TW201522574A - 用於自包含低k介電材料及銅的半導體裝置基材選擇性移除金屬硬遮罩及其他殘留物的方法和組成物 - Google Patents
用於自包含低k介電材料及銅的半導體裝置基材選擇性移除金屬硬遮罩及其他殘留物的方法和組成物 Download PDFInfo
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- TW201522574A TW201522574A TW103100235A TW103100235A TW201522574A TW 201522574 A TW201522574 A TW 201522574A TW 103100235 A TW103100235 A TW 103100235A TW 103100235 A TW103100235 A TW 103100235A TW 201522574 A TW201522574 A TW 201522574A
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- Prior art keywords
- ammonium
- acid
- composition
- weight
- tin
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- 239000000203 mixture Substances 0.000 title claims abstract description 216
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000000758 substrate Substances 0.000 title claims abstract description 23
- 239000004065 semiconductor Substances 0.000 title claims abstract description 22
- 239000010949 copper Substances 0.000 title claims description 68
- 229910052802 copper Inorganic materials 0.000 title claims description 37
- 229910052751 metal Inorganic materials 0.000 title claims description 29
- 239000002184 metal Substances 0.000 title claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 19
- 239000003989 dielectric material Substances 0.000 title claims description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 91
- -1 carboxylate compound Chemical class 0.000 claims abstract description 59
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 34
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- 239000000956 alloy Substances 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000005530 etching Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 27
- 238000005260 corrosion Methods 0.000 claims description 27
- 230000007797 corrosion Effects 0.000 claims description 27
- 239000003112 inhibitor Substances 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 15
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-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 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000004251 Ammonium lactate Substances 0.000 claims description 12
- 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 12
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 12
- 229940059265 ammonium lactate Drugs 0.000 claims description 12
- 235000019286 ammonium lactate Nutrition 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
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 11
- 239000005695 Ammonium acetate Substances 0.000 claims description 11
- 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 11
- 229940043376 ammonium acetate Drugs 0.000 claims description 11
- 235000019257 ammonium acetate Nutrition 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 11
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 11
- 229960001484 edetic acid Drugs 0.000 claims description 11
- 150000001413 amino acids Chemical class 0.000 claims description 10
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 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 8
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 8
- 239000001393 triammonium citrate Substances 0.000 claims description 8
- 235000011046 triammonium citrate Nutrition 0.000 claims description 8
- 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 7
- 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 7
- 229940090948 ammonium benzoate Drugs 0.000 claims description 7
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- 229910020366 ClO 4 Inorganic materials 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
- XNSPQPOQXWCGKC-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[N] Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[N] XNSPQPOQXWCGKC-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000006184 cosolvent Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 4
- 229960003330 pentetic acid Drugs 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-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
- 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 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 229910008599 TiW Inorganic materials 0.000 claims description 3
- 229910001080 W alloy Inorganic materials 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
- 229910001919 chlorite Inorganic materials 0.000 claims description 3
- 229910052619 chlorite group Inorganic materials 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940009662 edetate Drugs 0.000 claims description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 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
- 150000002978 peroxides Chemical class 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 2
- WBWLSSNGIDBRRM-UHFFFAOYSA-N O=C(C1=CC=CC=C1)[SH]=O Chemical compound O=C(C1=CC=CC=C1)[SH]=O WBWLSSNGIDBRRM-UHFFFAOYSA-N 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- MOOSBPSAZDOBSN-UHFFFAOYSA-N acetic acid;azane Chemical compound N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O MOOSBPSAZDOBSN-UHFFFAOYSA-N 0.000 claims 1
- ZDHQEHHEAFGBFJ-UHFFFAOYSA-N azanium 1H-pyrazole-5-carboxylate Chemical compound [NH4+].[O-]C(=O)C=1C=CNN=1 ZDHQEHHEAFGBFJ-UHFFFAOYSA-N 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 229960004106 citric acid Drugs 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000000267 glycino group Chemical group [H]N([*])C([H])([H])C(=O)O[H] 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- MSTBIMHNYHDDGU-UHFFFAOYSA-M hydrogen sulfate tetrabutylazanium hydrate Chemical compound O.OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC MSTBIMHNYHDDGU-UHFFFAOYSA-M 0.000 claims 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims 1
- 239000001384 succinic acid Substances 0.000 claims 1
- 229960005137 succinic acid Drugs 0.000 claims 1
- 238000009472 formulation Methods 0.000 description 23
- 239000012964 benzotriazole Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 18
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 230000009977 dual effect Effects 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000002738 chelating agent Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 150000007942 carboxylates Chemical class 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 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 description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
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- 239000005751 Copper oxide Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
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- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010586 diagram 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
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-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
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 2
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- BYPIKLIXBPMDBY-DKWTVANSSA-N (2s)-2-hydroxypropanoic acid;potassium Chemical compound [K].C[C@H](O)C(O)=O BYPIKLIXBPMDBY-DKWTVANSSA-N 0.000 description 1
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- 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
- 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
- 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
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- USYLIGCRWXYYPZ-UHFFFAOYSA-N [Cl].[Fe] Chemical compound [Cl].[Fe] USYLIGCRWXYYPZ-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
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HQFQTTNMBUPQAY-UHFFFAOYSA-N cyclobutylhydrazine Chemical compound NNC1CCC1 HQFQTTNMBUPQAY-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 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
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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
- 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 description 1
- 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 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- VRFQDZQUTDJJMF-UHFFFAOYSA-N toluene;2h-triazole Chemical compound C1=CNN=N1.CC1=CC=CC=C1 VRFQDZQUTDJJMF-UHFFFAOYSA-N 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/34—Alkaline compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
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Abstract
本發明係關於自其上具有TiN、TaN、TiNxOy、TiW、W或Ti或W之合金蝕刻遮罩且包括低k材料之半導體基材相對該等低k材料選擇性移除主要由TiN、TaN、TiNxOy、TiW、W或Ti或W之合金組成之蝕刻遮罩的具有在2至14之範圍內的pH的水性移除組成物及方法,其中該移除組成物包括至少一種氧化劑及羧酸鹽化合物。
Description
該申請案主張2013年10月11日申請之美國臨時申請案號61/889,968之權益,其全文係藉由引用之方式併入本文中。
當前所揭示及主張之本發明概念係關於自積體電路(IC)裝置基材選擇性移除金屬硬遮罩及其他殘留物的組成物及方法,及更特定言之,關於利用羧酸鹽化合物,自包括低k介電材料、TEOS、銅、鈷及其他低k介電材料之該等基材選擇性移除TiN、TaN、TiNxOy、TiW及W金屬硬遮罩及包括以上之合金的硬遮罩以及其他殘留物的組成物及方法。
具有約90奈米(nm)之臨界尺寸的裝置已涉及銅導體及低k介電質之集成,及其需要交替的材料沈積製程及平坦化製程。電漿乾式蝕刻在銅(Cu)/低k雙重鑲嵌製程中常用於製造垂直側壁溝槽及各向異性互連介層孔。由於技術節點提高至45nm及更小,因此半導體裝置之縮小尺寸使得實現介層孔及溝槽之臨界輪廓控制更具挑戰性。積體電路裝置公司正在研究各種金屬硬遮罩於改進對低k材料之蝕刻選擇性及
由此獲得更佳的輪廓控制的用途。
為了獲得高產率及低電阻,必須在下一製程步驟之前移除在蝕刻期間產生之位於側壁上之聚合物殘留物及位於介層孔底部的顆粒/聚合物殘留物。若清潔溶液亦可有效地蝕刻金屬硬遮罩而形成一種中間形態(例如,拉回/磨圓的形態),或完全移除該金屬硬遮罩,則將極為有利。拉回/磨圓的形態可預防底切硬遮罩,此可進一步實現屏障金屬、Cu晶種層及Cu填充物之可靠沈積。或者,利用相同組成物完全移除金屬硬遮罩可藉由省去屏障CMP而對下游製程步驟(特別化學機械拋光(CMP))提供諸多益處。
在製造製程中之幾乎每一步驟(例如平坦化步驟、光微影術步驟或蝕刻步驟)之後,需要清潔製程以移除電漿蝕刻殘留物、光阻劑、氧化劑、研磨物、金屬及/或殘留且若不有效地移除則可污染裝置表面的其他液體或顆粒。需要銅導體及低k介電材料(一般而言摻雜碳之氧化矽(SiOCH),或多孔低k材料)之高級一代的裝置的製造產生兩種材料均可與不同類別的先前技術清潔劑反應且被其損壞的問題。
特定而言,如蝕刻、孔隙率/尺寸之變化及介電性質之最終變化所證明,低k介電質可在清潔製程中被損壞。移除殘留物之所需時間取決於殘留物之性質、產生其之製程(加熱、交聯、蝕刻、烘烤及/或灰化)及是否可使用批次或單晶圓清潔製程。有些殘留物可在極短的時間內被清潔,而有些殘留物需要長久得多的清潔程序。在與清潔劑之接觸的持續時間中與低k介電質及銅導體兩者的相容性為所需特性。
在後段製程(BEOL)IC製造製程(即雙重鑲嵌製程)期間,TiN、TaN、TiNxOy、TiW及/或W(包括Ti及W之合金)係在乾蝕刻步驟期間於形成介層孔及溝槽中用作蝕刻硬遮罩以獲得對低k介電材料之高選擇性。要求有效清潔組成物可選擇性移除TiN、TaN、TiNxOy、TiW
或W;與低k材料、銅、鈷及其他介電材料相容及亦自所得雙重鑲嵌結構同時移除非所欲的蝕刻殘留物及Cu氧化物組成物。除了選擇性清潔,亦非常希望清潔組成物之可達到之移除速率(Å/min)在延續時段中實質上維持恒定。
隨著裝置臨界尺寸之持續縮小及對於高製造效率及可靠的裝置性能的相應要求,需要該等改進的清潔組成物。
當前揭示及主張之本發明概念係關於一種具有一或多種羧酸鹽化合物之改進的半導體加工組成物(即濕式清潔化學劑或移除組成物),其自雙重鑲嵌結構高度選擇性移除金屬硬遮罩而不損壞布線金屬及介電材料。在雙重鑲嵌後段金屬化中製造之該類半導體基材係由藉由夾層介電質分隔之多層或級別的金屬互連件組成。所述組成物可自介層孔及溝槽表面移除金屬硬遮罩殘留物、光阻劑、聚合材料及氧化銅而不損壞形成該結構的底層。該等基材一般包括銅、鈷、低k介電材料、SiON、SiCN、TEOS及選自TiN、TaN、TiNxOy、TiW及W(包括Ti及W之合金)之金屬硬遮罩。該移除組成物包括0.1重量%至90重量%之至少一種氧化劑、0.0001重量%至50重量%之羧酸鹽化合物、補足至100重量%之該移除組成物的剩餘部分,其包括水(例如去離子水)。
發現根據文中所述之本發明概念而產生極佳結果的羧酸鹽化合物為羧酸銨。羧酸銨之實例為草酸銨、乳酸銨、酒石酸銨、檸檬酸三銨、乙酸銨、胺基甲酸銨、碳酸銨、苯甲酸銨、乙二胺四乙酸四銨(tetraammonium EDTA)、乙二胺四乙酸二胺鹽、丁二酸銨、甲酸銨、1-H-吡唑-3-羧酸銨及其混合物。羧酸銨化合物在本發明移除組成物中之存在不僅增加以下實例中所示之TiN蝕刻速率,而且資料支持其存在亦用於在延長之時段(例如長達至少35小時)中穩定可達到的TiN蝕刻速率的結論。
儘管實行本發明未作要求,但至少一種腐蝕抑制劑亦可存在於該組成物中,例如,在該組成物待用於BEOL應用之半導體加工及其中涉及Cu或其他金屬組件之腐蝕的其他應用的情況中。
該組成物亦可包括(例如)選自由季銨盐(諸如四甲基氫氧化銨(TMAH)、四乙基氫氧化銨(TEAH)及苄基三甲基氫氧化銨(BTAH))及其混合物組成之群之鹼。該鹼亦可選自一級、二級或三級胺(諸如(例如),单乙醇胺(MEA)、二乙醇胺(DGA)、三乙醇胺(TEA))及四丁基氫氧化鏻(TBPH)及其混合物。此外,該組成物可包括一或多種酸,例如無機酸,諸如硫酸、硝酸、磷酸、氫氟酸(HF)或氫溴酸;或有機酸,諸如羧酸、羥基羧酸、聚羧酸、胺基酸;或該等酸之混合物,適當地將工作組成物之pH調整至2至14(但較佳在3至13之範圍內)的數值。在一個較佳實施例中,對於涉及Cu互連件製造的應用而言,該移除組成物的pH較佳在7至12之範圍內。
該組成物亦可包括0.001重量%至20重量%之胺基酸、聚羧酸胺(即胺基聚羧酸)及/或羧酸、聚羧酸螯合劑或其混合物,已經觀察到其與羧酸鹽化合物一起穩定該組成物。文中所用之術語「穩定」意指對硬遮罩之可達到的蝕刻速率(例如,對TiN之148Å/min之移除速率)在所選操作溫度(例如,50℃之操作溫度)下在延長之時段(例如二十二(22)小時及長達三十五(35)小時或更長的時段)中實質上維持恒定。
適用於進行本發明概念的氧化劑可選自由過氧化氫(H2O2)、過氧化苯甲醯、過氧單硫酸四丁銨、臭氧、n-甲基嗎啉氧化物(NMMO、NMO)、氯化鐵、過錳酸鹽、過氧硼酸鹽、過氯酸鹽、過硫酸鹽、過氧二硫酸銨、過氧乙酸、氫過氧化脲、過碳酸鹽、過硼酸鹽及其混合物組成之群。當氧化劑為過氧化氫(H2O2)時,已經觀察到最佳的結果。
在另一實施例中,本發明包括一種自其上具有TiN、TaN、
TiNxOy、TiW或W蝕刻遮罩(包括含有Ti或W之合金的蝕刻遮罩)之半導體基材相對底部低k、Cu、Co、SiON、SlCN及TEOS材料選擇性移除主要由TiN、TaN、TiNxOy、TiW或W(包括Ti或W之合金)組成之蝕刻遮罩的方法,其中該方法包括使包括如下之移除組成物與該基材在室溫至高達80℃之範圍內的溫度及在2至14之範圍內的pH下接觸:(a)0.1重量%至90重量%之至少一種氧化劑;(b)0.0001重量%至高達50重量%之羧酸銨,其係選自包括草酸銨、乳酸銨、酒石酸銨、檸檬酸三銨、乙酸銨、胺基甲酸銨、碳酸銨、苯甲酸銨、乙二胺四乙酸銨、乙二胺四乙酸二胺鹽、丁二酸銨、甲酸銨及1-H-吡唑-3-羧酸銨中之一或多種之群組;及(c)補足至100重量%之該移除組成物的剩餘部分,其包括去離子水,其中該移除組成物相對該低k、Cu、Co、TEOS及其他介電材料選擇性移除該TiN、TaN、TiNxOy、TiW或W(包括Ti及/或W之合金)蝕刻遮罩。
在另一實施例中,本發明包括一種自其上具有TiN、TaN、TiNxOy、TiW或W蝕刻遮罩(包括含有Ti及/或W之合金的蝕刻遮罩)之半導體基材相對底部低k、Cu、Co、SiON、SlCN及TEOS材料選擇性移除主要由TiN、TaN、TiNxOy、TiW或W(包括Ti及/或W之合金)組成之蝕刻遮罩的方法,其中該方法包括使包括如下之移除組成物與該基材在室溫至高達80℃之範圍內的溫度及在2至14之範圍內的pH下接觸:(a)0.1重量%至90重量%之至少一種氧化劑;(b)0.0001重量%至高達50重量%之羧酸銨,其係選自包括草酸銨、乳酸銨、酒石酸銨、柠檬酸三銨、乙酸銨、胺基甲酸銨、碳酸銨、苯甲酸銨、乙二胺四乙酸銨、乙二胺四乙酸二胺盐、丁二酸銨、甲酸銨及1-H-吡唑-3-羧酸銨中之一或多種之群組;
(c)0.001重量%至20重量%之胺基酸、聚羧酸胺(即胺基聚羧酸)及/或羧酸、聚羧酸螯合劑或其混合物;及(d)補足至100重量%之該移除組成物的剩餘部分,其包括去離子水,其中該移除組成物相對該低k、Cu、Co、TEOS及其他介電材料選擇性移除該TiN、TaN、TiNxOy、TiW及W(包括Ti及W之合金)蝕刻遮罩,及移除該蝕刻遮罩之速率在可長達三十五(35)個小時或更長的延續時段中維持恒定。
在另一實施例中,該(等)所述及主張之本發明概念涵蓋一種對自其上具有TiN、TaN、TiNxOy、TiW或W蝕刻遮罩(包括含有Ti或W之合金的蝕刻遮罩)之半導體基材相對底部低k、Cu、Co、SiON、SlCN及TEOS材料選擇性移除主要由TiN、TaN、TiNxOy、TiW或W(包括Ti或W之合金)組成之蝕刻遮罩的組成物及方法的改進,其中該改進包括將0.0001重量%至50重量%之選自包括草酸銨、乳酸銨、酒石酸銨、檸檬酸三銨、乙酸銨、胺基甲酸銨、碳酸銨、苯甲酸銨、乙二胺四乙酸銨、乙二胺四乙酸二胺鹽、丁二酸銨、甲酸銨、1-H-吡唑-3-羧酸銨之群的羧酸銨併入該移除組成物中,藉此,該移除組成物相對該等低k材料選擇性移除該TiN、TaN、TiNxOy、TiW、W或Ti或W之合金蝕刻遮罩。
在任何給定的加工步驟中待移除之非所需的殘留物的含量及類型將影響組成物之操作pH的選擇。
根據本文中所述之本發明概念的組成物及方法係僅可選擇性蝕刻TiN、TaN、TiNxOy、TiW及W(包括Ti及W之合金),可與Cu、Co、低k及TEOS介電材料相容,且亦可自基材(即待處理之雙重鑲嵌結構)同時移除氧化銅、聚合材料及蝕刻殘留物。
根據本發明調配且針對TiN、TaN、TiNxOy、TiW及W(包括Ti及W之合金)顯示固有高蝕刻速率的組成物允許在相對低的溫度(例如小
於65℃的溫度)下加工。相對低的溫度製程顯示低氧化劑分解速率,此進一步延長有用組成物槽壽命及適用期。此外,針對TiN、TaN、TiNxOy、TiW及W(包括Ti及W之合金)顯示選擇性高蝕刻速率之本發明組成物係理想,因為其可減少裝置加工時間及由此提高生產率。通常,藉由提高製程溫度已實現對TiN、TaN、TiNxOy、TiW及W(包括Ti及W之合金)之高蝕刻速率。然而,對於單晶圓製程應用而言,最高加工溫度為約75℃,此進一步可限制針對TiN之上限蝕刻速率,及由此限制組成物自雙重鑲嵌結構完全移除TiN金屬硬遮罩的能力。在20℃至60℃之溫度範圍之單晶圓工具應用下,本發明組成物可對TiN、TaN、TiNxOy、TiW及W(包括Ti及W之合金)有效地實現高蝕刻速率,且若有此需要,則可利用單晶圓應用製程設備完全移除TiN、TaN、TiNxOy、TiW及W(包括Ti及W之合金)金屬硬遮罩。
圖1A及1B為在雙重鑲嵌裝置製造期間,但在與本發明移除組成物接觸之前分別顯示溝槽及介層孔的半導體晶圓片段的橫斷面SEM影像。
圖2A及2B為圖1A及1B中所示之類型的半導體晶圓片段在與來自表1之移除組成物1於50℃下接觸90秒之後的橫斷面SEM影像。
圖3A及3B為類似於圖1A及1B中所示之類型的半導體晶圓片段在與來自表1之移除組成物2於50℃下接觸90秒之後的橫斷面SEM影像。
圖4A及4B為類似於圖1A及1B中所示之類型的半導體晶圓片段在與來自表1之移除組成物3於53℃下接觸90秒之後的SEM影像。
認識到本發明組成物之各種組分可相互作用,且因此,任何組成物表達為當一起添加時形成該組成物之各種組分之含量。除非另有明確闡明,否則以百分比給出之任何組成物均為已添加至該組成物中
之該組分的重量百分比(重量%)。當該組成物被描述為實質上不含特定組分時,提供的數值範圍可引導一般技術者知曉「實質上不含」的含義,但在所有情形中,「實質上不含」涵蓋其中該組成物完全不含該特定組分的較佳實施例。
如以上簡要闡明,雙重鑲嵌製程用於在後段金屬化中形成金屬互連件,其接著用於將半導體基材中之各種電性組件與功能電路電互連。包括藉由夾層介電層及/或屏障層所分隔之多級別或層的金屬互連件的製造的後段金屬化的論述可見於例如美國專利號8,080,475,其教示係藉由全文引用之方式併入本文中。新穎材料(諸如超低k介電質)於微電子裝置中之集成對清潔性能提出新要求。同時,縮減裝置尺寸會減少介層孔及溝槽之臨界尺寸的變化的容限。
根據第一實施例,本發明為一種半導體加工組成物,其包括水、至少一種氧化劑、視需要之至少一種鹼或酸(視工作組成物之所需pH而定)及0.0001重量%至高達50重量%之羧酸銨。藉由實例之方式且非藉由限制之方式,該羧酸銨可選自包括草酸銨、乳酸銨、酒石酸銨、檸檬酸三銨、乙酸銨、胺基甲酸銨、碳酸銨、苯甲酸銨、乙二胺四乙酸銨、乙二胺四乙酸二胺鹽、丁二酸銨、甲酸銨、1-H-吡唑-3-羧酸銨及其混合物之群。
在一個較佳實施例中,該羧酸銨之濃度為0.001重量%至高達50重量%。儘管實行本發明未作要求,但在該組成物待用於BEOL半導體加工應用及其中涉及金屬組件(例如Cu及Cu合金組件)之腐蝕的其他應用的情況中,至少一種腐蝕抑制劑亦可存在於該組成物中。在一個實施例中,該等調配物較佳地具有3至13的pH。對於BEOL Cu互連件製造而言,較佳具有在7至12之範圍內的pH。
本發明組成物可有效地自其上具有TiN、TaN、TiNxOy、TiW及W(包括Ti及/或W之合金)蝕刻遮罩之包括低k介電材料的半導體基材
相對該等低k材料選擇性移除主要由TiN、TaN、TiNxOy、TiW或W(包括Ti及/或W之合金)組成之蝕刻遮罩。此外,該組成物亦具有自基材同時移除光阻劑、聚合材料、蝕刻殘留物及氧化銅的功能。
本發明組成物亦可包括0.001重量%至20重量%之胺基酸、聚羧酸胺(即胺基聚羧酸)及/或羧酸、聚羧酸螯合劑或其混合物,較佳為0.001重量%至10重量%,及更佳為0.001重量%至5重量%。已經觀察到根據所述及主張之本發明概念,胺基酸、聚羧酸胺(即胺基聚羧酸)及/或羧酸、聚羧酸螯合劑或其混合物之存在可穩定該組成物。文中所用之術語「穩定」意指對硬遮罩之可達到的蝕刻速率(即移除速率)在所選操作溫度下在延長之時段中實質上維持恒定。該等螯合劑之實例包括但不限於1,2-環己二胺-N,N,N',N'-四乙酸;乙二胺四乙酸;氮基三乙酸;二乙三胺五乙酸;1,4,7,10-四氮雜環十二烷-1,4,7,10-四乙酸;乙二醇四乙酸(EGTA);1,2-雙(鄰-胺基苯氧基)乙烷-N,N,N',N'-四乙酸;N-{2-[雙(羧甲基)胺基]乙基}-N-(2-羥乙基)甘胺酸(HEDTA);及乙二胺-N,N'-雙(2-羥基苯乙酸)(EDDHA)。
文中所述之本發明概念的組成物及方法特別可應用於在單晶圓設備中加工單晶圓。當需要高TiN蝕刻速率時,常用的方法為在高製程溫度下處理晶圓。然而,已知較高的溫度會造成氧化劑的降解,此會縮短槽壽命及適用期。根據文中所述之本發明概念已經觀察到可在於20℃至60℃之範圍內的實質上較低溫度下實現滿意的結果以在當硬遮罩包括TiN時產生回縮樣式或完全移除金屬硬遮罩。
在本發明之一些實施例中,該組成物可包含一或多種與水可混溶之共溶劑。此等共溶劑增強殘留物移除。適宜的共溶劑包括但不限於環丁碸、N-甲基吡咯烷酮及二甲亞碸。
根據本發明概念之有用的氧化劑係選自具有與金屬硬遮罩進行化學反應並將其移除之能力的任何物質。該等氧化劑包括但不限於主要由過氧化氫(H2O2)、n-甲基嗎啉氧化物(NMMO或NMO)、過氧化苯甲醯、過氧單硫酸四丁銨、臭氧、氯化鐵、過錳酸鹽、過氧硼酸鹽、過氯酸鹽、過硫酸鹽、過氧二硫酸銨、過氧乙酸、氫過氧化脲、硝酸(HNO3)、亞氯酸銨(NH4ClO2)、氯酸銨(NH4ClO3)、碘酸銨(NH4IO3)、過硼酸銨(NH4BO3)、過氯酸銨(NH4ClO4)、過碘酸銨(NH4IO3)、過硫酸銨((NH4)2S2O8)、四甲基亞氯酸銨((N(CH3)4)ClO2)、四甲基氯酸銨((N(CH3)4)ClO3)、四甲基碘酸銨((N(CH3)4)IO3)、四甲基過硼酸銨((N(CH3)4)BO3)、四甲基過氯酸銨((N(CH3)4)ClO4)、四甲基過碘酸銨((N(CH3)4)IO4)、四甲基過硫酸銨((N(CH3)4)S2O8)、((CO(NH2)2)H2O2)、過乙酸(CH3(CO)OOH)及其混合物組成之群。在以上物質中,H2O2為一種不含金屬且提供易於處理及更低相對成本的最佳氧化劑。
氧化劑或其混合物可以約0.1重量%至約90重量%,較佳約5重量%至90重量%,及為求最佳結果,較佳10重量%至90重量%存在於組成物中。
該組成物亦可包括鹼或酸以適當地調整工作組成物之pH。該鹼可例如選自季銨盐,諸如四甲基氫氧化銨(TMAH)、四乙基氫氧化銨(TEAH)及苄基三甲基氫氧化銨(BTAH)及其混合物。該鹼亦可選自一級、二級或三級胺(诸如,单乙醇胺(MEA)、二乙醇胺(DGA)、三乙醇胺(TEA))、四丁基氫氧化鏻(TBPH)及其混合物。在一些實施例中,該鹼可為季銨鹽及胺之組合。適宜的酸包括例如無機酸,諸如硫酸、硝酸、磷酸、氫氟酸(HF)或氫溴酸;或有機酸,諸如羧酸、胺基酸、羥基羧酸、聚羧酸;或該等酸之混合物。該工作組成物之pH應維持
在2至14、但較佳在3至12之範圍內的數值。如上所述,當用於BEOL Cu互連件製造應用時,在使用過氧化氫作為氧化劑以實現高TiN蝕刻速率時,該工作組成物之較佳pH係在7至12之範圍內。
Cu或Co腐蝕抑制劑或其混合物為本發明組成物中的可選組分。當用於BEOL應用時,Cu或Co腐蝕抑制劑常存在於本發明組成物及相關的製程中,在BEOL應用中,需要存在腐蝕抑制劑以保護金屬表面不被蝕刻或不然降解。對於本發明組成物及相關方法之其他應用(包括FEOL)而言,一般不需要腐蝕抑制劑,即Cu或Co不曝露至清潔化學劑,Cu或Co不存在於晶圓基材中,或銅或鈷表面之略微蝕刻/降解通常不成問題。
金屬(Cu或Co)腐蝕抑制劑為有機化合物,諸如唑、硫醇及/或吲哚,其較佳選自由如下組成之群:包含至少一個氮原子之雜環化合物,諸如(例如)吡咯及其衍生物、吡唑及其衍生物、咪唑及其衍生物、三唑及其衍生物、吲唑及其衍生物及硫醇-三唑及其衍生物、苯并三唑(BTA)、甲苯基三唑、5-苯基-苯并三唑、5-硝基-苯并三唑、3-胺基-5-巰基-1,2,4-三唑、1-胺基-1,2,4-三唑、羥基苯并三唑、2-(5-胺基-戊基)苯并三唑、1-胺基-1,2,3-三唑、1-胺基-5-甲基-1,2,3-三唑、3-胺基-1,2,4-三唑、3-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、鹵基-苯并三唑(鹵基=F、Cl、Br或I)、萘并三唑、2-巰基苯并咪唑(MBI)、2-巰基苯并噻唑、4-甲基-2-苯基咪唑、2-巰基噻唑啉、5-胺基四唑、單水合5-胺基四唑、5-胺基-1,3,4-噻二唑-2-硫醇、2,4-二胺基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑啶酮、1,5-亞戊基四唑、1-苯基-5-巰基四唑、二胺基甲基三嗪、咪唑啉硫酮、巰基苯并咪唑、4-甲基-4H-1,2,4-三唑-3-硫醇、5-胺基-1,3,4-噻二唑-2-硫醇、苯并噻唑及其混合物。在以上物質中,
BTA、吡唑或BTA及吡唑之混合物或BTA及甲苯基三唑之混合物(可以名稱「Wintrol A-90」購自Wincom、Inc.)因具有更佳清潔性能而為較佳的Cu腐蝕抑制劑。
Cu或Co腐蝕抑制劑或其混合物可以約0.0001重量%至約50重量%,及較佳地,為求最佳結果以約0.0001重量%至約20重量%存在於該組成物中。
其他適宜的Cu或Co腐蝕抑制劑包括但不限於芳族醯肼及席夫鹼(Schiff base)化合物。
所述及主張之本發明概念在於以下發現:自半導體裝置完全移除金屬硬遮罩(其中該金屬硬遮罩與低k介電材料呈重疊關係)係可藉由將0.0001重量%至高達50重量%之羧酸鹽化合物(但特定言之羧酸銨)併入該移除組成物而實現。在一個較佳實施例中,羧酸銨之濃度為0.001重量%至高達10重量%。
如以下實例中所示,羧酸銨化合物在本發明移除組成物中之存在不僅增加TiN蝕刻速率,而且資料支持其存在亦用於在延長之時段(例如長達至少35小時)中穩定可達到的TiN蝕刻速率的結論。
文中所用之術語「羧酸鹽」係指通式M(RCOO)n,其中M為金屬且n為1、2、...,為具有通式RCOOR'之化合物中的羧酸酯的數目,其中R及R'為有機基團,限制條件為R'≠H。當文中所述之該類化學劑用於電子裝置製造時,諸如製造IC裝置,化學組成物中較佳不具有任何金屬雜質。在該等情形下,M係由NH4+替代。羧酸銨為用於該(等)移除調配物中之較佳的化學劑,及其可直接添加至該組成物中,或其可在加工期間藉由化學反應呈副產物或中間產物形式產生。
現藉由參考本發明概念及以下實例詳細闡釋本發明移除組成
物,但本發明不受此等實例及各測試中顯示的結果限制。如下文更充分描述,本發明組成物可包含在各種具體調配物中。在所有該等組成物中,其中該組成物之具體組分係參考包括零下限之重量百分比範圍論述,應理解該等組分可存在或不存在於組成物之各種具體實施例中,及在該等組分存在的情形下,其存在濃度可低達0.0001重量%(基於其中使用該等組分之組成物之總重量計)。
在以下實例中,根據文中所述之本發明概念製備100g移除組成物樣品。各樣品組成物包括以下各表中所列的對應調配物行中所示重量的每一組分。例如,表1中所示之命名為「1」的100g份量的樣品組成物包含2g 10%酒石酸銨水溶液、7.21g 10% DGA水溶液、12.43g 1.5% BTA水溶液、60g H2O2(30%水溶液)及18.36g去離子水(DIW)。
可在使用時調配該等移除組成物,或可在無氧化劑下提前將其等方便地調配並隨後在使用時添加氧化劑。對於混合或摻合各種組分而言,亦不存在特定順序。
分別在60℃及50℃下針對TiN化學處理1及2分鐘及針對Cu、Co、W及TEOS處理10分鐘之後進行蝕刻速率評估。利用四維四點探針測量儀333A(Four Dimensions Four Point Probe Meter 333A)測量TiN、Cu、Co及W厚度,其中膜之厚度係與在與本發明組成物接觸之後殘留的膜厚度相關。利用HORIBA JOBIN YVON之自動SE光譜橢偏計(Auto SE Spectroscopic Ellipsometer)測量TEOS厚度。蝕刻速率計算為厚度變化(化學處理之前及之後)除以化學處理時間。利用Beckman 260 pH/Temp/mV儀測量化學溶液之pH。用於該等實驗中之H2O2來自J.T.Baker。自SEM結果(Hitachi S-5500)評估殘留物移除效率及TiN硬遮罩蝕刻。
利用去離子水作為溶劑、BTA或BTA及吡唑之混合物作為Cu腐蝕抑制劑、H2O2作為氧化劑及二乙醇胺(DGA)或苄基三甲基氫氧化銨(BTAH)作為調整pH之鹼製備表1所示之組成物。按上述方式,在50℃之溫度及約8之pH下進行TiN及Cu蝕刻速率評估。
組成物1、2及3在位於50℃至53℃之範圍內的相對低的溫度下顯示位於178Å/min至高達340Å/min之範圍內的TiN移除速率。對於商業晶圓加工而言,2.5Å/min或更小之銅蝕刻速率視為優良。
現參考圖,圖1A及1B為分別顯示在雙重鑲嵌製造步驟之後,但在與移除組成物處理之前所接受之溝槽及介層孔的半導體晶圓片段的SEM影像。圖2A及2B為與圖1A及1B中所示之晶圓片段類似的晶圓片段在與移除組成物1於50℃之溫度下接觸90秒之後的圖。如圖2A所示,殘留物被移除,但殘留一些TiN硬遮罩。圖3A及3B為與圖1A及1B中所示之晶圓片段類似的晶圓片段在與移除組成物2於50℃之溫度下接觸90秒之後的圖,其中殘留物及TiN硬遮罩已被完全移除。圖4A及4B為與圖1A及1B中所示之晶圓片段類似的晶圓片段在與移除組成物3於53℃之溫度下接觸90秒之後的圖。TiN硬遮罩及殘留物已被完全移除。
利用去離子水作為溶劑、BTA作為Cu腐蝕抑制劑、H2O2作為氧化劑及四甲基氫氧化銨(TMAH)作為調整pH之鹼製備表2中所示之組成物。按上述方式,在60℃之溫度及約7.8之pH下進行TiN及Cu蝕刻
速率評估。
與不包含羧酸銨之相應對照組成物4相比,各自包含指示含量之化合物乳酸銨、酒石酸銨、碳酸銨及檸檬酸三銨的各移除組成物均顯示更高TiN蝕刻速率。
製備表3中所示之調配物,並按上述方式,在50℃之溫度及約8之pH下進行TiN及Cu蝕刻速率評估。當與不包含羧酸銨之對照組成物9相比時,該等移除組成物顯示更高TiN蝕刻速率及類似的Cu蝕刻速率。
利用調整pH之DGA製備表4中所示之調配物,且BTA係用作銅腐蝕抑制劑。按上述方式,在50℃之溫度及約8之pH下進行TiN及Cu蝕刻速率評估。當與不包含羧酸銨之對照組成物13相比時,該等移除組成物顯示更高TiN蝕刻速率及類似的Cu蝕刻速率。
利用調整pH之TMAH製備表5所示之調配物,且BTA係用作銅腐蝕抑制劑。按上述方式,在50℃之溫度及約8之pH下進行TiN及Cu蝕刻速率評估。當與不包含羧酸銨之對照組成物17相比時,該等移除組成物顯示更高的TiN蝕刻速率及類似的Cu蝕刻速率。
利用調整pH之苄基三甲基氫氧化銨(BTAH)製備表6中所示之調配物,且BTA係用作銅腐蝕抑制劑。按上述方式,在50℃之溫度及約8之pH下進行TiN及Cu蝕刻速率評估。當與不包含羧酸銨之對照組成物21相比時,該等移除組成物顯示更高的TiN蝕刻速率及類似的Cu蝕刻速率。
利用調整pH之四乙基氫氧化銨(TEAH)製備表7中所示之調配物,且BTA係用作銅腐蝕抑制劑。按上述方式,在50℃之溫度及8之pH下進行TiN及Cu蝕刻速率評估。當與不包含羧酸銨之對照組成物25相比時,該等移除組成物顯示更高的TiN蝕刻速率及類似的Cu蝕刻速率。
利用調整pH之DGA製備表8中所示之調配物,但不使用銅腐蝕抑制劑。按上述方式,在50℃之溫度及約8之pH下進行TiN及TEOS移除速率評估。當與具有87Å/min之TiN蝕刻速率的對照組成物31相比時,該等移除組成物顯示在低達144Å/min至高達179Å/min範圍內的高TiN蝕刻速率。以1.46重量%至小於3重量%之濃度存在之化合物碳酸銨、乙酸銨、草酸銨、乳酸銨及酒石酸銨用於提供本發明移除組成物在相對低的溫度(例如,50℃)下實現極高的TiN蝕刻速率的能力。根據所述及主張之本發明概念,值得注意的是:當與對照組成物31相比時,化合物碳酸銨、乙酸銨、草酸銨、乳酸銨或酒石酸銨均未對TEOS移除速率產生顯著影響。
在不使用pH調整劑的情況下,製備表9中所示之調配物。所用Cu腐蝕抑制劑為Wintrol A-90(一種BTA及甲苯基三唑之商業混合物)。藉由改變過氧化氫及羧酸銨濃度獲得所需TiN及Cu蝕刻速率及pH。在此等實例中,使用不同濃度的若干羧酸鹽。過氧化氫濃度為20重量%或80重量%。調配物pH在低達pH 5至高達pH 8.4之範圍內,及TiN蝕刻速率(即移除速率)在低達18Å/min至高達170Å/min之範圍內。
使用酒石酸或TMAH或不使用任何pH調整劑製備表10中所示之調配物。Wintrol A-90係用作Co腐蝕抑制劑。在此等實例中,使用不
同濃度的若干羧酸鹽。過氧化氫濃度在20重量%至80重量%之範圍內。調配物pH在低達pH 5至高達pH 11之範圍內。Co蝕刻速率在所有情形中均不顯著(即最高Co蝕刻速率為1.17Å/min)。
下表11中所示之結果表明:當與不包含羧酸銨之對照組成物53相比時,具有乳酸銨及酒石酸銨的混合物的移除組成物54顯示更高的TiN蝕刻速率。
利用調整pH之TMAH製備表12中所示之調配物,且BTA係用作銅腐蝕抑制劑。組成物56、57及58中所用之羧酸鹽分別為單水合檸檬酸三鉀、四水合酒石酸鉀鈉及L-乳酸鉀。當與不包含羧酸鹽之對照組成物55相比時,此等組成物之各者均顯示更高的TiN蝕刻速率及類似的Cu蝕刻速率。
表13中所示之結果表明:當與對照組成物59相比時,在低達0.001重量%之羧酸銨濃度下,移除組成物60至63顯示更高的TiN蝕刻速率及類似的Cu及Co蝕刻速率。
表14中所示之結果表明:當與不包含羧酸銨之對照組成物64相比時,在50重量%之乙酸銨濃度下,移除組成物65顯示更高的TiN蝕刻速率及類似的Cu及Co蝕刻速率。
製備表15中所示之調配物,並按以上有關TiN移除所述之方式,
在45℃及55℃之溫度下進行W(鎢)蝕刻速率評估。
當與在相同pH下之相應的不含羧酸銨之對照組成物66、70及72相比時,存在1.46重量%至3重量%之濃度及在約4至略高於11之範圍內的pH的羧酸銨顯示顯著地增加W移除速率。
如上所述,觀察到胺基酸、聚羧酸胺(即胺基聚羧酸)及/或羧酸、聚羧酸螯合劑或其混合物之存在出乎意料地穩定本發明組成物。文中所用之術語「穩定」意指對硬遮罩之可達到的蝕刻速率(即移除硬遮罩之速率)在所選操作溫度下在延長之時段(例如二十二(22)小時至長達至少三十五(35)小時的時段)中實質上維持恒定。如文中所用,術語「實質上恒定」用於意指移除硬遮罩的可達到的蝕刻速率在所選操作溫度下在組成物之有用期期間的下降不超過15Å/min。可根據所述及主張之本發明概念操作的螯合劑的實例包括但不限於1,2-環己二胺-N,N,N',N'-四乙酸(CDTA);乙二胺四乙酸;氮基三乙酸;二乙三胺五乙酸;1,4,7,10-四氮雜環十二烷-1,4,7,10-四乙酸;乙二醇四乙酸(EGTA);1,2-雙(鄰-胺基苯氧基)乙烷-N,N,N',N'-四乙酸;N-{2-[雙(羧甲基)胺基]乙基}-N-(2-羥乙基)甘胺酸(HEDTA);及乙二胺-N,N'-雙(2-
羥基苯乙酸)(EDDHA)。
適用期為一種移除組成物配方隨著時間最佳地表現及隨著時間不顯著地改變功能之能力的衡量。適用期為溫度的強函數。在高溫下處理許多小時之後,混合物中之化學劑可分解及該配方將失去功能。
如下般進行適用期研究(以確定其中本發明移除組成物之蝕刻速率維持恒定的時段及程度):製備800公克儲備溶液並維持在50℃。自經加熱之儲備溶液移出150公克樣品並在50℃及特定時間下用於TiN及Cu蝕刻速率及pH研究。樣品在每次蝕刻速率測量之後作廢。
根據所述及主張之本發明概念製備移除組成物,其中選定0.3重量%之濃度的酒石酸銨作為羧酸銨。在調配物74及75中,選定1,2-環己二胺-N,N,N',N'-四乙酸(CDTA)作為胺基聚羧酸螯合劑,且對照調配物76不包括螯合劑。該等組成物顯示於表16中。
在0、2、4、7.5及22小時之間隔下,自該等移除組成物取得樣品以測量TiN及Cu蝕刻速率。結果顯示於表17中。
表17中呈現的數據說明:在存在CDTA的移除組成物74及75中,TiN蝕刻速率在22小時的時段中維持穩定(即實質上恒定)。對於組成物75而言,初始的TiN蝕刻速率為157Å/min,及其在22小時的時段中維持在156Å/min。對於組成物74而言,初始的TiN蝕刻速率為168Å/min,及其在22小時的時段中維持在157Å/min。在無CDTA的組成物76中,TiN蝕刻速率在22小時之後從219Å/min之初始的蝕刻速率下降至99Å/min的蝕刻速率。
根據所述及主張之本發明概念製備移除組成物,其中選定0.3重量%之濃度的酒石酸銨作為羧酸銨。在調配物77及78中,選定1,2-環己二胺-N,N,N',N'-四乙酸(CDTA)作為胺基聚羧酸螯合劑。該等組成物顯示於表18中。
在0、2、4、7及24小時之間隔下,自移除組成物獲得樣品以測量TiN及Cu蝕刻速率。結果顯示於表19中。
表19中呈現的數據說明:在分別存在0.001%及0.005%的CDTA的移除組成物77及78中,TiN蝕刻速率在24小時的時段中維持穩定(即實質上恒定)。對於組成物77而言,初始的TiN蝕刻速率為27.33Å/min,及其在24小時的時段中維持在24.41Å/min。對於組成物78而言,初始的TiN蝕刻速率為26.91Å/min,及其在24小時的時段中維持在26.24Å/min。
利用調整pH之DGA製備表20中所示之調配物,且BTA係用作銅腐蝕抑制劑。乙二胺四乙酸銨係用於穩定TiN蝕刻速率。
根據上述方法進行適用期研究。在0、2、4、8、24、28及35小時之間隔下,獲得樣品以測量TiN及Cu蝕刻速率及pH。結果顯示於表21中。
表21中顯示的實驗結果說明:在存在乙二胺四乙酸銨之移除組成物79中,TiN蝕刻速率在三十五(35)小時的時段中維持穩定(即實質上維持恒定)。初始的TiN蝕刻速率為208Å/min,及其在三十五(35)小時的時段中維持在194Å/min。在無乙二胺四乙酸銨的組成物80中,TiN蝕刻速率在24小時之後從209Å/min之初始速率下降至106Å/min的速率。
利用調整pH之DGA製備表22中所示之調配物。BTA係用作銅腐蝕抑制劑。所選羧酸銨選為乙二胺四乙酸銨。表22中所示之結果表明:當與不包含羧酸銨之對照組成物82相比時,存在乙二胺四乙酸銨之移除組成物81顯示更高的TiN蝕刻速率。
如表2至8、11、13至15及22中所示,羧酸銨於本發明移除組成物中之存在不僅增加TiN蝕刻速率,而且資料支持其存在亦用於在延長之時段(例如長達至少35小時)中穩定TiN蝕刻速率的結論。
已描述本發明概念的若干實施例。然而,一般技術者應知曉本發明不限於所述實施例。可在附屬申請專利範圍之精神及範圍內,實踐本發明概念並作修改及變動。
Claims (13)
- 一種移除組成物,其具有在2至14之範圍內的pH,其用於自其上具有TiN、TaN、TiNxOy、TiW、W或Ti或W之合金蝕刻遮罩之包括低k介電材料之半導體裝置基材相對該低k介電材料選擇性移除主要由TiN、TaN、TiNxOy、TiW、W及Ti及W之合金組成之蝕刻遮罩,其中該移除組成物包括:(a)0.1重量%至90重量%之氧化劑;(b)0.0001重量%至50重量%之羧酸銨;及(c)補足至100重量%之該移除組成物的剩餘部分,其包括去離子水。
- 如請求項1之移除組成物,其進一步包括可與水混溶的有機共溶劑。
- 如請求項1或請求項2之移除組成物,其中(a)該氧化劑係選自主要由過氧化氫(H2O2)、n-甲基嗎啉氧化物(NMMO或NMO)、過氧化苯甲醯、過氧單硫酸四丁銨、臭氧、氯化鐵、過錳酸鹽、過氧硼酸鹽、過氯酸鹽、過硫酸鹽、過氧二硫酸銨、過氧乙酸、氫過氧化脲、硝酸(HNO3)、亞氯酸銨(NH4ClO2)、氯酸銨(NH4ClO3)、碘酸銨(NH4IO3)、過硼酸銨(NH4BO3)、過氯酸銨(NH4ClO4)、過碘酸銨(NH4IO3)、過硫酸銨((NH4)2S2O8)、四甲基亞氯酸銨((N(CH3)4)ClO2)、四甲基氯酸銨((N(CH3)4)ClO3)、四甲基碘酸銨((N(CH3)4)IO3)、四甲基過硼酸銨((N(CH3)4)BO3)、四甲基過氯酸銨((N(CH3)4)ClO4)、四甲基過碘酸銨((N(CH3)4)IO4)、四甲基過硫酸銨((N(CH3)4)S2O8)、((CO(NH2)2)H2O2)、過乙酸(CH3(CO)OOH)及其混合物組成之群;及(b)該羧酸銨係選自包括草酸銨、乳酸銨、酒石酸銨、檸檬酸 三銨、乙酸銨、胺基甲酸銨、碳酸銨、苯甲酸銨、乙二胺四乙酸銨、乙二胺四乙酸二胺鹽、丁二酸銨、甲酸銨、1-H-吡唑-3-羧酸銨及其混合物之群。
- 如請求項3之移除組成物,其中該氧化劑為過氧化氫。
- 如請求項1之移除組成物,其進一步包括0.001重量%至20重量%之胺基酸、胺基聚羧酸、羧酸、聚羧酸或其混合物,其係選自主要由如下組成之群:1,2-環己二胺-N,N,N',N'-四乙酸;乙二胺四乙酸;氮基三乙酸;二乙三胺五乙酸;1,4,7,10-四氮雜環十二烷-1,4,7,10-四乙酸;乙二醇四乙酸(EGTA);1,2-雙(鄰-胺基苯氧基)乙烷-N,N,N',N'-四乙酸;N-{2-[雙(羧甲基)胺基]乙基}-N-(2-羥乙基)甘胺酸(HEDTA);及乙二胺-N,N'-雙(2-羥基苯基乙酸)(EDDHA)。
- 如請求項1之移除組成物,其進一步包括0.0001重量%至高達50重量%之金屬腐蝕抑制劑。
- 如請求項1之移除組成物,其中該pH係在3至13之範圍內且該氧化劑為過氧化氫。
- 如請求項7之移除組成物,其中該pH係在7至12之範圍內。
- 一種方法,其用於自其上具有主要由TiN、TaN、TiNxOy、TiW、W或Ti或W之合金組成之蝕刻遮罩的包括低k材料的半導體基材相對該等低k材料選擇性移除主要由TiN、TaN、TiNxOy、TiW、W或Ti或W之合金組成的蝕刻遮罩,其中該方法包括使包括如下之移除組成物與該基材在室溫至高達80℃之範圍內的溫度及在3至13之範圍內的pH下接觸一段時間:(a)0.1重量%至90重量%之至少一種氧化劑,(b)0.0001重量%至50重量%之羧酸銨;及(c)補足至100重量%之該移除組成物的剩餘部分,其包括去 離子水,其中該移除組成物相對該等低k材料選擇性移除該TiN、TaN、TiNxOy、TiW、W或Ti或W之合金蝕刻遮罩,且該組成物之可達到的蝕刻速率在延長之時段中實質上維持恒定。
- 如請求項9之方法,其中:(a)該氧化劑係選自主要由過氧化氫(H2O2)、n-甲基嗎啉氧化物(NMMO或NMO)、過氧化苯甲醯、過氧單硫酸四丁銨、臭氧、氯化鐵、過錳酸鹽、過氧硼酸鹽、過氯酸鹽、過硫酸鹽、過氧二硫酸銨、過氧乙酸、氫過氧化脲、硝酸(HNO3)、亞氯酸銨(NH4ClO2)、氯酸銨(NH4ClO3)、碘酸銨(NH4IO3)、過硼酸銨(NH4BO3)、過氯酸銨(NH4ClO4)、過碘酸銨(NH4IO3)、過硫酸銨((NH4)2S2O8)、四甲基亞氯酸銨((N(CH3)4)ClO2)、四甲基氯酸銨((N(CH3)4)ClO3)、四甲基碘酸銨((N(CH3)4)IO3)、四甲基過硼酸銨((N(CH3)4)BO3)、四甲基過氯酸銨((N(CH3)4)ClO4)、四甲基過碘酸銨((N(CH3)4)IO4)、四甲基過硫酸銨((N(CH3)4)S2O8)、((CO(NH2)2)H2O2)、過乙酸(CH3(CO)OOH)及其混合物組成之群;及(b)該羧酸銨係選自包括草酸銨、乳酸銨、酒石酸銨、檸檬酸三銨、乙酸銨、胺基甲酸銨、碳酸銨、苯甲酸銨、乙二胺四乙酸銨、乙二胺四乙酸二胺鹽、丁二酸銨、甲酸銨、1-H-吡唑-3-羧酸銨及其混合物之群。
- 如請求項10之方法,其中該移除組成物進一步包括0.0001重量%至高達20重量%之銅腐蝕抑制劑。
- 如請求項10之方法,其中該移除組成物進一步包括0.001重量%至20重量%之胺基酸、胺基聚羧酸、羧酸、聚羧酸或其混合物,其係選自主要由如下組成之群:1,2-環己二胺-N,N,N',N'-四乙 酸;乙二胺四乙酸;氮基三乙酸;二乙三胺五乙酸;1,4,7,10-四氮雜環十二烷-1,4,7,10-四乙酸;乙二醇四乙酸(EGTA);1,2-雙(鄰-胺基苯氧基)乙烷-N,N,N',N'-四乙酸;N-{2-[雙(羧甲基)胺基]乙基}-N-(2-羥乙基)甘胺酸(HEDTA);及乙二胺-N,N'-雙(2-羥基苯基乙酸)(EDDHA),藉此,對蝕刻遮罩之可達到之移除速率在長達至少35小時之延長之時段中實質上維持恒定。
- 一種方法,其用於自其上具有主要由TiN、TaN、TiNxOy、TiW、W或Ti或W之合金組成之蝕刻遮罩的包括低k材料的半導體基材相對該等低k材料選擇性移除主要由TiN、TaN、TiNxOy、TiW、W或Ti或W之合金組成的蝕刻遮罩,其中該方法包括使包括如下之移除組成物與該基材在室溫至高達80℃之範圍內的溫度及在3至13之範圍內的pH下接觸一段時間:(a)0.1重量%至90重量%之過氧化氫;(b)0.0001重量%至50重量%之羧酸銨,其係選自包括草酸銨、乳酸銨、酒石酸銨、檸檬酸三銨、乙酸銨、胺基甲酸銨、碳酸銨、苯甲酸銨、乙二胺四乙酸銨、乙二胺四乙酸二胺鹽、丁二酸銨、甲酸銨、1-H-吡唑-3-羧酸銨及其混合物之群;(c)0.001重量%至20重量%之胺基酸、胺基聚羧酸、羧酸、聚羧酸或其混合物,其係選自主要由如下組成之群:1,2-環己二胺-N,N,N',N'-四乙酸;乙二胺四乙酸;氮基三乙酸;二乙三胺五乙酸;1,4,7,10-四氮雜環十二烷-1,4,7,10-四乙酸;乙二醇四乙酸(EGTA);及1,2-雙(鄰-胺基苯氧基)乙烷-N,N,N',N'-四乙酸;及(d)補足至100重量%之該移除組成物的剩餘部分,其包括去離子水,其中該移除組成物相對該等低k材料選擇性移除該TiN、TaN、TiNxOy、TiW、W或Ti或W之合金蝕刻遮罩,藉此該蝕刻遮罩被 選擇性移除且對該蝕刻遮罩之可達到之移除速率在延長之時段中實質上維持恒定。
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-
2013
- 2013-12-11 US US14/103,303 patent/US20150104952A1/en not_active Abandoned
-
2014
- 2014-01-03 TW TW103100235A patent/TW201522574A/zh unknown
- 2014-10-09 TW TW103135159A patent/TWI650415B/zh active
- 2014-10-09 JP JP2016522060A patent/JP6523269B2/ja active Active
- 2014-10-09 KR KR1020167012242A patent/KR102327432B1/ko active IP Right Grant
- 2014-10-09 US US15/028,501 patent/US10155921B2/en active Active
- 2014-10-09 JP JP2016521931A patent/JP2016535819A/ja active Pending
- 2014-10-09 CN CN201480055153.4A patent/CN105874562B/zh active Active
- 2014-10-09 CN CN201480055151.5A patent/CN105612599B/zh active Active
- 2014-10-09 TW TW103135158A patent/TWI650414B/zh active
- 2014-10-09 KR KR1020167012243A patent/KR102334603B1/ko active IP Right Grant
- 2014-10-09 US US15/028,573 patent/US10005991B2/en active Active
- 2014-11-14 KR KR1020167012240A patent/KR20170076616A/ko not_active Application Discontinuation
- 2014-11-14 WO PCT/US2013/074356 patent/WO2015053800A2/en active Application Filing
- 2014-11-14 US US15/028,491 patent/US20160240368A1/en not_active Abandoned
- 2014-11-14 CN CN201480055154.9A patent/CN105874568A/zh active Pending
- 2014-11-14 JP JP2016521999A patent/JP2017502491A/ja active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20220389592A1 (en) * | 2021-06-01 | 2022-12-08 | C. Uyemura & Co., Ltd. | Copper etching solution |
Also Published As
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KR20160068903A (ko) | 2016-06-15 |
US20150104952A1 (en) | 2015-04-16 |
WO2015053800A3 (en) | 2015-06-18 |
TW201527519A (zh) | 2015-07-16 |
JP2016535819A (ja) | 2016-11-17 |
CN105874562A (zh) | 2016-08-17 |
KR20170076616A (ko) | 2017-07-04 |
WO2015053800A2 (en) | 2015-04-16 |
US10155921B2 (en) | 2018-12-18 |
US20160254182A1 (en) | 2016-09-01 |
KR102327432B1 (ko) | 2021-11-17 |
TWI650415B (zh) | 2019-02-11 |
KR20160068902A (ko) | 2016-06-15 |
CN105612599B (zh) | 2019-05-14 |
TW201527518A (zh) | 2015-07-16 |
JP2016536785A (ja) | 2016-11-24 |
KR102334603B1 (ko) | 2021-12-06 |
JP6523269B2 (ja) | 2019-05-29 |
US10005991B2 (en) | 2018-06-26 |
TWI650414B (zh) | 2019-02-11 |
US20160240368A1 (en) | 2016-08-18 |
JP2017502491A (ja) | 2017-01-19 |
CN105612599A (zh) | 2016-05-25 |
US20160312162A1 (en) | 2016-10-27 |
CN105874562B (zh) | 2019-05-14 |
CN105874568A (zh) | 2016-08-17 |
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