * | 2008-09-09 | 2011-05-18 | Showa Denko K.K. | Etchant for titanium-based metal, tungsten-based metal, titanium-tungsten-based metal or nitrides thereof |
US8080475B2 (en) | 2009-01-23 | 2011-12-20 | Intel Corporation | Removal chemistry for selectively etching metal hard mask |
KR20120051488A (en) * | 2010-11-12 | 2012-05-22 | 오씨아이 주식회사 | Composition for etching metal layer |
US20120153287A1 (en) * | 2010-12-15 | 2012-06-21 | Dongwoo Fine-Chem Co., Ltd. | Etchant, display device and method for manufacturing display device using the same |
WO2013101907A1 (en) * | 2011-12-28 | 2013-07-04 | Advanced Technology Materials, Inc. | Compositions and methods for selectively etching titanium nitride |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016213461A (en) * | 2015-05-01 | 2016-12-15 | エア プロダクツ アンド ケミカルズ インコーポレイテッドAir Products And Chemicals Incorporated | Titanium nitride hard mask and etch residue removal |
US9976111B2 (en) | 2015-05-01 | 2018-05-22 | Versum Materials Us, Llc | TiN hard mask and etch residual removal |
US10711227B2 (en) | 2015-05-01 | 2020-07-14 | Versum Materials Us, Llc | TiN hard mask and etch residue removal |
JP2017162967A (en) * | 2016-03-09 | 2017-09-14 | 株式会社Adeka | Etchant composition for tantalum-containing layer, and etching method |
EP4029050A4 (en) * | 2019-09-10 | 2022-10-12 | FUJIFILM Electronic Materials U.S.A, Inc. | Etching composition |
US11499099B2 (en) | 2019-09-10 | 2022-11-15 | Fujifilm Electronic Materials U.S.A., Inc. | Etching composition |
Also Published As
Publication number | Publication date |
---|---|
WO2015054464A1 (en) | 2015-04-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10155921B2 (en) | Removal composition for selectively removing hard mask and methods thereof | |
KR102266832B1 (en) | TiN HARD MASK AND ETCH RESIDUE REMOVAL | |
US9972485B2 (en) | Method and composition for removing resist, etch residue, and copper oxide from substrates having copper, metal hardmask and low-k dielectric material | |
KR101444468B1 (en) | Oxidizing aqueous cleaner for the removal of post-etch residues | |
TWI525701B (en) | Method and composition for removing resist, etch residue, and copper oxide from substrates having copper, metal hardmask and low-k dielectric material | |
WO2015054460A1 (en) | Removal composition for selectively removing hard mask | |
JP2008546036A (en) | Metal and dielectric compatible sacrificial antireflective coating purification and removal composition | |
TW201348405A (en) | Methods for the selective removal of ashed spin-on glass | |
WO2018136466A1 (en) | Post-etch residue removal for advanced node beol processing | |
CN109642159B (en) | Non-aqueous tungsten compatible metal nitride selective etchants and cleaners | |
CN113430060B (en) | Tungsten compatible cleaning solution for removing hard mask, preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14819110 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016522060 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15028501 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20167012242 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14819110 Country of ref document: EP Kind code of ref document: A1 |