CN112442374A - 用于去除金属硬掩模和蚀刻后残余物的具有Cu/W相容性的水性制剂 - Google Patents
用于去除金属硬掩模和蚀刻后残余物的具有Cu/W相容性的水性制剂 Download PDFInfo
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- CN112442374A CN112442374A CN202011374468.9A CN202011374468A CN112442374A CN 112442374 A CN112442374 A CN 112442374A CN 202011374468 A CN202011374468 A CN 202011374468A CN 112442374 A CN112442374 A CN 112442374A
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- Prior art keywords
- acid
- ammonium
- composition
- ether
- glycol
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title abstract description 28
- 239000013011 aqueous formulation Substances 0.000 title abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 151
- 239000000463 material Substances 0.000 claims abstract description 70
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 37
- 238000005260 corrosion Methods 0.000 claims abstract description 35
- 230000007797 corrosion Effects 0.000 claims abstract description 35
- 239000003112 inhibitor Substances 0.000 claims abstract description 35
- 238000004377 microelectronic Methods 0.000 claims abstract description 35
- 239000007800 oxidant agent Substances 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 238000005530 etching Methods 0.000 claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011810 insulating material Substances 0.000 claims abstract description 5
- -1 tetraalkylammonium cation Chemical class 0.000 claims description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 26
- 239000008139 complexing agent Substances 0.000 claims description 23
- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 claims description 21
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 8
- APSPVJKFJYTCTN-UHFFFAOYSA-N tetramethylazanium;silicate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-][Si]([O-])([O-])[O-] APSPVJKFJYTCTN-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 7
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 239000004327 boric acid Substances 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
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 claims description 5
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 5
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 4
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 4
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 4
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 4
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 4
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 4
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 claims description 4
- 229960003330 pentetic acid Drugs 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical compound C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 claims description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 claims description 2
- WEGOLYBUWCMMMY-UHFFFAOYSA-N 1-bromo-2-propanol Chemical compound CC(O)CBr WEGOLYBUWCMMMY-UHFFFAOYSA-N 0.000 claims description 2
- YYTSGNJTASLUOY-UHFFFAOYSA-N 1-chloropropan-2-ol Chemical compound CC(O)CCl YYTSGNJTASLUOY-UHFFFAOYSA-N 0.000 claims description 2
- NVLADMORQQMDKF-UHFFFAOYSA-N 1-ethyl-1-oxidopyrrolidin-1-ium Chemical compound CC[N+]1([O-])CCCC1 NVLADMORQQMDKF-UHFFFAOYSA-N 0.000 claims description 2
- YIZTVEDOQDZLOH-UHFFFAOYSA-N 1-methyl-1-oxidopyrrolidin-1-ium Chemical compound C[N+]1([O-])CCCC1 YIZTVEDOQDZLOH-UHFFFAOYSA-N 0.000 claims description 2
- JMVIVASFFKKFQK-UHFFFAOYSA-N 1-phenylpyrrolidin-2-one Chemical compound O=C1CCCN1C1=CC=CC=C1 JMVIVASFFKKFQK-UHFFFAOYSA-N 0.000 claims description 2
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 claims description 2
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 claims description 2
- AIACLXROWHONEE-UHFFFAOYSA-N 2,3-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=C(C)C(=O)C=CC1=O AIACLXROWHONEE-UHFFFAOYSA-N 0.000 claims description 2
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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Abstract
本发明涉及用于去除金属硬掩模和蚀刻后残余物的具有Cu/W相容性的水性制剂。本发明提供可用于从上面具有氮化钛和/或光致抗蚀剂蚀刻残余物材料的微电子器件相对于金属导电材料例如钨和绝缘材料而言选择性去除所述氮化钛和/或光致抗蚀剂蚀刻残余物材料的组合物。所述去除组合物具有低pH,并含有至少一种氧化剂和至少一种蚀刻剂以及用于使金属腐蚀最小化的腐蚀抑制剂和用于保护电介质材料的钝化剂。
Description
本申请是申请日为2014年7月31日、申请号为201480043488.4、发明名称为“用于去除金属硬掩模和蚀刻后残余物的具有Cu/W相容性的水性制剂”的发明专利申请的分案申请。
技术领域
本发明涉及在金属导体和绝缘体材料(即,低k电介质)存在下选择性蚀刻氮化钛和/或光致抗蚀剂蚀刻残余物的组合物和方法,并且更具体地涉及以比铜、钨和低k电介质材料的暴露层或下伏层更高的蚀刻速率和选择性有效且高效地蚀刻氮化钛和/或光致抗蚀剂蚀刻残余物的组合物和方法。
背景技术
光致抗蚀剂掩模通常用于半导体工业中以对材料如半导体或电介质进行图案化。在一种应用中,光致抗蚀剂掩模被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连。所述双镶嵌工艺包括在覆盖金属导体层如铜层的低k电介质层上形成光致抗蚀剂掩模。然后根据所述光致抗蚀剂掩模蚀刻所述低k电介质层以形成暴露所述金属导体层的通孔和/或沟槽。所述通孔和沟槽通常被称为双镶嵌结构,其通常是使用两个光刻步骤来限定的。然后从低k电介质层去除光致抗蚀剂掩模,之后将导电材料沉积在通孔和/或沟槽中以形成互连。
随着微电子器件尺寸降低,实现通孔和沟槽的临界尺寸(critical dimension)变得更困难。因此,使用金属硬掩模来提供通孔和沟槽的更好轮廓控制。所述金属硬掩模可由钛或氮化钛制成,并且在形成双镶嵌结构的通孔和/或沟槽后通过湿式蚀刻工艺去除。至关重要的是所述湿式蚀刻工艺使用有效去除金属硬掩模和/或光致抗蚀剂蚀刻残余物而不影响下伏的金属导体层和低k电介质材料的去除化学。换句话说,去除化学需要对金属导体层和低k电介质层具高度选择性。
因此,本发明的一个目的在于提供相对于所存在的金属导体层和低k电介质层而言选择性去除硬掩模材料而不损害硬掩模的蚀刻速率的改进组合物。
发明内容
本发明涉及用于相对于所存在的金属导体层和低k电介质层而言选择性蚀刻硬掩模层和/或光致抗蚀剂蚀刻残余物的组合物和方法。更具体地,本发明涉及用于选择性蚀刻氮化钛和/或光致抗蚀剂蚀刻残余物并在同时与铜、钨和低k电介质层相容的组合物和方法。
在一个方面,描述了用于从上面具有氮化钛和/或光致抗蚀剂蚀刻残余物材料的微电子器件的表面选择性去除所述氮化钛和/或光致抗蚀剂蚀刻残余物材料的组合物,所述组合物包含至少一种氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、至少一种钝化剂、至少一种溶剂和任选地至少一种络合剂,其中所述组合物基本上不含过氧化氢。
在另一个方面,描述了用于从上面具有氮化钛和/或光致抗蚀剂蚀刻残余物材料的微电子器件的表面选择性去除所述氮化钛和/或光致抗蚀剂蚀刻残余物材料的组合物,所述组合物包含至少一种含碘氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、至少一种钝化剂、至少一种溶剂、至少一种碘清除剂和任选地至少一种络合剂,其中所述组合物基本上不含过氧化氢。
在另一个方面,描述了从上面具有氮化钛材料的微电子器件的表面蚀刻所述氮化钛材料的方法,所述方法包括使所述表面与包含至少一种氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、至少一种钝化剂、至少一种溶剂和任选地至少一种络合剂的组合物接触,其中所述组合物基本上不含过氧化氢,并且其中所述组合物从所述表面相对于金属和绝缘材料而言选择性去除氮化钛材料。
在另一个方面,描述了从上面具有氮化钛材料的微电子器件的表面蚀刻所述氮化钛材料的方法,所述方法包括使所述表面与包含至少一种含碘氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、至少一种钝化剂、至少一种碘清除剂、至少一种溶剂和任选地至少一种络合剂的组合物接触,其中所述组合物基本上不含过氧化氢,并且其中所述组合物从所述表面相对于金属和绝缘材料而言选择性去除氮化钛材料。
根据随后的公开内容和权利要求书,本发明的其它方面、特征和实施方式将更完全地显而易见。
具体实施方式
一般来说,本发明涉及用于相对于所存在的金属导体层和低k电介质层而言选择性蚀刻硬掩模层和/或光致抗蚀剂蚀刻残余物的组合物和方法。更具体地,本发明涉及用于相对于铜、钨和低k电介质层而言选择性蚀刻氮化钛和/或光致抗蚀剂蚀刻残余物的组合物和方法。微电子器件上可能存在的其它材料应该基本上不被所述组合物去除或腐蚀。
为便于参考,“微电子器件”对应于半导体衬底、平板显示器、相变存储器件、太阳能面板和其它产品,包括太阳能电池器件、光伏器件和微机电***(MEMS),其被制造用于微电子、集成电路、能量收集或计算机芯片应用中。应理解,术语“微电子器件”、“微电子衬底”和“微电子器件结构”并不意在以任何方式进行限制,并且包括最终将变成微电子器件或微电子组件的任何衬底或结构。所述微电子器件可以被图案化、毯覆,可以是控制件和/或测试器件。
本文中使用的“硬掩模封盖层”对应于在等离子体蚀刻步骤期间沉积在电介质材料上以保护所述电介质材料的材料。硬掩模封盖层在传统上是氮化硅、氧氮化硅、氮化钛、氧氮化钛、钛和其它类似化合物。
在本文中使用时,“氮化钛”和“TiNx”对应于纯氮化钛以及包括不同的化学计量比和氧含量的不纯的氮化钛(TiOxNy)。
在本文中使用时,“约”旨在对应于所陈述的值的±5%。
如本文所定义,“低k电介质材料”对应于在层状微电子器件中用作电介质材料的任何材料,其中所述材料具有小于约3.5的介电常数。优选地,所述低k电介质材料包括低极性材料如含硅有机聚合物、含硅杂化有机/无机材料、有机硅酸盐玻璃(OSG)、TEOS、氟化硅酸盐玻璃(FSG)、二氧化硅和碳掺杂氧化物(CDO)玻璃。应理解,所述低k电介质材料可具有不同的密度和不同的孔隙率。
如本文所定义,“金属导体层”包含铜、钨、钴、钼、铝、钌、包含上述金属的合金以及其组合。
如本文所定义,“胺”物质包括至少一种伯、仲和叔胺,其条件是(i)包括羧酸基团和胺基团两者的物质(例如氨基酸、氨基多羧酸等)、(ii)包括胺基团的表面活性剂(例如,醚胺如(Air Products)和胺氧化物表面活性剂),(iii)其中胺基团是取代基(例如,连接至芳基或杂环部分)的物质,(iv)胺-N-氧化物,以及(v)吡啶和吡啶衍生物根据这个定义不被视为“胺”。所述胺的分子式由NR1R2R3表示,其中R1、R2和R3可以彼此相同或不同并选自氢、直链或支链的C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)、C6-C10芳基(例如,苄基)、直链或支链的C1-C6烷醇(例如,甲醇、乙醇、丙醇、丁醇、戊醇、己醇)和其组合,其条件是R1、R2和R3不能都是氢。
如本文所定义,“光致抗蚀剂蚀刻残余物”对应于包含光致抗蚀剂材料或作为在蚀刻或灰化步骤后的光致抗蚀剂副产物的材料的任何残余物,正如本领域技术人员所容易理解的。
“基本上不含”在本文中被定义为小于2重量%,优选小于1重量%、更优选小于0.5重量%,甚至更优选小于0.1重量%并且最优选0重量%。
在本文中使用时,“氟化物”物质对应于包括氟离子(F-)或共价键合的氟的物质。应理解,氟化物物质可以以氟化物物质形式而被包括或在原位产生。
本发明的组合物可以以如下文更充分描述的多种特定制剂来实施。
在所有这些组合物(其中根据包括零下限的重量百分比范围讨论了所述组合物的特定组分)中,应理解,这些组分在所述组合物的各种特定实施方式中可能存在或不存在,并且在存在这些组分的情况下,以其中使用这些组分的组合物的总重量计,它们可以以低至0.001重量%的浓度存在。
本发明的实施方式包括用于去除硬掩模和/或光致抗蚀剂蚀刻残余物的化学。在一个实施方式中,去除组合物是去除电介质层上的金属硬掩模和/或光致抗蚀剂蚀刻残余物并且相对于所述电介质层下面的金属导体层和所述电介质层本身而言具有高度选择性的湿式蚀刻溶液。在一个更具体实施方式中,所述去除组合物是相对于铜、钨和低k电介质材料中的至少一种而言高度选择性去除氮化钛层和/或光致抗蚀剂蚀刻残余物的湿式蚀刻溶液。
在一个方面,描述了用于从上面具有氮化钛和/或光致抗蚀剂蚀刻残余物材料的微电子器件的表面选择性去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的组合物,所述组合物包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、至少一种钝化剂、至少一种溶剂和任选地至少一种络合剂,其中所述组合物基本上不含过氧化氢。在另一个实施方式中,所述第一方面的组合物包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种含碘氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、至少一种钝化剂、至少一种溶剂、至少一种碘清除剂和任选地至少一种络合剂,其中所述组合物基本上不含过氧化氢。优选地,以组合物的总重量计,所述组合物包含至少95重量%的水、更优选至少97重量%的水、最优选至少98重量%的水。有利的是,所述组合物具有高于50:1的TiN:钨选择性和小于的钨去除速率。所述组合物基本上不含如本文所定义的胺、研磨材料、金属卤化物和其组合。所述组合物具有在0至4、优选在1至3范围内的pH值。
添加蚀刻剂是为了提高氮化钛的蚀刻速率。设想的蚀刻剂包括但不限于HF、氟化铵、四氟硼酸、六氟硅酸、含有B-F或Si-F键的其它化合物、四氟硼酸四丁基铵(TBA-BF4)、氟化四烷基铵(NR1R2R3R4F)、强碱例如氢氧化四烷基铵(NR1R2R3R4OH)(其中R1、R2、R3、R4可以彼此相同或不同并选自氢、直链或支链的C1-C6烷基基团(例如,甲基、乙基、丙基、丁基、戊基、己基)、C1-C6烷氧基基团(例如,羟基乙基、羟基丙基)、被取代或未被取代的芳基基团(例如,苄基))、弱碱和其组合。优选地,氟化物源包括HF、四氟硼酸、六氟硅酸、H2ZrF6、H2TiF6、HPF6、氟化铵、氟化四甲基铵、氢氧化四甲基铵、六氟硅酸铵、六氟钛酸铵,或氟化铵与氟化四甲基铵的组合。最优选地,所述蚀刻剂包含HF、六氟硅酸或四氟硼酸。
所述第一方面的组合物包含至少一种低k钝化剂以减少低k电介质层的化学攻击并保护晶片免于另外的氧化。优选的低k钝化剂包括但不限于硼酸、硼酸盐(例如,五硼酸铵、四硼酸钠、二硼酸铵)、烷氧基硅烷(例如,甲基三甲氧基硅烷、二甲基二甲氧基硅烷、苯基三甲氧基硅烷、四乙氧基硅烷(TEOS)、N-丙基三甲氧基硅烷、N-丙基三乙氧基硅烷、己基三甲氧基硅烷、己基三乙氧基硅烷、六氟硅酸铵、硅酸钠、硅酸四甲基铵(TMAS))、3-羟基-2-萘甲酸、丙二酸和亚氨基二乙酸。优选地,使用本文描述的组合物,以下伏的低k材料的总重量计,少于2重量%、更优选少于1重量%、最优选少于0.5重量%的下伏的低k材料被蚀刻/去除。专业技术人员应理解,氢氟酸与硼酸(或硼酸盐)的组合将导致四氟硼酸的形成。专业技术人员还应理解,氢氟酸与烷氧基硅烷的组合将导致六氟硅酸的形成。
包括氧化剂是为了氧化TiNx中的Ti3+。本文设想的氧化剂包括但不限于过氧化氢(H2O2)、FeCl3、FeF3、Fe(NO3)3、Sr(NO3)2、CoF3、MnF3、过硫酸氢钾复合盐(2KHSO5·KHSO4·K2SO4)、高碘酸、碘酸、氧化钒(V)、氧化钒(IV,V)、钒酸铵、多原子酸铵盐(例如,过氧单硫酸铵、亚氯酸铵(NH4ClO2)、氯酸铵(NH4ClO3)、碘酸铵(NH4IO3)、硝酸铵(NH4NO3)、过硼酸铵(NH4BO3)、高氯酸铵(NH4ClO4)、高碘酸铵(NH4IO4)、过硫酸铵((NH4)2S2O8)、次氯酸铵(NH4ClO))、钨酸铵((NH4)10H2(W2O7))、多原子酸钠盐(例如,过硫酸钠(Na2S2O8)、次氯酸钠(NaClO)、过硼酸钠)、多原子酸钾盐(例如,碘酸钾(KIO3)、高锰酸钾(KMnO4)、过硫酸钾、硝酸(HNO3)、过硫酸钾(K2S2O8)、次氯酸钾(KClO))、多原子酸四甲基铵盐(例如,亚氯酸四甲基铵((N(CH3)4)ClO2)、氯酸四甲基铵((N(CH3)4)ClO3)、碘酸四甲基铵((N(CH3)4)IO3)、过硼酸四甲基铵((N(CH3)4)BO3)、高氯酸四甲基铵((N(CH3)4)ClO4)、高碘酸四甲基铵((N(CH3)4)IO4)、过硫酸四甲基铵((N(CH3)4)S2O8))、多原子酸四丁基铵盐(例如,过氧单硫酸四丁基铵)、过氧单硫酸、硝酸铁(Fe(NO3)3)、过氧化氢脲((CO(NH2)2)H2O2)、过乙酸(CH3(CO)OOH)、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯苯醌、阿脲和其组合。当所述氧化剂是盐时,它可以是水合的或无水的。可在制造商处、在将组合物引入器件晶片之前,或可选地在器件晶片处(即在原位)将所述氧化剂引入所述组合物。优选地,用于所述第二方面的组合物的氧化剂包含过氧化氢。优选地,用于所述第一方面的组合物的氧化剂包含胺-N-氧化物、氧化钒、碘酸铵、高碘酸铵、碘酸或高碘酸。
添加金属腐蚀抑制剂是为了阻断所述氧化剂和羧酸盐(当存在时)的氧化活性。本文设想的金属腐蚀抑制剂包括但不限于5-氨基-1,3,4-噻二唑-2-硫醇(ATDT)、苯并***(BTA)、1,2,4-***(TAZ)、甲苯基***、5-甲基-苯并***(MBTA)、5-苯基-苯并***、5-硝基-苯并***、苯并***羧酸、3-氨基-5-巯基-1,2,4-***、1-氨基-1,2,4-***、羟基苯并***、2-(5-氨基-戊基)-苯并***、1-氨基-1,2,3-***、1-氨基-5-甲基-1,2,3-***、3-氨基-1,2,4-***、3-巯基-1,2,4-***、3-异丙基-1,2,4-***、5-苯基硫醇-苯并***、卤代-苯并***(卤代=F、Cl、Br或I)、萘并***、2-巯基苯并咪唑(MBI)、2-巯基苯并噻唑、4-甲基-2-苯基咪唑、2-巯基噻唑啉、5-氨基四唑、戊四唑、5-苯基-1H-四唑、5-苄基-1H-四唑、Ablumine O(Taiwan Surfactant)、琥珀酰亚胺、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑烷酮、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、二氨基甲基三嗪、咪唑啉硫酮、4-甲基-4H-1,2,4-***-3-硫醇、苯并噻唑、咪唑、吲唑、腺苷、咔唑、糖精、苯偶姻肟、胺-N-氧化物(例如,N-甲基吗啉N-氧化物(NMMO)、三甲基胺N-氧化物、三乙基胺-N-氧化物、吡啶-N-氧化物、N-乙基吗啉-N-氧化物、N-甲基吡咯烷-N-氧化物和N-乙基吡咯烷-N-氧化物)和其组合。另外的腐蚀抑制剂包括阳离子型季铵盐例如苯扎氯铵、氯化苄基二甲基十二烷基铵、溴化十四烷基三甲基铵、溴化十二烷基三甲基铵、氯化十六烷基吡啶Aliquat 336(Cognis)、氯化苄基二甲基苯基铵、Crodaquat TES(Croda Inc.)、Rewoquat CPEM(Witco)、对甲苯磺酸十六烷基三甲基铵、氢氧化十六烷基三甲基铵、二氯化1-甲基-1’-十四烷基-4,4’-联吡啶溴化烷基三甲基铵、盐酸氨丙啉、氢氧化苄乙氧铵、苄索氯铵、氯化苄基二甲基十六烷基铵、氯化苄基二甲基十四烷基铵、溴化苄基十二烷基二甲基铵、氯化苄基十二烷基二甲基铵、西吡氯铵、胆碱对甲苯磺酸盐、溴化二甲基二-十八烷基铵、溴化十二烷基乙基二甲基铵、氯化十二烷基三甲基铵(DTAC)、溴化乙基十六烷基二甲基铵、溴化十二烷基(2-羟基乙基)二甲基铵、氯化十六烷基(2-羟基乙基)二甲基铵、对甲苯磺酸十六烷基三甲基铵、氯化十二烷基吡啶(十二烷基吡啶)、甲磺酸十二烷基三甲基铵、对甲苯磺酸十二烷基三甲基铵、氯化[9-(2-羧基苯基)-6-二乙基氨基-3-亚呫吨基]-二乙基铵(罗丹明B)、吉拉德试剂、磷酸二氢十六烷基(2-羟基乙基)二甲基铵、溴化十六烷基吡啶溴化十六烷基三甲基铵、氯化十六烷基三甲基铵、氯化甲基苄乙氧铵、1622、LuviquatTM、N,N',N'-聚氧乙烯(10)-N-牛脂-1,3-二氨基丙烷液体、奥芬溴铵、溴化四庚基铵、溴化四(癸基)铵、通佐溴铵、氯化三-十二烷基铵、溴化三甲基十八烷基铵、四氟硼酸1-甲基-3-正辛基咪唑四氟硼酸1-癸基-3-甲基咪唑氯化1-癸基-3-甲基咪唑溴化三-十二烷基甲基铵、氯化二甲基二硬脂基铵和氯化六甲双铵。其它腐蚀抑制剂包括非离子型表面活性剂如PolyFox PF-159(OMNOVA Solutions)、聚(乙二醇)(“PEG”)、聚(丙二醇)(“PPG”)、PEG-PPG共聚物如Pluronic F-127(BASF),阴离子型表面活性剂如十二烷基苯磺酸、十二烷基硫酸钠、十二烷基苯磺酸钠和其组合。季铵盐可以充当腐蚀抑制剂(特别是对于铜和钨)和润湿剂两者。优选的钨腐蚀抑制剂包括醚胺,包括但不限于醚季胺(例如,Q-系列如氯化异癸氧基丙基双-(2-羟基乙基)甲基铵、氯化异十三烷氧基丙基双-(2-羟基乙基)甲基铵、氯化单大豆甲基铵、牛脂二胺双季铵盐、氯化椰油基聚(15)氧乙烯甲基铵)、醚胺氧化物(例如,AO系列如双-(2-羟基乙基)异癸氧基丙基胺氧化物)、直链烷氧基丙基胺氧化物、低泡烷氧基丙基胺氧化物(AO-405和AO-455)和其组合。其它胺氧化物表面活性剂也将是有用的钨腐蚀抑制剂,包括但不限于十二烷基二甲基胺氧化物、双-(2-羟基乙基)-椰油烷基胺氧化物(C/12W、Azko Nobel)、二甲基椰油烷基胺氧化物(DMC)、4-(苄氧基)吡啶N-氧化物、4-(3-苯基丙基)吡啶N-氧化物和其组合。其它有用的钨腐蚀抑制剂包括杂环化合物例如吡啶、喹啉、喹唑啉、异喹啉、吡嗪、嘧啶、哒嗪、喹喔啉、吩嗪、菲啶、2,2’-吡啶、1,4’-吡啶、4,4’-吡啶和吖啶,以及包括至少一个下列基团的所述杂环化合物的衍生物:C1-6烷基、苯基、苄基、苯乙基、3-苯基丙基、苄氧基、羧基、氯、溴、甲氧基、硝基和氰基,包括但不限于2-苄基吡啶和4-(4-硝基苄基)吡啶。对于本领域技术人员来说显而易见的是,虽然季铵盐最通常以氯化物或溴化物形式市售,但使卤化物阴离子与非卤化物阴离子如硫酸盐、甲磺酸盐、硝酸盐、氢氧化物等进行离子交换是容易的。本文中也设想了这些转化的季铵盐,并且它们是优选的。优选的腐蚀抑制剂包括阳离子型季铵盐,更优选为溴化十四烷基三甲基铵、苯扎氯铵、对甲苯磺酸十六烷基三甲基铵、DTAC和氢氧化十六烷基三甲基铵,其中在使用前已将氯化物进行了离子交换。可选地,优选的腐蚀抑制剂包括5-甲基-苯并***,以及四唑例如5-苄基-1H-四唑。在另一个可选实施方式中,优选的腐蚀抑制剂包括胺-N-氧化物、胺氧化物表面活性剂和/或醚胺,其中已将氯化物进行了离子交换。
所述至少一种溶剂可以包含水、至少一种与水混溶的有机溶剂或其组合,其中所述至少一种与水混溶的有机溶剂选自式R1R2R3C(OH)的化合物,其中R1、R2和R3是彼此独立的并选自氢、C2-C30烷基、C2-C30烯烃、环烷基、C2-C30烷氧基和其组合。例如,所述至少一种溶剂可以包含选自以下的至少一种物质:水、甲醇、乙醇、异丙醇、丁醇和更高级的醇、四氢糠醇(THFA)、3-氯-1,2-丙二醇、3-氯-1-丙烷硫醇、1-氯-2-丙醇、2-氯-1-丙醇、3-氯-1-丙醇、3-溴-1,2-丙二醇、1-溴-2-丙醇、3-溴-1-丙醇、3-碘-1-丙醇、4-氯-1-丁醇、2-氯乙醇、二氯甲烷、氯仿、乙酸、丙酸、三氟乙酸、四氢呋喃(THF)、N-甲基吡咯烷酮(NMP)、环己基吡咯烷酮、N-辛基吡咯烷酮、N-苯基吡咯烷酮、甲基二乙醇胺、甲酸甲酯、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、四亚甲基砜(环丁砜)、二乙基醚、苯氧基-2-丙醇(PPh)、苯丙酮、乳酸乙酯、乙酸乙酯、苯甲酸乙酯、乙腈、丙酮、乙二醇、丙二醇(PG)、1,3-丙二醇、1,4-丙二醇、二烷、丁内酯、碳酸丁烯酯、碳酸乙烯酯、碳酸丙烯酯、二丙二醇、二乙二醇单甲醚、三乙二醇单甲醚、二乙二醇单***、三乙二醇单***、乙二醇单丙醚、乙二醇单丁醚、二乙二醇单丁醚(即丁基卡必醇)、三乙二醇单丁醚、乙二醇单己醚、二乙二醇单己醚、乙二醇苯醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二丙二醇二甲醚、二丙二醇***、丙二醇正丙醚、二丙二醇正丙醚(DPGPE)、三丙二醇正丙醚、丙二醇正丁醚、二丙二醇正丁醚、三丙二醇正丁醚、丙二醇苯醚、乙酸二丙二醇甲醚、四乙二醇二甲醚(TEGDE)、二元酸酯、碳酸甘油酯、N-甲酰基吗啉、磷酸三乙基酯和其组合。优选地,所述至少一种溶剂包含水,更优选地去离子水。
当存在络合剂时,添加络合剂是为了减少粒子产生和生长并提高组合物的储存期限。设想的螯合剂包括但不限于β-二酮(β-diketonate)化合物例如2,4-戊二酮、乙酰丙酮化物(acetylacetonate)、1,1,1-三氟-2,4-戊二酮和1,1,1,5,5,5-六氟-2,4-戊二酮;氨基酸例如甘氨酸、丝氨酸、脯氨酸、亮氨酸、丙氨酸、天冬酰胺、天冬氨酸、谷氨酰胺、组氨酸、谷氨酸、精氨酸、半胱氨酸、缬氨酸和赖氨酸;选自以下的多元酸和氨基多羧酸:亚氨基二乙酸(IDA)、丙二酸、草酸、琥珀酸、硼酸、次氮基三乙酸、苹果酸、柠檬酸、乙酸、马来酸、乙二胺四乙酸(EDTA)、EDTA-2NH3(乙二胺四乙酸二铵盐)、(1,2-亚环己基二次氮基)四乙酸(CDTA)、二亚乙基三胺五乙酸(DTPA)、2-膦酰基丁烷-1,2,4-三羧酸(PBTCA)、乙二胺二琥珀酸和丙二胺四乙酸;膦酸;膦酸衍生物例如羟基亚乙基二膦酸(HEDP)(Dequest 2010)、1-羟基乙烷-1,1-二膦酸、次氮基-三(亚甲基膦酸)(NTMP)、氨基三(亚甲基膦酸)(Dequest 2000)、二亚乙基三胺五(亚甲基膦酸)(Dequest 2060S)、乙二胺四(亚甲基膦酸)(EDTMPA);和其组合。可替选地或除此之外,所述至少一种络合剂可以包括阴离子型表面活性剂,包括但不限于烷基硫酸钠例如乙基己基硫酸钠(08)、烷基硫酸铵、烷基(C10-C18)羧酸铵盐、磺基琥珀酸钠和其酯例如二辛基磺基琥珀酸钠、烷基(C6-C18)磺酸钠盐,以及二阴离子磺酸盐表面活性剂。优选的阴离子型表面活性剂包括二苯基氧化物二磺酸盐,例如可以从Dow Chemical获得的DOWFAX系列的阴离子型表面活性剂,包括DOWFAX 2A1(四丙基二苯基氧化物二磺酸钠)、DOWFAX 3A2、DOWFAX 8390和DowFaxTMC6L(烷基二苯基氧化物二磺酸盐),以及可以从Rhone-Poulenc获得的RHODACAL DSB、可以从Olin获得的POLY-TERGENT 2A1、POLY-TERGENT 2EP、可以从Cytec获得的AEROSOL DPOS-45、可以从Pilot Chemicals获得的CALFAX DBA-40、CALFAX 16L-35等。二苯基氧化物二磺酸盐代表了一类高阴离子型表面活性剂,其由二磺酸化的烷基二苯基氧化物分子构成,其中电荷由两个磺酸基团产生,并提供出色的乳液稳定性。可替选地或除此之外,所述至少一种络合剂可以包括阻垢剂聚合物,包括但不限于多氨基酰胺(PAMAM)树枝状聚合物、聚(2-乙基-2-唑啉)、聚乙烯亚胺(PEI)、羟基化的聚乙烯亚胺、改性的聚乙烯亚胺、聚烯丙基胺盐酸盐(PALAM)、聚(丙烯酰胺)、聚(丙烯酸)、聚(氯化二烯丙基二甲基铵)、氯化二烯丙基二甲基铵、丙烯酰胺、乙酰胍胺、聚(丙烯酰胺-共-氯化二烯丙基-二甲基铵)(PAMALAM)和其组合。可替选地或除此之外,络合剂包括包含铵阳离子或四烷基铵阳离子([NR1R2R3R4]+,其中R1、R2、R3和R4可以彼此相同或不同并选自氢和C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基))和选自以下的阴离子的盐:乙酸根、氯离子、溴离子、碘离子、硫酸根、苯甲酸根、丙酸根、柠檬酸根、甲酸根、草酸根、酒石酸根、琥珀酸根、乳酸根、马来酸根、丙二酸根、延胡索酸根、苹果酸根、抗坏血酸根、扁桃酸根和邻苯二甲酸根。例如,所述盐可以包括溴化铵和/或氯化铵。最优选地,所述络合剂包含以下至少一者:烷基二苯基氧化物二磺酸盐、2,4-戊二酮、丝氨酸和其任何组合。
当所述氧化剂包含碘酸盐或高碘酸盐时,碘清除剂可任选地被添加至半水性组合物。虽然不希望受理论束缚,但据认为,随着碘酸盐或高碘酸盐被还原,碘积聚,这增加了铜蚀刻速率。碘清除剂包括但不限于酮,更优选地为在羰基的α位上具有氢的酮,例如4-甲基-2-戊酮、2,4-二甲基-3-戊酮、环己酮、5-甲基-3-庚酮、3-戊酮、5-羟基-2-戊酮、2,5-己二酮、4-羟基-4-甲基-2-戊酮、丙酮、丁酮、2-甲基-2-丁酮、3,3-二甲基-2-丁酮、4-羟基-2-丁酮、环戊酮、2-戊酮、3-戊酮、1-苯基乙酮、苯乙酮、二苯甲酮、2-己酮、3-己酮、2-庚酮、3-庚酮、4-庚酮、2,6-二甲基-4-庚酮、2-辛酮、3-辛酮、4-辛酮、二环己基酮、2,6-二甲基环己酮、2-乙酰基环己酮、2,4-戊二酮、薄荷酮和其组合。优选地,碘清除剂包括4-甲基-2-戊酮、2,4-二甲基-3-戊酮或环己酮。
在另一个实施方式中,本发明的任何组合物可进一步包含氮化钛和/或光致抗蚀剂蚀刻材料残余物,其中所述残余物被悬浮和/或溶解在所述水性组合物中。
在一个实施方式中,第一方面的组合物包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、至少一种钝化剂、至少一种溶剂和任选地至少一种络合剂,其中所述组合物基本上不含过氧化氢,所述物质以所述组合物的总重量计以下列范围存在:
在另一个实施方式中,第一方面的组合物包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种含碘氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、至少一种钝化剂、至少一种溶剂、至少一种碘清除剂和任选地至少一种络合剂,其中所述组合物基本上不含过氧化氢,所述物质以所述组合物的总重量计以下列范围存在:
优选地,第一方面的去除组合物的一个实施方式包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种高碘酸盐氧化剂、至少一种蚀刻剂、至少一种溶剂、至少一种腐蚀抑制剂和至少一种钝化剂,其中所述组合物基本上不含过氧化氢。更优选地,这个实施方式的去除组合物包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种高碘酸盐氧化剂、六氟硅酸、水、至少一种腐蚀抑制剂和至少一种钝化剂,其中所述组合物基本上不含过氧化氢。甚至更优选地,这个实施方式的去除组合物包含以下物质,由以下物质组成或基本上由以下物质组成:高碘酸、六氟硅酸、水、TMAS和至少一种腐蚀抑制剂,其中所述组合物基本上不含过氧化氢。最优选地,这个实施方式的去除组合物包含以下物质,由以下物质组成或基本上由以下物质组成:高碘酸、六氟硅酸、水、TMAS和选自苯扎氯铵、胺-N-氧化物、胺氧化物表面活性剂和/或醚胺的至少一种腐蚀抑制剂,其中所述组合物基本上不含过氧化氢。
优选地,第一方面的去除组合物的另一个实施方式包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种氧化剂、至少一种蚀刻剂、至少一种溶剂、至少一种胺氧化物腐蚀抑制剂和至少一种钝化剂,其中所述组合物基本上不含过氧化氢。更优选地,这个实施方式的去除组合物包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种氧化剂、四氟硼酸、水、至少一种钝化剂和选自胺-N-氧化物、胺氧化物表面活性剂和/或醚胺的至少一种腐蚀抑制剂,其中所述组合物基本上不含过氧化氢。甚至更优选地,这个实施方式的去除组合物包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种氧化剂、四氟硼酸、水、硼酸或硼酸盐,以及选自苯扎氯铵、胺-N-氧化物、胺氧化物表面活性剂和/或醚胺的至少一种腐蚀抑制剂,其中所述组合物基本上不含过氧化氢。
在另一个实施方式中,第一方面的去除组合物包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种碘酸盐氧化剂、至少一种蚀刻剂、至少一种溶剂、至少一种腐蚀抑制剂、至少一种碘清除剂和至少一种钝化剂,其中所述组合物基本上不含过氧化氢。更优选地,这个实施方式的去除组合物包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种碘酸盐氧化剂、六氟硅酸、水、至少一种腐蚀抑制剂、至少一种碘清除剂和至少一种钝化剂,其中所述组合物基本上不含过氧化氢。
应理解,通常的做法是制造待在使用前稀释的浓缩形式的组合物。例如,所述组合物可以被制造成更浓缩的形式并且其后在制造商处、在使用前和/或在制造厂使用期间用至少一种溶剂稀释。稀释比率可在约0.1份稀释剂:1份组合物浓缩物至约100份稀释剂:1份组合物浓缩物范围内。还应理解,本文所述的组合物包括可能随时间不稳定的氧化剂。因此,浓缩形式可以基本上不含氧化剂并且所述氧化剂可由制造商在使用前和/或在制造厂使用期间引入到浓缩物或稀释的组合物。
本文所述的组合物容易通过简单添加各个成分并混合至均质条件来配制。此外,所述组合物可容易地配制成单包装制剂或在使用地点处或之前混合的多部分制剂,优选地为多部分制剂。所述多部分制剂的单独的部分可在工具处或在混合区/区域如在线混合器中或在工具上游的储罐中混合。设想了多部分制剂的各个部分可含有当混合在一起时形成所需组合物的成分/组分的任何组合。各个成分的浓度可在组合物的特定倍数内广泛改变,即,更稀释或更浓缩,并且应理解,组合物可不同地和可选地包含以下物质,由以下物质组成或基本上由以下物质组成:与本文公开内容一致的成分的任何组合。
因此,第二方面涉及一种试剂盒,所述试剂盒在一个或多个容器中包括一种或多种适于形成本文所述的组合物的组分。所述试剂盒的容器必须适合储存和运输所述去除组合物组分,例如,容器(Advanced Technology Materials,Inc.,Danbury,Conn.,USA)。含有所述组合物的组分的一个或多个容器优选包括用于使所述一个或多个容器中的组分流体连通以共混和分配的机构。例如,对于容器来说,可将气体压力施加至所述一个或多个容器中的衬里外部以造成所述衬里的内含物的至少一部分被排出并且因此能够实现流体连通以用于共混和分配。可选地,可将气体压力施加至常规可加压容器的顶空或者可使用泵来实现流体连通。另外,所述***优选包括分配端口以将共混的组合物分配至处理工具。
优选使用基本上化学惰性、不含杂质、柔性和弹性的聚合物膜材料如高密度聚乙烯来制造用于所述一个或多个容器的衬里。处理所需的衬里材料而无需共挤出或阻挡层,并且无需可能不利地影响有待放置在衬里中的组分的纯度要求的任何颜料、UV抑制剂或加工剂。所需衬里材料的列表包括包含未处理(不含添加剂)的聚乙烯、未处理的聚四氟乙烯(PTFE)、聚丙烯、聚氨酯、聚偏二氯乙烯、聚氯乙烯、聚缩醛、聚苯乙烯、聚丙烯腈、聚丁烯等的膜。这些衬里材料的优选厚度在约5密耳(0.005英寸)至约30密耳(0.030英寸)范围内,例如20密耳(0.020英寸)的厚度。
关于用于试剂盒的容器,以下专利和专利申请的公开内容以全文引用的方式并入本文中:名称为“用于在超纯液体中使粒子的产生最小化的装置和方法(APPARATUS ANDMETHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS)”的美国专利No.7,188,644;名称为“可回收和可重复使用的泡包袋型流体存储和分配容器***(RETURNABLE AND REUSABLE,BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINERSYSTEM)”的美国专利No.6,698,619;和2008年5月9日提交的名称为“用于材料的共混和分布的***和方法(SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION)”的PCT/US08/63276。
在第三方面,本发明涉及使用本文所述的组合物从上面具有氮化钛材料的微电子器件的表面蚀刻氮化钛材料的方法。例如,可去除氮化钛材料而不显著破坏/去除所述微电子器件上存在的金属导体和绝缘体材料。因此,在一个优选实施方式中,描述了使用本文所述的组合物从上面具有氮化钛和/或光致抗蚀剂蚀刻残余物材料的微电子器件的表面相对于金属导体和绝缘体材料而言选择性和基本上去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的方法。在另一个优选实施方式中,描述了使用本文所述的组合物从上面具有氮化钛和/或光致抗蚀剂蚀刻残余物材料的微电子器件的表面相对于金属导体(例如,铜)、钨和绝缘体材料而言选择性和基本上去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的方法。
在蚀刻应用中,以任何合适方式向上面具有氮化钛和/或光致抗蚀剂蚀刻残余物材料的微电子器件的表面施加组合物,例如,通过将组合物喷涂在器件表面上,通过浸渍(在静态或动态体积的组合物中)包括氮化钛和/或光致抗蚀剂蚀刻残余物材料的器件,通过使所述器件与另一种材料例如上面吸收有组合物的垫或纤维状吸收剂施用器元件接触,通过使包括氮化钛和/或光致抗蚀剂蚀刻残余物材料的器件与循环的组合物接触,或通过使组合物与氮化钛和/或光致抗蚀剂蚀刻残余物材料进行去除接触的任何其它合适手段、方式或技术。可在分批或单一晶片装置中进行施加,用于动态或静态清洁。有利的是,本文所述的组合物凭借其相对于可能存在于微电子器件结构上并暴露于所述组合物的其它材料如金属和绝缘材料(即,低k电介质)而言对氮化钛和/或光致抗蚀剂蚀刻残余物材料的选择性,以高效和高选择性方式实现氮化钛和/或光致抗蚀剂蚀刻残余物材料的至少部分去除。
在本文所述的组合物用于从上面具有氮化钛和/或光致抗蚀剂蚀刻残余物材料的微电子器件结构去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的应用中,所述组合物通常在单晶片工具中与器件结构在约20℃至约100℃、优选约30℃至约60℃的范围内的温度下接触约0.3分钟至约30分钟、优选约0.5分钟至约3分钟的充分时间。这些接触时间和温度是说明性的,并且可使用可有效从器件结构至少部分去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的任何其它合适的时间和温度条件。
在一个实施方式中,所述组合物在递送至器件结构期间在线加热。通过在线而非在浴本身中加热,所述组合物寿命增加。
在完成所需蚀刻/去除动作后,所述组合物可容易地从先前已进行施加的微电子器件去除,例如,通过如在本文所述组合物的给定最终用途应用中可能需要和有效的冲洗、洗涤或其它去除步骤。例如,所述器件可用包括去离子水的冲洗溶液冲洗和/或干燥(例如,旋干、N2、蒸汽干燥等)。
本发明的第四方面涉及根据本文所述的方法制造的改进的微电子器件,并且涉及含有这些微电子器件的产品。
第五方面涉及制造包含微电子器件的物品的方法,所述方法包括使所述微电子器件与组合物接触足够时间以从上面具有氮化钛和/或光致抗蚀剂蚀刻残余物材料的微电子器件的表面蚀刻性去除氮化钛和/或光致抗蚀剂蚀刻残余物材料,以及将所述微电子器件并入所述物品中,其中所述组合物包含以下物质,由以下物质组成或基本上由以下物质组成:至少一种氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、至少一种低k钝化剂、至少一种溶剂和任选地至少一种络合剂,其中所述组合物基本上不含过氧化氢。当所述至少一种氧化剂包含含碘氧化剂时,所述组合物还可包含至少一种碘清除剂。
本发明的第六方面涉及一种制造物品,其包含以下物质,由以下物质组成或基本上由以下物质组成:微电子器件衬底、所述衬底上的氮化钛层和本文所述的组合物。
本发明的特征和优点通过下文讨论的说明性实施例更充分地示出。
实施例1
制备包含以下组分的制剂:0.01重量%高碘酸、1.80重量%H2SiF6、0.004重量%苯扎氯铵、0.24重量%TMAS、注明的络合剂和量,其余为水(至100重量%),并在50℃下测定W、TiN和TEOS的蚀刻速率。
表1:制剂和蚀刻速率。
可以看到,许多包括络合剂的组合物产生与制剂M和N(即,无络合剂)等同的TiN蚀刻速率,并具有相称的W蚀刻速率和/或更低的TEOS蚀刻速率(制剂A-L)。
对许多制剂进行了粒子测量,由此确定了在接近一周的过程中0.1μm、0.3μm和0.5μm粒子的液体粒子计数。确定了制剂A随时间产生最高稳定性,尽管制剂E也足够稳定。
实施例2
制备包含以下组分的制剂:0.01重量%碘酸铵、0.80重量%H2SiF6、0.005重量%溴化十四烷基三甲基铵、0.5重量%MBTA、0.2重量%TEOS、0.1重量%4-甲基-2-戊酮、注明的络合剂和量,其余为水(至100重量%),并在50℃下测定Cu、W、TiN和TEOS的蚀刻速率。
表2:制剂和蚀刻速率。
可以看到,许多包括络合剂的组合物产生与制剂Y和Z(即,无络合剂)等同的TiN蚀刻速率,并具有更低的W蚀刻速率和/或更低的TEOS蚀刻速率。
实施例3
制备包含以下组分的制剂:0.01重量%高碘酸、1.80重量%H2SiF6、0.24重量%TMAS、注明的腐蚀抑制剂和量,其余为水(至100重量%),并在将W、TiN和PETEOS的样片在制剂中在50℃下浸泡20分钟后测定W、TiN和PETEOS的蚀刻速率。在配制之前对含有氯化物和溴化物的腐蚀抑制剂进行离子交换。
表3:制剂和蚀刻速率。
***
虽然已参考本发明的特定方面、特征和说明性实施方式对本发明进行了描述,但应理解本发明的效用不因此受限制,而是延伸至并涵盖如本发明领域的普通技术人员基于本文的公开内容所想到的众多其它变化、修改和替代实施方式。相应地,如权利要求书中所要求保护的发明旨在被广泛地理解和解释为将所有这些变化、修改和替代实施方式包括在其精神和范围内。
Claims (10)
1.一种用于从上面具有氮化钛和/或光致抗蚀剂蚀刻残余物材料的微电子器件的表面选择性去除所述氮化钛和/或光致抗蚀剂蚀刻残余物材料的组合物,所述组合物包含至少一种氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、至少一种钝化剂、至少一种溶剂和至少一种络合剂,其中所述组合物基本上不含过氧化氢,其中所述至少一种腐蚀抑制剂包括选自由以下所组成的群组的物质:N-乙基吗啉-N-氧化物、N-甲基吡咯烷-N-氧化物和N-乙基吡咯烷-N-氧化物、喹啉及其衍生物、喹唑啉及其衍生物、异喹啉及其衍生物、吡嗪及其衍生物、嘧啶及其衍生物、哒嗪及其衍生物、喹喔啉及其衍生物、吩嗪及其衍生物、菲啶及其衍生物、吖啶及其衍生物和其组合,
其中所述氧化剂包括选自以下的物质:FeCl3(水合的和未水合的)、Fe(NO3)3、Sr(NO3)2、CoF3、FeF3、MnF3、过硫酸氢钾复合盐(2KHSO5·KHSO4·K2SO4)、高碘酸、碘酸、氧化钒(V)、氧化钒(IV,V)、钒酸铵、过氧单硫酸铵、亚氯酸铵(NH4ClO2)、氯酸铵(NH4ClO3)、碘酸铵(NH4IO3)、硝酸铵(NH4NO3)、过硼酸铵(NH4BO3)、高氯酸铵(NH4ClO4)、高碘酸铵(NH4IO3)、过硫酸铵((NH4)2S2O8)、次氯酸铵(NH4ClO)、钨酸铵((NH4)10H2(W2O7))、过硫酸钠(Na2S2O8)、次氯酸钠(NaClO)、过硼酸钠、碘酸钾(KIO3)、高锰酸钾(KMnO4)、过硫酸钾、硝酸(HNO3)、过硫酸钾(K2S2O8)、次氯酸钾(KClO)、亚氯酸四甲基铵((N(CH3)4)ClO2)、氯酸四甲基铵((N(CH3)4)ClO3)、碘酸四甲基铵((N(CH3)4)IO3)、过硼酸四甲基铵((N(CH3)4)BO3)、高氯酸四甲基铵((N(CH3)4)ClO4)、高碘酸四甲基铵((N(CH3)4)IO4)、过硫酸四甲基铵((N(CH3)4)S2O8)、过氧单硫酸四丁基铵、过氧单硫酸、硝酸铁(Fe(NO3)3)、过乙酸(CH3(CO)OOH)、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯苯醌、阿脲和其组合,其中所述组合物的pH在0至4的范围内;并且
其中所述络合剂是β-二酮、多元酸、氨基多羧酸、膦酸、膦酸衍生物、阴离子型表面活性剂、阻垢剂聚合物或盐,所述盐包括铵或四烷基铵阳离子。
2.权利要求1的组合物,其中所述蚀刻剂包括选自以下的物质:H2ZrF6、H2TiF6、HPF6、HF、氟化铵、四氟硼酸、六氟硅酸、四氟硼酸四丁基铵(TBA-BF4)、六氟硅酸铵、六氟钛酸铵、氟化四烷基铵(NR1R2R3R4F)、氢氧化四烷基铵(NR1R2R3R4OH)、弱碱和其组合,其中R1、R2、R3、R4可以彼此相同或不同并选自由以下所组成的群组:直链C1-C6烷基基团、支链的C1-C6烷基基团、取代的芳基基团和未取代的芳基基团。
3.权利要求1的组合物,其中所述蚀刻剂包括HF、六氟硅酸或四氟硼酸。
4.权利要求1的组合物,其中所述氧化剂包括选自以下的物质:氧化钒、碘酸铵、高碘酸铵、钒酸铵、高碘酸、碘酸、1,4-苯醌和其组合。
5.权利要求1的组合物,其中所述至少一种溶剂包括水。
6.权利要求5的组合物,其中所述组合物包含以所述组合物的总重量计至少约95重量%的水。
7.权利要求1的组合物,其中所述至少一种溶剂包括选自以下的物质:甲醇、乙醇、异丙醇、丁醇和更高级的醇,四氢糠醇(THFA)、3-氯-1,2-丙二醇、3-氯-1-丙烷硫醇、1-氯-2-丙醇、2-氯-1-丙醇、3-氯-1-丙醇、3-溴-1,2-丙二醇、1-溴-2-丙醇、3-溴-1-丙醇、3-碘-1-丙醇、4-氯-1-丁醇、2-氯乙醇、二氯甲烷、氯仿、乙酸、丙酸、三氟乙酸、四氢呋喃(THF)、N-甲基吡咯烷酮(NMP)、环己基吡咯烷酮、N-辛基吡咯烷酮、N-苯基吡咯烷酮、甲基二乙醇胺、甲酸甲酯、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、四亚甲基砜(环丁砜)、二乙基醚、苯氧基-2-丙醇(PPh)、苯丙酮、乳酸乙酯、乙酸乙酯、苯甲酸乙酯、乙腈、丙酮、乙二醇、丙二醇(PG)、1,3-丙二醇、1,4-丙二醇、二烷、丁内酯、碳酸丁烯酯、碳酸乙烯酯、碳酸丙烯酯、二丙二醇、二乙二醇单甲醚、三乙二醇单甲醚、二乙二醇单***、三乙二醇单***、乙二醇单丙醚、乙二醇单丁醚、二乙二醇单丁醚(即丁基卡必醇)、三乙二醇单丁醚、乙二醇单己醚、二乙二醇单己醚、乙二醇苯醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二丙二醇二甲醚、二丙二醇***、丙二醇正丙醚、二丙二醇正丙醚(DPGPE)、三丙二醇正丙醚、丙二醇正丁醚、二丙二醇正丁醚、三丙二醇正丁醚、丙二醇苯醚、乙酸二丙二醇甲醚、四乙二醇二甲醚(TEGDE)、二元酸酯、碳酸甘油酯、N-甲酰基吗啉、磷酸三乙基酯和其组合。
8.权利要求1的组合物,其中所述至少一种钝化剂包括选自以下的物质:甲基三甲氧基硅烷、二甲基二甲氧基硅烷、苯基三甲氧基硅烷、四乙氧基硅烷(TEOS)、N-丙基三甲氧基硅烷、N-丙基三乙氧基硅烷、己基三甲氧基硅烷、己基三乙氧基硅烷、六氟硅酸铵、硅酸钠、硅酸四甲基铵(TMAS)、硼酸、五硼酸铵、四硼酸钠、二硼酸铵、3-羟基-2-萘甲酸、丙二酸、亚氨基二乙酸和其组合。
9.权利要求1的组合物,其中所述至少一种络合剂包括选自以下的物质:2,4-戊二酮、乙酰丙酮化物、1,1,1-三氟-2,4-戊二酮、1,1,1,5,5,5-六氟-2,4-戊二酮、甘氨酸、丝氨酸、脯氨酸、亮氨酸、丙氨酸、天冬酰胺、天冬氨酸、谷氨酰胺、组氨酸、谷氨酸、精氨酸、半胱氨酸、缬氨酸、赖氨酸、亚氨基二乙酸(IDA)、丙二酸、草酸、琥珀酸、硼酸、次氮基三乙酸、苹果酸、柠檬酸、乙酸、马来酸、乙二胺四乙酸(EDTA)、EDTA-2NH3(乙二胺四乙酸二铵盐)、(1,2-亚环己基二次氮基)四乙酸(CDTA)、二亚乙基三胺五乙酸(DTPA)、2-膦酰基丁烷-1,2,4-三羧酸(PBTCA)、乙二胺二琥珀酸、丙二胺四乙酸、羟基亚乙基二膦酸(HEDP)、1-羟基乙烷-1,1-二膦酸、次氮基-三(亚甲基膦酸)(NTMP)、氨基三(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)、乙二胺四(亚甲基膦酸)(EDTMPA)、烷基硫酸钠、烷基硫酸铵、烷基(C10-C18)羧酸铵盐、磺基琥珀酸钠及其酯、烷基(C6-C18)磺酸钠盐、二阴离子磺酸盐和其组合。
10.一种从上面具有氮化钛材料的微电子器件的表面蚀刻所述氮化钛材料的方法,所述方法包括将所述表面与根据前述权利要求中任一项所述的组合物相接触,其中所述组合物从所述表面相对于金属和绝缘材料而言选择性去除所述氮化钛材料。
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US10138117B2 (en) | 2018-11-27 |
US20160185595A1 (en) | 2016-06-30 |
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TWI683889B (zh) | 2020-02-01 |
EP3027709A4 (en) | 2017-03-29 |
WO2015017659A1 (en) | 2015-02-05 |
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