CN113130292A - 一种等离子体刻蚀残留物清洗液 - Google Patents
一种等离子体刻蚀残留物清洗液 Download PDFInfo
- Publication number
- CN113130292A CN113130292A CN201911407714.3A CN201911407714A CN113130292A CN 113130292 A CN113130292 A CN 113130292A CN 201911407714 A CN201911407714 A CN 201911407714A CN 113130292 A CN113130292 A CN 113130292A
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- China
- Prior art keywords
- acid
- ammonium
- cleaning solution
- residue cleaning
- plasma etch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004140 cleaning Methods 0.000 title claims abstract description 84
- 238000001020 plasma etching Methods 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 238000005260 corrosion Methods 0.000 claims abstract description 25
- 230000007797 corrosion Effects 0.000 claims abstract description 25
- -1 organic acid ammonium salt Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000012964 benzotriazole Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical group 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 4
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 4
- HIMXGTXNXJYFGB-UHFFFAOYSA-N alloxan Chemical compound O=C1NC(=O)C(=O)C(=O)N1 HIMXGTXNXJYFGB-UHFFFAOYSA-N 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- 235000013772 propylene glycol Nutrition 0.000 claims description 4
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 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 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 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
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 claims description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- JVQOASIPRRGMOS-UHFFFAOYSA-M dodecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCC[N+](C)(C)C JVQOASIPRRGMOS-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- 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 3
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- NHAZGSRLKBTDBF-UHFFFAOYSA-N 1,2,4-triazol-1-amine Chemical compound NN1C=NC=N1 NHAZGSRLKBTDBF-UHFFFAOYSA-N 0.000 claims description 2
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- WITMXBRCQWOZPX-UHFFFAOYSA-N 1-phenylpyrazole Chemical compound C1=CC=NN1C1=CC=CC=C1 WITMXBRCQWOZPX-UHFFFAOYSA-N 0.000 claims description 2
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 2
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 claims description 2
- FYIHPNCKLYPALH-UHFFFAOYSA-N 2-[2-(2-aminophenoxy)ethenoxy]aniline Chemical compound NC1=CC=CC=C1OC=COC1=CC=CC=C1N FYIHPNCKLYPALH-UHFFFAOYSA-N 0.000 claims description 2
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 claims description 2
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims description 2
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 claims description 2
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 claims description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 2
- LBOQZDCAYYCJBU-UHFFFAOYSA-N 4-methyl-2h-benzotriazole;5-methyl-2h-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21.CC1=CC=CC2=NNN=C12 LBOQZDCAYYCJBU-UHFFFAOYSA-N 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- YZTYEGCWRPJWEE-UHFFFAOYSA-N 5-(benzotriazol-2-yl)pentan-1-amine Chemical compound C1=CC=CC2=NN(CCCCCN)N=C21 YZTYEGCWRPJWEE-UHFFFAOYSA-N 0.000 claims description 2
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 claims description 2
- QZBGOTVBHYKUDS-UHFFFAOYSA-N 5-amino-1,2-dihydropyrazol-3-one Chemical compound NC1=CC(=O)NN1 QZBGOTVBHYKUDS-UHFFFAOYSA-N 0.000 claims description 2
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 2
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 claims description 2
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- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
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- 235000019293 ammonium adipate Nutrition 0.000 claims description 2
- 229940090948 ammonium benzoate Drugs 0.000 claims description 2
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 2
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- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229940059265 ammonium lactate Drugs 0.000 claims description 2
- 235000019286 ammonium lactate Nutrition 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 2
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 claims description 2
- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 claims description 2
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 2
- 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 2
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 2
- JCXKHYLLVKZPKE-UHFFFAOYSA-N benzotriazol-1-amine Chemical compound C1=CC=C2N(N)N=NC2=C1 JCXKHYLLVKZPKE-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
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- OEDPMSDASHAOCT-UHFFFAOYSA-N diazanium;2-(carboxylatomethylamino)acetate Chemical compound [NH4+].[NH4+].[O-]C(=O)CNCC([O-])=O OEDPMSDASHAOCT-UHFFFAOYSA-N 0.000 claims description 2
- FRRMMWJCHSFNSG-UHFFFAOYSA-N diazanium;propanedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC([O-])=O FRRMMWJCHSFNSG-UHFFFAOYSA-N 0.000 claims description 2
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- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 claims description 2
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000594 mannitol Substances 0.000 claims description 2
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- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
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- 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 2
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- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 claims description 2
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- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 claims description 2
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- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 2
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- 229960000744 vinpocetine Drugs 0.000 claims description 2
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 229940113165 trimethylolpropane Drugs 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 21
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 14
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000007769 metal material Substances 0.000 abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 42
- 239000010949 copper Substances 0.000 description 31
- 229910052802 copper Inorganic materials 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
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- 239000004065 semiconductor Substances 0.000 description 11
- 150000005846 sugar alcohols Polymers 0.000 description 11
- 239000003989 dielectric material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
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- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 238000004377 microelectronic Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000009977 dual effect Effects 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 229950007919 egtazic acid Drugs 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940078916 carbamide peroxide Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000001039 wet etching Methods 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
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
本发明提供一种等离子体刻蚀残留物清洗液,包括氧化剂、pH调节剂、稳定剂、有机酸铵盐、金属缓蚀剂、以及水。本发明提供了一种等离子体刻蚀残留物清洗液,可有效去除晶圆清洗过程中的等离子体刻蚀残留物,并且,在金属孔道中的残留物少;对氮化钛的刻蚀具有高选择性,能够高效去除氮化钛硬掩模;并且在高转速单片机清洗中对金属材料和非金属材料以及Low‑k介质材料均有较小的腐蚀速率;操作窗口较大;本申请的清洗液中不含氟,即使是小于14nm的晶圆也不会影响其电性能。
Description
技术领域
本发明涉及半导体制造过程中的晶圆清洗液领域,尤其涉及一种等离子体刻蚀残留物清洗液。
背景技术
晶圆清洗是集成电路制程中重复次数最多的工序,清洗效果的好坏较大程度地影响芯片制程及积体电路特性等质量问题。清洗液使用的各种化学品处理不当就会严重污染环境,清洗次数繁多消耗大量的化学品和水。面对刻线更细、集成度更高的IC制程,人们还在研究更有效的清洗方案。光致抗蚀剂掩模通常用于半导体工业中以将诸如半导体或电解质材料形成图案。在一种应用中,将光致抗蚀剂掩模用于双镶嵌工艺中以在微电子器件的后端金属化中形成互联。双镶嵌工艺涉及在金属导体层如铜(Cu)层上面的低介电常数(Low-k,或低k)介电层上形成光致抗蚀剂掩模。然后根据光致抗蚀剂掩模对 Low-k介电层进行刻蚀以形成通道和/或开槽以露出金属导体层。通常使用两个平板印刷对通常称作双镶嵌结构的通道和开槽进行限定。然后将光致抗蚀剂掩模从Low-k介电层去除,然后将导电材料沉积入通道和/或开槽以形成互联。
随着微电子器件尺寸的下降,实现通道和开槽的临界尺寸变得更加困难。在半导体制造领域中使用金属铜、Low-k介质材料越来越多。尤其是铜双大马士革工艺越来越广泛的情况下,寻找能够有效去除刻蚀残留物的同时又能保护Low-k介质材料、非金属材料和金属材料的清洗液就越来越重要。同时随着半导体制程尺寸越来越小,清洗方式也越来越广泛的使用到高速旋转单片清洗。由此,使用金属硬掩模以提供通道和开槽更好的轮廓控制。金属硬掩模由钛或氮化钛制成,并在形成双镶嵌结构的通道和/或开槽之后通过湿蚀刻法去除,其具体步骤一般为清洗液清洗/漂洗/去离子水漂洗。在此过程中,只能除去残留的聚合物光阻层和无机物,而不能攻击损害金属层。关键的是,湿蚀刻法使用去除化学品,其有效去除金属硬掩模和/或光抗蚀剂蚀刻残余物而不影响下面的金属导电层和Low-k介电材料。换言之,需要去除化学品对金属导电层和Low-k介电层具有较高的选择性。
国内外对于半导体清洗液的报道较多,US20150027978A1公开了高选择蚀刻TiN,主要通过加入铵盐以及双氧水的分解来提高TiN的蚀刻速率,加入5-甲基苯并三氮唑抑制铜的腐蚀,添加氟化铵来提高清洗能力。此配方虽然对铜有很好地保护,但是5-甲基苯并三氮唑会吸附在晶圆表面,难以脱附,会对电性能造成较大影响。WO201603729A1在此基础上做了进一步的研究,公开了一种通过氟硅酸、碘酸铵、氧化钒、钒酸铵等来调整金属和非金属的蚀刻速率,此方法可以进一步提高TiN的蚀刻速率,对铜也有很好的保护,但是仍然没有解决晶圆表面缓蚀剂吸附的问题,并且引入了新的金属离子,从而影响电性能,也没有解决在高速旋转下清洗液对金属腐蚀的控制情况。US20179546321B2公开的配方中有含氟组分、有机或无机酸等,可以较好地解决晶圆表面吸附问题,但是对厚 TiN硬掩模难以彻底去除,蚀刻不完全,清洗不干净,影响电性能。最新报道中,美国EKC 公司在专利US10155921B2中公开了一种通过氧化剂、羧酸盐以及金属缓蚀剂来去除氮化钛,同时兼容铜和低k介电材料的方法。以双氧水作为氧化剂,吡咯、吡唑、吲唑及其衍生物作为金属缓蚀剂,配合以铵盐作为氮化钛蚀刻增强剂,在pH值7~12的环境下, 20~60℃条件下选择性去除硬掩模及其残留物而不影响下面的金属导电层和低k介电层,这样可以获得更好的剖面控制。专利中明确阐述产品中不含氟,这样产品的清洗效果较差,特别对于14nm及更小技术节点的晶圆来说,很大程度上影响电性能。
发明内容
为解决现有技术中在晶圆清洗过程中的清洗液无法同时满足有效去除刻蚀残留物以及同时保护低k介电材料、非金属材料和金属材料的技术问题,本发明提供一种等离子体刻蚀残留物清洗液,包括氧化剂、pH调节剂、稳定剂、有机酸铵盐、金属缓蚀剂、以及水。
进一步地,所述氧化剂的质量浓度为0.1wt%-30wt%。
进一步地,所述氧化剂为H2O2、N-甲基吗啉氧化物(NMMO或NMO)、过氧化苯甲酰、过氧单硫酸四丁铵、臭氧、高锰酸、高氯酸、碘酸、高碘酸、过硫酸、过氧二硫酸铵、过乙酸(CH3(CO)OOH)、过氧化脲((CO(NH2)2)H2O2)、硝酸、次氯酸铵、氯酸铵、碘酸铵、高氯酸铵、高碘酸铵、亚氯酸四甲铵、氯酸四甲铵、碘酸四甲铵、过硼酸四甲铵、高氯酸四甲铵、高碘酸四甲铵、过硫酸四甲铵、过氧乙酸、过氧苯甲酸、四氧嘧啶中的一种或多种。所述氧化剂优选为H2O2。
进一步地,所述有机酸铵盐的质量浓度为0.01wt%-50wt%。
进一步地,所述有机酸铵盐为甲酸铵、草酸铵、乳酸铵、酒石酸铵、柠檬酸三铵、乙酸铵、氨基甲酸铵、碳酸铵、苯甲酸铵、乙二胺四乙酸四铵(EDTA四铵)、乙二胺四乙酸三铵(EDTA三铵)、乙二胺四乙酸二铵(EDTA二铵)、琥珀酸铵、1-H-吡唑-3- 甲酸铵、丙二酸铵、己二酸铵、亚氨基二乙酸铵中的一种或多种。优选地,所述有机酸铵盐为螯合能力强的有机酸铵盐。
进一步地,所述pH调节剂的质量浓度为0.1wt%-20wt%。
进一步地,所述pH调节剂为碱性调节剂。
进一步地,所述pH调节剂为季胺氢氧化物、有机胺、有机醇胺中的一种或多种。
进一步地,所述季胺氢氧化物为四甲基氢氧化铵(TMAH)、四乙基氢氧化铵(TEAH)、三甲基苯基氢氧化铵、苄基三甲基氢氧化铵(BTMAH)、苄基三乙基氢氧化铵(BTEAH)、四丁基氢氧化铵、四丁基氢氧化磷(TBPH)、胆碱氢氧化物、氢氧化铵、十二烷基三甲基氢氧化铵(DTAH)、十六烷基三甲基氢氧化铵(CTOH)中的一种或多种。
进一步地,所述有机胺为单乙胺、二乙胺、三乙胺、三丙胺、N'N-二乙基乙二胺、羟乙基乙二胺、环己胺、1,2-丙二胺、五甲基二乙烯三胺中的一种或多种。
进一步地,所述有机醇胺为单乙醇胺(MEA)、二乙醇胺(DEA)、三乙醇胺(TEA)、二甘醇胺(DGA)、异丙醇胺、N-甲基乙醇胺中的一种或多种。
进一步地,所述pH调节剂为金属离子含量少的碱性pH调节剂。优选地,为金属离子含量<50ppb的碱性pH调节剂。
进一步地,所述稳定剂的质量浓度为0.05-1000ppm。所述稳定剂的质量浓度优选为 0.1-100ppm。
进一步地,所述稳定剂为甘氨酸、乙二胺四乙酸(EDTA)、反式-1,2环己二胺四乙酸(CDTA)、尿酸、吡啶甲酸、次氮基三乙酸(NTA)、乙二胺-N,N’-二琥铂酸(EDDS)、谷氨酸、二乙烯三胺五乙酸(DTPA)、羟乙基乙二胺三乙酸(HEDTA)、羟基乙叉二膦酸 (HEDP)、亚氨基二乙酸(IDA)、氨三乙酸、烟酸、酒石酸、柠檬酸、1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸(DOTA)、乙二醇四乙酸(EGTA)、1,2-双(邻氨基苯氧基)乙烷 -N,N,N’,N’-四乙酸、磺胺、丙二胺四乙酸中的一种或多种。
进一步地,所述金属缓蚀剂的质量浓度为0.02wt%-29wt%。
进一步地,所述金属缓蚀剂为多元醇与包含至少一个氮元素的杂环化合物的混合物。优选地,所述多元醇为含羟基数较多的多元醇。
进一步地,所述包含至少一个氮元素的杂环化合物为苯并三氮唑(BTA)、1,2,4-三氮唑、5-甲基苯并三氮唑(TTA)、羟基苯并***、吡唑、甲苯***、3,5-二甲基吡唑、四氮唑、4-氨基-1,2,4-***、苯并噻唑、甲基-1H-苯并***(TTL)、2-氨基苯并噻唑、2- 巯基苯并噻唑、3-氨基-5-羟基吡唑、1-苯基吡唑、巯基苯并咪唑、5-氨基四唑、3-巯基-1,2,4- ***、3-异丙基-1,2,4-***、2-(5-氨基-戊基)-苯并***、5-苯硫醇-苯并***、甲基四唑、 5-苯基-苯并***、5-硝基-苯并***、3-氨基-5-巯基-1,2,4-***、1-氨基-1,2,4***、羟苯并***、1-氨基-1,2,3-苯并***、噻唑中的一种或多种。所述包含至少一个氮元素的杂环化合物优选为苯并三氮唑(BTA)。
进一步地,所述多元醇的结构通式为CnH2n+2Om(n≥2,m≥2)。
进一步地,所述多元醇为甘油、季戊四醇、木糖醇、三羟甲基乙烷(TME)、三羟甲基丙烷(TMP)、乙二醇(EG)、丙二醇、1,2-丙二醇(1,2-PG)、1,4-丁二醇(BDO)、一缩二丙二醇、新戊二醇(NPG)、二缩二乙二醇、1,6-己二醇、葡萄塘、葡萄糖醇、果糖、核糖、丁四醇、戊五醇、己六醇、聚乙二醇400(PEG-400)、聚乙二醇600(PEG-600)、聚丙二醇400(PPG-400)、甘露醇、山梨醇中的一种或多种。
进一步地,所述水的质量浓度为28.4wt%-96.9wt%。
进一步地,所述的等离子体刻蚀残留物清洗液的pH为7-12。
本发明中的所有试剂均市售可得。
本发明中的ppm是指用溶质质量占全部溶液质量的百万分比来表示的质量浓度,称百万分比浓度;本发明的wt%为质量百分比浓度。
与现有技术相比较,本发明的优势在于:
本发明提供了一种等离子体刻蚀残留物清洗液,可有效去除晶圆清洗过程中的等离子体刻蚀残留物,例如,多元醇能够进一步降低BTA及其衍生物在铜表面的吸附,并且,在金属孔道中的残留物少;对氮化钛的刻蚀具有高选择性,能够高效去除氮化钛硬掩模;并且在高转速单片机清洗中对金属材料(如Cu和Co等)和非金属材料以及Low-k介质材料(如SiON、TEOS、BDII(低介电常数氧化硅)等)均有较小的腐蚀速率,例如,通过 BTA及其衍生物与多元醇的协同效应,能够很好地控制金属铜和钴的腐蚀;操作窗口较大,清洗温度范围广,可在20℃-80℃条件下使用;本申请的清洗液中不含氟,即使是小于14nm的晶圆也不会影响其电性能。本申请的等离子体刻蚀残留物清洗液在半导体晶圆清洗等微电子领域具有良好的应用前景。
具体实施方式
下面结合具体实施例,详细阐述本发明的优势。
以下通过实施例以及测试结果来详细阐明根据本发明所述的清洗液组合物,但不限于这些实施例和以及各测试显示的结果。本发明的清洗液组合物可体现为多种特定配方,其中所述的组合物具体组分以重量百分比来论述所有此类清洗液组合物。
实施例
制备方法:按照下述表1中各个实施例和对比例的配方(特定组分及其对应的特定含量)将各个组分进行简单混合。
表1.不同实施例及对比例的配方和清洗温度
效果实施例
用于测试蚀刻速率的测试对象及其来源:
TiN(氮化钛)空白晶片——Ramco Specialties Inc.(美国拉姆科专业有限公司)
Cu(铜)空白晶片——Ramco Specialties Inc.
Co(钴)空白晶片——Shanghai Huali Microelectronics Corporation.(上海华力微电子有限公司)
SiON(氮氧化硅)空白晶片——Ramco Specialties Inc.
TEOS(二氧化硅)空白晶片——Ramco Specialties Inc.
BDII(低介电常数氧化硅)空白晶片——Ramco Specialties Inc.
TiN、Cu、Co等金属蚀刻速率测试方法:
(1)利用Napson四点探针仪测试5*5cm金属空白晶片(TiN空白晶片、Cu空白晶片、Co空白晶片)的电阻初值(Rs1);
(2)将该5*5cm金属空白晶片在迷你单片机mini-SWT上400rpm,TiN空白晶片经清洗液处理5min,Cu空白晶片和Co空白晶片化学处理10min;
(3)取出该5*5cm金属空白晶片,用去离子水(DIW)清洗,高纯氮气吹干,再利用Napson四点探针仪测试5*5cm金属空白晶片的电阻值(Rs2);
(4)将上述电阻值和蚀刻时间输入到合适的程序可计算出金属的蚀刻速率。
SiON、TEOS、BDII等非金属蚀刻速率(Etch Rate)测试方法:
1)按照标准开启Nanospec6100测厚仪,选用合适的测试程序,将5*5cm非金属空白晶片(SiON空白晶片、TEOS空白晶片、BDII空白晶片)放入Nanospec6100 测厚仪上测试非金属空白晶片厚度,将非金属空白晶片旋转90°继续测试,连续测试4次,记录数值;
2)若非金属空白晶片为BDII,需用水冲洗干净,马弗炉350℃处理20min,干燥器冷却至室温再测试前值;(其他晶片无需步骤2)
3)将该5*5cm非金属空白晶片在mini-SWT上400rpm,清洗液处理10min;
4)取出该5*5cm非金属空白晶片,用DIW清洗,高纯氮气吹干,在Nanospec6100 测厚仪上按程序1测试晶片厚度,记录数值;
5)若非金属空白晶片为BDII,需用水冲洗干净,马弗炉350℃处理20min,干燥器冷却至室温再测试后值;(其他晶片无需步骤5)
6)将上述前后厚度值和蚀刻时间输入合适的程序中,蚀刻速率计算为厚度变化除以化学处理时间。
将按照表1的实施例与对比例制备得到的不同清洗液,按照上述蚀刻速率测试方法测试不同空白晶片的蚀刻速率,并利用X射线光电子能谱分析XPS测试金属缓蚀剂在铜晶圆表面的吸附情况,同时在50℃、400rpm/min的条件下,使用mini-SWT单片机清洗图案晶圆90s,水漂洗干净,氮气吹干。使用的介质为:TiN——氮化钛;Cu——铜;Co ——钴;SiON——氮氧化硅;TEOS——低介质材料;BDII——低介质材料。不同空白晶片的蚀刻速率、表面吸附结果、及清洗效果见表2。
表2.不同实施例与对比例的蚀刻速率、表面吸附结果、及清洗效果
表面吸附结果(XPS) | 晶圆清洗结果 |
◎基本无吸附 | ◎基本清洗干净 |
○轻微吸附 | ○少量残留物 |
△较多吸附 | △较多残留物 |
×严重吸附 | ×大量残留物 |
从表2中可以看出:本发明的清洗液对半导体制程中所用的金属(如Cu和Co)和非金属(SiON、TEOS、BDII)基本不会侵蚀,其腐蚀情况在高转速条件下均满足半导体业界通常在单片高速旋转清洗下的要求而对氮化钛的蚀刻有较高的选择性,蚀刻速率较高。对比例1与实施例18对照表明:在对比例1中,不添加BTA和多元醇的清洗液,金属Cu和Co腐蚀严重,且金属孔道中有大量残留物。对比例2与对比例1相比,对比例2中单独添加多元醇,对Cu和Co的腐蚀有一定的控制作用,但对比例2与实施例18相比,对比例2的清洗液对Cu和Co的腐蚀速率仍然较大,还是难以满足要求,但是,金属孔道被基本清洗干净,基本无残留。相对于对比例1、对比例2,对比例3中单独添加BTA能够有效抑制金属Cu和Co的腐蚀,其抑制效果比对比例2 中的单独添加多元醇效果好,但是,单独添加BTA的对比例3的清洗液对铜表面吸附物的去除能力差,即铜表面会有较多的BTA吸附。对比例3与实施例18相比,其Cu和 Co的腐蚀的腐蚀速率还有进一步降低的空间。综合对比实施例18以及对比例1-3可以说明,多元醇和BTA对金属的腐蚀有协同控制作用。相对于未添加多元醇的对比例3,此外,添加多元醇的清洗液(如对比例2和实施例18),BTA在铜表面吸附相对较少,说明多元醇的加入能够促进BTA从铜表面脱附,降低铜表面的残留,有利于提高半导体器件的良率。对比例4与实施例18相比,不添加有机酸铵盐的清洗液,氮化钛的蚀刻速率降低很多,说明有机酸铵盐能够促进氮化钛硬掩模的去除。
综上,本发明的积极进步效果在于:本发明开发的一种等离子体刻蚀残留物清洗液,通过BTA及其衍生物与多元醇的协同效应,能够很好地控制金属铜和钴的腐蚀,并且多元醇能够进一步降低BTA及其衍生物在铜表面的吸附。该清洗液能够高效地去除TiN硬掩模,并且在高转速单片机清洗中对非金属材料和Low-k介质材料(如SiON、TEOS、 BDII等)均有较小的腐蚀速率,操作窗口较大,在半导体晶片清洗等微电子领域具有良好的应用前景。
以上对本发明的具体实施例进行了详细描述,但其只是作为范例,本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言,任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此,在不脱离本发明的精神和范围下所作的均等变换和修改,都应涵盖在本发明的范围内。
Claims (24)
1.一种等离子体刻蚀残留物清洗液,其特征在于,包括氧化剂、pH调节剂、稳定剂、有机酸铵盐、金属缓蚀剂、以及水。
2.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述氧化剂的质量浓度为0.1wt%-30wt%。
3.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述氧化剂为H2O2、N-甲基吗啉氧化物、过氧化苯甲酰、过氧单硫酸四丁铵、臭氧、高锰酸、高氯酸、碘酸、高碘酸、过硫酸、过氧二硫酸铵、过乙酸、过氧化脲、硝酸、次氯酸铵、氯酸铵、碘酸铵、高氯酸铵、高碘酸铵、亚氯酸四甲铵、氯酸四甲铵、碘酸四甲铵、过硼酸四甲铵、高氯酸四甲铵、高碘酸四甲铵、过硫酸四甲铵、过氧乙酸、过氧苯甲酸、四氧嘧啶中的一种或多种。
4.如权利要求3所述的等离子体刻蚀残留物清洗液,其特征在于,所述氧化剂为H2O2。
5.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述有机酸铵盐的质量浓度为0.01wt%-50wt%。
6.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述有机酸铵盐为甲酸铵、草酸铵、乳酸铵、酒石酸铵、柠檬酸三铵、乙酸铵、氨基甲酸铵、碳酸铵、苯甲酸铵、乙二胺四乙酸四铵、乙二胺四乙酸三铵、乙二胺四乙酸二铵、琥珀酸铵、1-H-吡唑-3-甲酸铵、丙二酸铵、己二酸铵、亚氨基二乙酸铵中的一种或多种。
7.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述pH调节剂的质量浓度为0.1wt%-20wt%。
8.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述pH调节剂为碱性调节剂。
9.如权利要求8所述的等离子体刻蚀残留物清洗液,其特征在于,所述pH调节剂为季胺氢氧化物、有机胺、有机醇胺中的一种或多种。
10.如权利要求9所述的等离子体刻蚀残留物清洗液,其特征在于,所述季胺氢氧化物为四甲基氢氧化铵、四乙基氢氧化铵、三甲基苯基氢氧化铵、苄基三甲基氢氧化铵、苄基三乙基氢氧化铵、四丁基氢氧化铵、四丁基氢氧化磷、胆碱氢氧化物、氢氧化铵、十二烷基三甲基氢氧化铵、十六烷基三甲基氢氧化铵中的一种或多种。
11.如权利要求9所述的等离子体刻蚀残留物清洗液,其特征在于,所述有机胺为单乙胺、二乙胺、三乙胺、三丙胺、N'N-二乙基乙二胺、羟乙基乙二胺、环己胺、1,2-丙二胺、五甲基二乙烯三胺中的一种或多种。
12.如权利要求9所述的等离子体刻蚀残留物清洗液,其特征在于,所述有机醇胺为单乙醇胺、二乙醇胺、三乙醇胺、二甘醇胺、异丙醇胺、N-甲基乙醇胺中的一种或多种。
13.如权利要求9所述的等离子体刻蚀残留物清洗液,其特征在于,所述pH调节剂为金属离子含量小于50ppb的碱性pH调节剂。
14.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述稳定剂的质量浓度为0.05-1000ppm。
15.如权利要求14所述的等离子体刻蚀残留物清洗液,其特征在于,所述稳定剂的质量浓度为0.1-100ppm。
16.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述稳定剂为甘氨酸、乙二胺四乙酸、反式-1,2环己二胺四乙酸、尿酸、吡啶甲酸、次氮基三乙酸、乙二胺-N,N’-二琥铂酸、谷氨酸、二乙烯三胺五乙酸、羟乙基乙二胺三乙酸、羟基乙叉二膦酸、亚氨基二乙酸、氨三乙酸、烟酸、酒石酸、柠檬酸、1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸、乙二醇四乙酸、1,2-双(邻氨基苯氧基)乙烷-N,N,N’,N’-四乙酸、磺胺、丙二胺四乙酸中的一种或多种。
17.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述金属缓蚀剂的质量浓度为0.02wt%-29wt%。
18.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述金属缓蚀剂为多元醇与包含至少一个氮元素的杂环化合物的混合物。
19.如权利要求18所述的等离子体刻蚀残留物清洗液,其特征在于,所述包含至少一个氮元素的杂环化合物为苯并三氮唑、1,2,4-三氮唑、5-甲基苯并三氮唑、羟基苯并***、吡唑、甲苯***、3,5-二甲基吡唑、四氮唑、4-氨基-1,2,4-***、苯并噻唑、甲基-1H-苯并***、2-氨基苯并噻唑、2-巯基苯并噻唑、3-氨基-5-羟基吡唑、1-苯基吡唑、巯基苯并咪唑、5-氨基四唑、3-巯基-1,2,4-***、3-异丙基-1,2,4-***、2-(5-氨基-戊基)-苯并***、5-苯硫醇-苯并***、甲基四唑、5-苯基-苯并***、5-硝基-苯并***、3-氨基-5-巯基-1,2,4-***、1-氨基-1,2,4***、羟苯并***、1-氨基-1,2,3-苯并***、噻唑中的一种或多种。
20.如权利要求19所述的等离子体刻蚀残留物清洗液,其特征在于,所述包含至少一个氮元素的杂环化合物为苯并三氮唑。
21.如权利要求18所述的等离子体刻蚀残留物清洗液,其特征在于,所述多元醇的结构通式为CnH2n+2Om(n≥2,m≥2)。
22.如权利要求21所述的等离子体刻蚀残留物清洗液,其特征在于,所述多元醇为甘油、季戊四醇、木糖醇、三羟甲基乙烷、三羟甲基丙烷、乙二醇、丙二醇、1,2-丙二醇、1,4-丁二醇、一缩二丙二醇、新戊二醇、二缩二乙二醇、1,6-己二醇、葡萄塘、葡萄糖醇、果糖、核糖、丁四醇、戊五醇、己六醇、聚乙二醇400、聚乙二醇600、聚丙二醇400、甘露醇、山梨醇中的一种或多种。
23.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,所述水的质量浓度为28.4wt%-96.9wt%。
24.如权利要求1所述的等离子体刻蚀残留物清洗液,其特征在于,pH为7-12。
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