CN112080279A - 蚀刻组合物 - Google Patents
蚀刻组合物 Download PDFInfo
- Publication number
- CN112080279A CN112080279A CN201910574759.3A CN201910574759A CN112080279A CN 112080279 A CN112080279 A CN 112080279A CN 201910574759 A CN201910574759 A CN 201910574759A CN 112080279 A CN112080279 A CN 112080279A
- Authority
- CN
- China
- Prior art keywords
- acid
- etching
- ether
- etching composition
- hydroxide
- 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.)
- Pending
Links
- 238000005530 etching Methods 0.000 title claims abstract description 146
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003112 inhibitor Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000002738 chelating agent Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims description 35
- 229910052802 copper Inorganic materials 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- -1 organic acid compound Chemical class 0.000 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 claims description 6
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 150000007514 bases Chemical class 0.000 claims description 6
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 6
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 5
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-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
- 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
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-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
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- CWRVKFFCRWGWCS-UHFFFAOYSA-N Pentrazole Chemical compound C1CCCCC2=NN=NN21 CWRVKFFCRWGWCS-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-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
- 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
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 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
- 235000013922 glutamic acid Nutrition 0.000 claims description 4
- 239000004220 glutamic acid Substances 0.000 claims description 4
- 229960002449 glycine Drugs 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N lysine Chemical compound NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- 229960003330 pentetic acid Drugs 0.000 claims description 4
- 229960005152 pentetrazol Drugs 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
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-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
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-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
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 claims description 4
- IJGSGCGKAAXRSC-UHFFFAOYSA-M tris(2-hydroxyethyl)-methylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(CCO)CCO IJGSGCGKAAXRSC-UHFFFAOYSA-M 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 3
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- WAKHLWOJMHVUJC-FYWRMAATSA-N (2e)-2-hydroxyimino-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(=N/O)\C(O)C1=CC=CC=C1 WAKHLWOJMHVUJC-FYWRMAATSA-N 0.000 claims description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 2
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 claims description 2
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 claims description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-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
- 229940083957 1,2-butanediol Drugs 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
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-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
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims description 2
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 2
- NXRIDTLKJCKPOG-UHFFFAOYSA-N 1,4-dihydroimidazole-5-thione Chemical compound S=C1CN=CN1 NXRIDTLKJCKPOG-UHFFFAOYSA-N 0.000 claims description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
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- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 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
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- 229960003540 oxyquinoline Drugs 0.000 claims description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 2
- 239000001230 potassium iodate Substances 0.000 claims description 2
- 229940093930 potassium iodate Drugs 0.000 claims description 2
- 235000006666 potassium iodate Nutrition 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 235000013930 proline Nutrition 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 2
- 229940081974 saccharin Drugs 0.000 claims description 2
- 235000019204 saccharin Nutrition 0.000 claims description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 2
- 235000004400 serine Nutrition 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 229960001922 sodium perborate Drugs 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 claims description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 2
- 229960002317 succinimide Drugs 0.000 claims description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 2
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 claims description 2
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 claims description 2
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 claims description 2
- 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
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- MPSUGQWRVNRJEE-UHFFFAOYSA-N triazol-1-amine Chemical compound NN1C=CN=N1 MPSUGQWRVNRJEE-UHFFFAOYSA-N 0.000 claims description 2
- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-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
- 229940116269 uric acid Drugs 0.000 claims description 2
- 239000004474 valine Substances 0.000 claims description 2
- 235000014393 valine Nutrition 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims 1
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims 1
- MUGOZZGWFXRGJG-UHFFFAOYSA-N 4,6-dimethyltriazine Chemical compound CC1=CC(C)=NN=N1 MUGOZZGWFXRGJG-UHFFFAOYSA-N 0.000 claims 1
- KPBDDCHVARVOII-UHFFFAOYSA-N 5,5-dimethyltetrazole Chemical compound CC1(C)N=NN=N1 KPBDDCHVARVOII-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 239000003619 algicide Substances 0.000 claims 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 claims 1
- 150000001565 benzotriazoles Chemical class 0.000 claims 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000004323 potassium nitrate Substances 0.000 claims 1
- 235000010333 potassium nitrate Nutrition 0.000 claims 1
- 239000002516 radical scavenger Substances 0.000 claims 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims 1
- 229910001935 vanadium oxide Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 239000004020 conductor Substances 0.000 abstract description 8
- 238000001312 dry etching Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 10
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- 239000005416 organic matter Substances 0.000 description 6
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- 230000004888 barrier function Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 230000009977 dual effect Effects 0.000 description 2
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 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 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
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- UUEDINPOVKWVAZ-UHFFFAOYSA-N bis(2-ethylhexyl) 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OCC(CC)CCCC UUEDINPOVKWVAZ-UHFFFAOYSA-N 0.000 description 1
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- LDGFRUUNCRYSQK-UHFFFAOYSA-N triazin-4-ylmethanediamine Chemical compound NC(N)C1=CC=NN=N1 LDGFRUUNCRYSQK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
本发明公开了蚀刻组合物。具体地,本发明涉及一种用于选择性蚀刻氮化钛硬光罩的蚀刻组合物,包括碱性化合物、螯合剂、腐蚀抑制剂以及溶剂。本发明的蚀刻组合物具有优异的蚀刻选择性,能快速清除氮化钛(TiN)及干式蚀刻残留物,不会损及low‑k层及金属导体层,且重复使用蚀刻组合物仍保有一定的氧化能力、蚀刻选择性及pH值等特性,适合用于再循环式过程中。
Description
技术领域
本发明涉及一种蚀刻组合物,尤其涉及一种选择性蚀刻氮化钛(TiN)硬光罩及残留物的蚀刻组合物。
背景技术
由于市场需求,业界持续投入研究以开发出效能更高、耗能更低的微电子装置,且随着时代演进,市场上亦需求更小尺寸的微电子装置,然而,随着微电子装置的尺寸减小,集成电路(IC)可靠度成为IC装配技术领域极为重要的议题。
双镶嵌(dual damascene)结构过程是微电子装置后段金属化以形成互连体的制程,是将通孔与金属导线一起以镶嵌的方式制作,其以金属硬光罩(hard mask)形成在覆盖金属导体层(如钴或铜)的低介电系数(low-k)材料层上,再根据金属硬光罩蚀刻low-k层以形成暴露部分金属导体层的沟渠及孔洞,最后移除该金属硬光罩并进行扩散阻障层沉积及金属沉积。金属硬光罩例如氮化钛(TiN),于蚀刻low-k层形成沟渠及孔洞后,可以经湿式化学品清洁制程来移除金属硬光罩。该湿式化学品清洁过程是一种湿式蚀刻,并可以一并除去干式蚀刻的残留物,该残留物可能为高分子或与金属结合的高分子,若未将残渣清除干净,则会导致导线的电阻值上升,尤其在孔洞的部份影响更为显著。此外,湿式蚀刻时,亦不能影响下方经暴露的金属导体层及low-k层,因此,湿式蚀刻所使用的化学物质必须具高度选择性。
传统上,用在铜制程的干式蚀刻后清洁液为含氟的半水溶液,借由氟离子与晶片表面的反应,微蚀表面的氧化物,使有机物脱离晶片表面以达到清洁的目的。市面已经有该产品广泛地用于旧世代的铜制程上。但因氟离子会蚀刻low-k材料,使得在半导体过程持续微缩后,氟离子微蚀会使得原先设计的沟渠及孔洞的尺寸变大,造成铜导线的失准(misalignment),使得元件失效的机会变大,致使不符先进半导体过程需求,而且氟离子的活性大,对于底层铜腐蚀抑制难度较高。
下一代的干式蚀刻后清洁液为含双氧水的半水或水溶液。其利用双氧水的氧化能力将有机物氧化,使其带有亲水性的官能团,以增加有机物在水中的溶解度,另外溶剂可膨润有机物,使其脱离晶片表面,以溶解或悬浮的方式存在溶液中,之后于水洗阶段,一并将残渣和清洗液清洗干净。此产品不含氟离子,不会腐蚀low-k材料,而针对底部金属导体层的铜材料,则添加了适当的铜腐蚀抑制剂,以保护铜不被腐蚀。含双氧水的清洗液可微蚀TiN硬光罩,以扩大沟渠和孔洞的开孔,以利接下来的扩散阻障层沉积和铜电镀制程。后续则使用化学机械研磨(CMP)去除表面的铜和扩散阻障层金属,TiN硬光罩也一并在CMP制程中去除。
然而,先进半导体过程中应用了新颖的金属材料作为扩散阻障层,进而产生须在沉积扩散阻障层前去除TiN硬光罩的需求,为了在有限时间内将TiN硬光罩去除干净,因此,亟待开发对TiN硬光罩及干蚀刻残留物具有高移除能力,且同时又不腐蚀底部金属导体铜或钴的湿式蚀刻液。
发明内容
为了解决上述问题,本发明提供一种蚀刻组合物,用于选择性蚀刻氮化钛硬光罩,该组合物包括:碱性化合物、螯合剂、腐蚀抑制剂以及溶剂,其中,以该碱性化合物、该螯合剂、该腐蚀抑制剂及该溶剂的总重量计,该碱性化合物占1至25重量%、该螯合剂占0.1至2重量%、该腐蚀抑制剂占1至7重量%。
于一些具体实施方案中,以该碱性化合物、该螯合剂、该腐蚀抑制剂及该溶剂的总重量计,该碱性化合物占1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25重量%,螯合剂可占0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1、1.5、2重量%,以及腐蚀抑制剂可占1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6、6.5、7重量%。
该蚀刻组合物可进一步包括氧化剂,其中,该氧化剂包括但不限于过氧化氢、过硫酸铵、过苯甲酸、FeCl3、FeF3、Fe(NO3)3、Sr(NO3)2、CoF3、MnF3、过碘酸、碘酸、氧化钒、钒酸铵、过氧单硫酸铵、次氯酸铵、亚氯酸铵、氯酸铵、过氯酸铵、碘酸铵、过碘酸铵、硝酸铵、过硼酸铵、次溴酸铵、钨酸铵、过硫酸钠、次氯酸钠、过硼酸钠、次溴酸钠、碘酸钾、过锰酸钾、过硫酸钾、硝酸钾、过硫酸钾、次氯酸钾、亚氯酸四甲铵、氯酸四甲铵、过氯酸四甲铵、碘酸四甲铵、过碘酸四甲铵、过硼酸四甲铵、过硫酸四甲铵、过氧单硫酸四丁铵、过氧单硫酸、硝酸铁、尿素过氧化氢、过乙酸、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯苯醌以及四氧嘧啶。于一具体实施方案中,该氧化剂是过氧化氢,以该蚀刻组合物的重量计,该过氧化氢溶液占10至20重量%,例如10、10.5、11、11.5、12、12.5、13、13.5、14、14.5、15、15.5、16、16.5、17、17.5、18、18.5、19、19.5、20重量%。
该碱性化合物包括但不限于乙基三甲基氢氧化铵(ETMAH)、四乙基氢氧化铵(TEAH)、苄基三甲基氢氧化铵(BTMAH)、AFR-240(4-(2-羟乙基)-吗啉)、4-甲基吗啉N-氧化物(NMMO)、三甲基苯基氢氧化铵(TMPAH)、四丁基氢氧化铵(TBAH)、四丙基氢氧化铵(TPAH)、四甲基氢氧化铵(TMAH)、苄基三乙基氢氧化铵(BTEAH)、氢氧化钾、四丁基氢氧化膦(TBPH)、(2-羟乙基)三甲基氢氧化铵、(2-羟乙基)三乙基氢氧化铵、(2-羟乙基)三丙基氢氧化铵、(2-羟丙基)三甲基氢氧化铵、二乙基二甲基氢氧化铵(DEDMAH)、三(2-羟乙基)甲基氢氧化铵(THEMAH)、氢氧化铵、氢氧化胆碱、1,1,3,3-四甲基胍、碳酸胍、精氨酸、单乙醇胺、二乙醇胺、三乙醇胺、乙二胺以及半胱氨酸。
该蚀刻组合物可进一步包括有机酸化合物,其中,以该蚀刻组合物的总重量计,该有机酸化合物占15重量%以下,例如15、14.5、14、13.5、13、12.5、12、11.5、11、10.5、10、9.5、9、8.5、8、7.5、7、6.5、6、5.5、5、4.5、4、3.5、3、2.5、2、1.5、1、0.5重量%以下。
该有机酸化合物包括但不限于柠檬酸、柠檬酸铵、苹果酸、戊二酸、马来酸、丙二酸、己二酸、乙酸、亚胺基二乙酸、乳酸、草酸、丁二酸、甘氨酸、丝氨酸、脯氨酸、亮氨酸、丙氨酸、天冬酰胺、天冬氨酸、谷氨酸、缬氨酸、赖氨酸以及顺丁烯二酸。
该螯合剂包括但不限于环己二胺四乙酸(CDTA)、羟基亚乙基二膦酸(HEDP)、胺基乙酸、亚胺基二乙酸、次氮基三乙酸、谷氨酸、吡啶-2-甲酸、乙二胺四乙酸(EDTA)、乙二胺二丁二酸(EDDS)、溴化铵、氯化铵、膦酸、二乙三胺五乙酸(DTPA)、二乙三胺五(亚甲基膦酸)、次氮基三(亚甲基膦酸)(NTMP)、2-膦酰丁烷-1,2,4-三羧酸(PBTCA)、乙二胺、乙二胺二丁二酸、丙二胺四乙酸、乙二胺四(亚甲基膦酸)(EDTMPA)、胺基三(亚甲基膦酸)、五甲基二亚乙三胺(PMDETA)、四甘醇二甲醚、硼酸、2,4-戊二酮、咪唑以及杀藻胺。
该腐蚀抑制剂包括但不限于苯并***(BTA)、甲苯***(TTA)、1,2,4-***、3-胺基-1,2,4-***、5-胺基-1,2,4-***、3-胺基-5-巯基-1,2,4-***、3,5-二胺基-1,2,4-***、甲基-1H-苯并***、5-苯基苯并***、羟基苯并***、卤苯并***(卤=F、Cl、Br、I)、5-硝基苯并***、苯并***羧酸、1-胺基-1,2,4-***、3-胺基-1,2,4-***、3-胺基-5-巯基-1,2,4-***、3-巯基-1,2,4-***、3-异丙基-1,2,4-***、4-甲基-4H-1,2,4-***-硫醇、4-胺基-4H-1,2,4-***、3-胺基-5-甲硫基-1H-1,2,4-***、2-(5-胺基戊基)苯并***、5-苯基硫醇-苯并***、1-胺基-1,2,3-***、1-胺基-5-甲基-1,2,3-***、萘并***、噻唑、咔唑、苯并噻唑、2-胺基苯并噻唑、2-巯基苯并噻唑、苯并咪唑、2-胺基苯并咪唑、咪唑、1-甲基咪唑、2-巯基苯并咪唑、2-巯基-5-甲基苯并咪唑、4-甲基-2-苯基咪唑、2-巯基噻唑啉、甲基四唑、亚戊基四唑、5-苯基-1H-四唑、5-苄基-1H-四唑、5-巯基1-甲基四唑、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、1-苯基-1H-四唑-硫醇、8-羟基喹啉、1-硫代甘油、抗坏血酸、吡唑、吲唑、三嗪、二胺甲基三嗪、2,4-二胺基-6-甲基-1,3,5-三嗪、2-胺基-5-乙基-1,3,4-噻二唑、5-胺基-1,3,4-噻二唑-2硫醇、1,3-二甲基-2-咪唑啶酮、2-苄基吡啶、咪唑啉硫酮、十二烷基硫酸钠、丁二酰亚胺、腺嘌呤、腺苷酸、糖精、尿酸以及安息香肟。
该溶剂包括但不限于二乙二醇丁醚(BDG)、二甲基亚砜(DMSO)、环丁砜、二乙二醇二***(DEDG)、二甲基砜、二甲基硫、N-甲基吡咯烷酮(NMP)、二丙二醇甲基醚(DPGME)、三丙二醇甲基醚(TPGME)、甲醇、乙醇、异丙醇、丁醇、戊醇、己醇、2-乙基-1-己醇、庚醇、辛醇、乙二醇、丙二醇、丁二醇、己二醇、碳酸丁二酯、碳酸乙二酯、碳酸丙二酯、胆碱碳酸氢盐、二丙二醇、四氢噻吩砜、四氢呋喃甲醇(THFA)、1,2-丁二醇、1,4-丁二醇、四甲基脲、二乙二醇单甲基醚、三乙二醇单甲基醚、三乙二醇单乙基醚、乙二醇单丙基醚、乙二醇单丁基醚、二乙二醇单丁基醚、三乙二醇单丁基醚、乙二醇单己基醚、二乙二醇单己基醚、乙二醇苯基醚、丙二醇甲基醚、二丙二醇二甲基醚、二丙二醇乙基醚、丙二醇正丙基醚、二丙二醇正丙基醚(DPGPE)、三丙二醇正丙基醚、丙二醇正丁基醚、二丙二醇正丁基醚、三丙二醇正丁基醚、丙二醇苯基醚、2,3-二氢十氟戊烷、乙基全氟丁基醚、甲基全氟丁基醚、碳酸烷酯、4-甲基-2-戊醇以及水。
该蚀刻组合物可进一步包括添加剂,例如自由基抑制剂及自由基捕获剂。
于一具体实施方案中,该蚀刻组合物的pH值为6.5至9.5之间,例如6.5、7.0、7.5、8.0、8.5、9.0、9.5,于添加氧化剂后,该蚀刻组合物的pH值为6至8.5之间,例如6.0、6.5、7.0、7.5、8.0、8.5。
于一具体实施方案中,该蚀刻组合物于60℃条件下蚀刻氮化钛的蚀刻速率为12nm/min以上、蚀刻铜的蚀刻速率为0.3nm/min以下、且蚀刻钴的蚀刻速率为0.4nm/min以下。
于一具体实施方案中,该蚀刻组合物蚀刻氮化钛的蚀刻速率与蚀刻铜的蚀刻速率比,即对氮化钛相对于铜的蚀刻选择性为85以上,而该蚀刻组合物蚀刻氮化钛的蚀刻速率与蚀刻钴的蚀刻速率比,即该蚀刻组合物对氮化钛相对于钴的蚀刻选择性为100以上。
本发明的蚀刻组合物蚀刻氮化钛的蚀刻速率与蚀刻铜的蚀刻速率比至少为85以上,还可以为90、95、100、110、120、130、140、150、160、170以上,依据实际需求而选用最合适的蚀刻氮化钛的蚀刻速率与蚀刻铜的蚀刻速率比。另一方面,本发明的蚀刻组合物蚀刻氮化钛的蚀刻速率与蚀刻钴的蚀刻速率比至少为100以上,还可以为110、120、130、140、150、200、250、300、350、400、450、500、550、600、650以上,依据实际需求而选用最合适的蚀刻氮化钛的蚀刻速率与蚀刻钴的蚀刻速率比。
于一具体实施方案中,该蚀刻组合物可用于再循环式过程,以在选择性蚀刻氮化钛后回收再利用。
本发明所提供的蚀刻组合物具有优异的蚀刻选择性,对TiN的蚀刻速率高,而对铜及钴的蚀刻速率极低,能够于湿式蚀刻时快速且准确地清除TiN及干式蚀刻残留物,不会损及low-k层及金属导体层。此外,本发明的蚀刻组合物稳定性高,经测试显示,重复使用蚀刻组合物仍保有一定的氧化能力、蚀刻选择性以及pH值等特性,极适合应用于再循环式过程中。
附图说明
图1A至图1D显示本发明的蚀刻组合物的稳定性测试结果,分别为TiN蚀刻速率、Cu及Co蚀刻速率、H2O2浓度及pH值随时间的变化。
具体实施方式
以下借由特定的具体实施方案说明本发明的实施方式,该领域技术人员可由本说明书所揭示的内容轻易地了解本发明的优点及功效。
须知,本说明书所附图式所绘示的结构、比例、大小等,均仅用以配合说明书所揭示的内容,以供该领域技术人员了解与阅读,并非用以限定本发明可实施的限定条件,故不具技术上的实质意义,任何结构的修饰、比例关系的改变或大小的调整,在不影响本发明所能产生的功效及所能达合的目的下,均应仍落在本发明所揭示的技术内容所能涵盖的范围内。同时,本说明书中所引用的如“一”等用字,亦仅为便于叙述的明了,而非用以限定本发明可实施的范围,其相对关系的改变或调整,再无实质变更技术内容下,当亦视为本发明可实施的范畴。此外,本文所有范围和值包含边值且可合并。落在本文中所述范围内的任何数值或点,例如任何整数都可以作为最小值或最大值以导出下位范围等。
本发明的蚀刻组合物包括碱性化合物、螯合剂、腐蚀抑制剂以及溶剂,可进一步包括有机酸化合物、氧化剂及添加剂。
螯合剂可以络合组合物中的游离金属离子。金属离子可能来自于金属导体层,金属离子会影响氧化剂,使其容易分解,导致蚀刻组合物的氧化、蚀刻能力受到影响。
腐蚀抑制剂为含氮、硫、氧等化学元素的成分,一般为杂环类化合物,腐蚀抑制剂分子上的氮、硫和氧等原子带有孤对电子对,可以和金属表面的氧化物形成配位键,使得腐蚀抑制剂吸附在金属表面,而可以在表面上形成钝化层,以避免金属与湿式蚀刻溶液直接接触而受到腐蚀。
本发明的蚀刻组合物是浓缩型组合物,可以在使用前稀释,稀释剂与浓缩组合物的比例为0.1:1至100:1。另外,由于氧化剂随时间的不安定性较高,故浓缩型组合物可不包含氧化剂,而令该氧化剂在稀释时一并加入,以完成最终组合物。氧化剂可以添加至稀释剂中,随稀释剂引入至浓缩型组合物,或者,亦可添加至经稀释的组合物中。
以下,本发明通过实施例的示例来说明细节。不过,本发明的诠释不应当被限制于以下实施例的阐述。
本发明实施例1至17各自选用下列成分:
溶剂:二乙二醇丁醚(BDG)、二甲基亚砜(DMSO)及二乙二醇二***(DEDG)。
腐蚀抑制剂:苯并***(BTA)及甲苯***(TTA)。
螯合剂:环己二胺四乙酸(CDTA)及羟基亚乙基二膦酸(HEDP)。
有机酸化合物:柠檬酸、戊二酸、苹果酸及马来酸。
碱性化合物:乙基三甲基氢氧化铵(ETMAH)、四乙基氢氧化铵(TEAH)、苄基三甲基氢氧化铵(BTMAH)、4-(2-羟乙基)-吗啉(AFR-240)及4-甲基吗啉N-氧化物(NMMO)。
各实施例中成分的用量配比及各项测试结果如下表1所示。
其中,TiN蚀刻速率使用市售以物理气相沉积(PVD)镀上TiN薄膜的晶片进行测试。TiN薄膜的厚度为100nm,裁切成2cm x 2cm大小,并以浸泡的方法进行TiN薄膜的蚀刻。将装有蚀刻组合物的烧杯置于水浴槽中,待蚀刻组合物的温度升到60℃后即可进行蚀刻测试,蚀刻时间为1至3mins。以四点探针量测仪量测蚀刻前和蚀刻后TiN薄膜厚度差异,除以蚀刻时间即可得到TiN蚀刻速率。
而Cu及Co的蚀刻速率分别使用以电化学电镀(ECP)镀上Cu薄膜的晶片及以PVD镀上Co薄膜的晶片进行测试。Cu薄膜的厚度为2000nm、Co薄膜的厚度为40nm,裁切成2cm x2cm大小,以草酸进行预处理后以浸泡的方法进行Cu薄膜及Co薄膜的蚀刻,蚀刻时间为10mins。以电感耦合等离子体质谱仪(ICP/MS)量测蚀刻前和蚀刻后蚀刻组合物中的Cu和Co离子浓度,换算成溶出量,而得到Cu和Co的蚀刻速率,计算式如下式I所示。
式I中,C为由ICP/MS所测得的金属离子浓度(ppb),W为蚀刻组合物的重量(g),D为金属的密度:Cu为8.93g/cm3、Co为8.9g/cm3,A为晶片面积(cm2),T为蚀刻时间(min)。
表1中,TiN/Cu的蚀刻选择性由TiN蚀刻速率/Cu蚀刻速率计算而得;TiN/Co的蚀刻选择性由TiN蚀刻速率/Co蚀刻速率计算而得。
由表1可知,本发明的蚀刻组合物能快速地清除TiN,蚀刻速率可达12nm/min以上,具有优异的蚀刻选择性,其TiN/Cu蚀刻选择性至少具有85以上的水平,而TiN/Co蚀刻选择性亦至少具有100以上的水平。
再将本发明的蚀刻组合物进行稳定性测试,每2.4hrs进行一次TiN蚀刻测试,每次的TiN蚀刻时间为1至3mins,且适时添加水以维持同样的蚀刻组合物重量,蚀刻测试至24hrs;而Cu及钴的蚀刻测试则每4.8hrs进行一次,每次的Cu及Co蚀刻时间为10mins,且适时添加水以维持同样的蚀刻组合物重量,蚀刻测试至24hrs。蚀刻组合物的H2O2及pH值亦随着时刻次数进行量测。
稳定性测试结果如图1A至图1D所示。图1A是TiN蚀刻速率随时间(蚀刻次数)的变化,随着蚀刻次数增加,TiN蚀刻速率逐渐下降,24小时后的蚀刻速率约为初次蚀刻的蚀刻速率的50%,仍能维持12nm/min以上的水平;图1B是Cu及Co蚀刻速率随时间(蚀刻次数)的变化,结果显示,第二次蚀刻以后的Cu及Co蚀刻速率相对于初次蚀刻的Cu及Co蚀刻速率并未有显著变化,皆维持在较低的蚀刻速率水平,其中,24小时后的Cu蚀刻速率为0.2nm/min以下、24小时后的Co蚀刻速率为0.1nm/min以下。综合图1A及图1B的结果,显示本发明的蚀刻组合物回收再利用后仍能维持优异的TiN/Cu选择性及TiN/Co选择性。
图1C是蚀刻组合物的H2O2浓度随时间(蚀刻次数)的变化,随着蚀刻次数增加,H2O2浓度逐渐下降,24小时后的H2O2浓度约为初次蚀刻的H2O2浓度的70%,趋势与TiN蚀刻速率相同;而图1D是蚀刻组合物的pH值随时间(蚀刻次数)的变化,随着蚀刻次数增加,pH值缓慢下降,24小时后pH值与初次蚀刻的pH值仅有些许差异。由图1A至图1D的结果可知,本发明的蚀刻组合物稳定性高,重复使用蚀刻组合物仍保有一定的氧化能力、蚀刻选择性以及pH值等特性,极适合应用于再循环式过程中。
Claims (20)
1.一种用于选择性蚀刻氮化钛硬光罩的蚀刻组合物,包括:
碱性化合物;
螯合剂;
腐蚀抑制剂;以及
溶剂,
其特征在于,以所述碱性化合物、所述螯合剂、所述腐蚀抑制剂及所述溶剂的总重量计,所述碱性化合物占1至25重量%、所述螯合剂占0.1至2重量%、以及所述腐蚀抑制剂占1至7重量%。
2.如权利要求1所述的蚀刻组合物,还包括氧化剂。
3.如权利要求2所述的蚀刻组合物,其特征在于,所述氧化剂选自过氧化氢、过硫酸铵、过苯甲酸、FeCl3、FeF3、Fe(NO3)3、Sr(NO3)2、CoF3、MnF3、过碘酸、碘酸、氧化钒、钒酸铵、过氧单硫酸铵、次氯酸铵、亚氯酸铵、氯酸铵、过氯酸铵、碘酸铵、过碘酸铵、硝酸铵、过硼酸铵、次溴酸铵、钨酸铵、过硫酸钠、次氯酸钠、过硼酸钠、次溴酸钠、碘酸钾、过锰酸钾、过硫酸钾、硝酸钾、过硫酸钾、次氯酸钾、亚氯酸四甲铵、氯酸四甲铵、过氯酸四甲铵、碘酸四甲铵、过碘酸四甲铵、过硼酸四甲铵、过硫酸四甲铵、过氧单硫酸四丁铵、过氧单硫酸、硝酸铁、尿素过氧化氢、过乙酸、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯苯醌及四氧嘧啶所组成组中的至少一者。
4.如权利要求3所述的蚀刻组合物,其特征在于,所述氧化剂是过氧化氢。
5.如权利要求4所述的蚀刻组合物,其特征在于,以所述蚀刻组合物的重量计,所述过氧化氢溶液占10至20重量%。
6.如权利要求1所述的蚀刻组合物,其特征在于,所述碱性化合物选自乙基三甲基氢氧化铵(ETMAH)、四乙基氢氧化铵(TEAH)、苄基三甲基氢氧化铵(BTMAH)、4-(2-羟乙基)-吗啉(AFR-240)、4-甲基吗啉N-氧化物(NMMO)、三甲基苯基氢氧化铵(TMPAH)、四丁基氢氧化铵(TBAH)、四丙基氢氧化铵(TPAH)、四甲基氢氧化铵(TMAH)、苄基三乙基氢氧化铵(BTEAH)、氢氧化钾、四丁基氢氧化膦(TBPH)、(2-羟乙基)三甲基氢氧化铵、(2-羟乙基)三乙基氢氧化铵、(2-羟乙基)三丙基氢氧化铵、(2-羟丙基)三甲基氢氧化铵、二乙基二甲基氢氧化铵(DEDMAH)、三(2-羟乙基)甲基氢氧化铵(THEMAH)、氢氧化铵、氢氧化胆碱、1,1,3,3-四甲基胍、碳酸胍、精氨酸、单乙醇胺、二乙醇胺、三乙醇胺、乙二胺及半胱氨酸所组成组中的至少一者。
7.如权利要求1所述的蚀刻组合物,还包括有机酸化合物,且以所述蚀刻组合物的总重量计,所述有机酸化合物占15重量%以下。
8.如权利要求7所述的蚀刻组合物,其特征在于,所述有机酸化合物选自柠檬酸、柠檬酸铵、苹果酸、戊二酸、马来酸、丙二酸、己二酸、乙酸、亚胺基二乙酸、乳酸、草酸、丁二酸、甘氨酸、丝氨酸、脯氨酸、亮氨酸、丙氨酸、天冬酰胺、天冬氨酸、谷氨酸、缬氨酸、赖氨酸及顺丁烯二酸所组成组中的至少一者。
9.如权利要求1所述的蚀刻组合物,其特征在于,所述螯合剂选自环己二胺四乙酸(CDTA)、羟基亚乙基二膦酸(HEDP)、胺基乙酸、亚胺基二乙酸、次氮基三乙酸、谷氨酸、吡啶-2-甲酸、乙二胺四乙酸(EDTA)、乙二胺二丁二酸(EDDS)、溴化铵、氯化铵、膦酸、二乙三胺五乙酸(DTPA)、二乙三胺五(亚甲基膦酸)、次氮基三(亚甲基膦酸)(NTMP)、2-膦酰丁烷-1,2,4-三羧酸(PBTCA)、乙二胺、乙二胺二丁二酸、丙二胺四乙酸、乙二胺四(亚甲基膦酸)(EDTMPA)、胺基三(亚甲基膦酸)、五甲基二乙三胺(PMDETA)、四甘醇二甲醚、硼酸、2,4-戊二酮、咪唑及杀藻胺所组成组中的至少一者。
10.如权利要求1所述的蚀刻组合物,其特征在于,所述腐蚀抑制剂选自苯并***(BTA)、甲苯***(TTA)、1,2,4-***、3-胺基-1,2,4-***、5-胺基-1,2,4-***、3-胺基-5-巯基-1,2,4-***、3,5-二胺基-1,2,4-***、甲基-1H-苯并***、5-苯基苯并***、羟基苯并***、卤苯并***且卤=F、Cl、Br或I、5-硝基苯并***、苯并***羧酸、1-胺基-1,2,4-***、3-胺基-1,2,4-***、3-胺基-5-巯基-1,2,4-***、3-巯基-1,2,4-***、3-异丙基-1,2,4-***、4-甲基-4H-1,2,4-***-硫醇、4-胺基-4H-1,2,4-***、3-胺基-5-甲硫基-1H-1,2,4-***、2-(5-胺基戊基)苯并***、5-苯基硫醇-苯并***、1-胺基-1,2,3-***、1-胺基-5-甲基-1,2,3-***、萘并***、噻唑、咔唑、苯并噻唑、2-胺基苯并噻唑、2-巯基苯并噻唑、苯并咪唑、2-胺基苯并咪唑、咪唑、1-甲基咪唑、2-巯基苯并咪唑、2-巯基-5-甲基苯并咪唑、4-甲基-2-苯基咪唑、2-巯基噻唑啉、甲基四唑、亚戊基四唑、5-苯基-1H-四唑、5-苄基-1H-四唑、5-巯基1-甲基四唑、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、1-苯基-1H-四唑-硫醇、8-羟基喹啉、1-硫代甘油、抗坏血酸、吡唑、吲唑、三嗪、二胺甲基三嗪、2,4-二胺基-6-甲基-1,3,5-三嗪、2-胺基-5-乙基-1,3,4-噻二唑、5-胺基-1,3,4-噻二唑-2硫醇、1,3-二甲基-2-咪唑啶酮、2-苄基吡啶、咪唑啉硫酮、十二烷基硫酸钠、丁二酰亚胺、腺嘌呤、腺苷酸、糖精、尿酸及安息香肟所组成组中的至少一者。
11.如权利要求1所述的蚀刻组合物,其特征在于,所述溶剂选自二乙二醇丁醚(BDG)、二甲基亚砜(DMSO)、环丁砜、二乙二醇二***(DEDG)、二甲基砜、二甲基硫、N-甲基吡咯烷酮(NMP)、二丙二醇甲基醚(DPGME)、三丙二醇甲基醚(TPGME)、甲醇、乙醇、异丙醇、丁醇、戊醇、己醇、2-乙基-1-己醇、庚醇、辛醇、乙二醇、丙二醇、丁二醇、己二醇、碳酸丁二酯、碳酸乙二酯、碳酸丙二酯、胆碱碳酸氢盐、二丙二醇、四氢噻吩砜、四氢呋喃甲醇(THFA)、1,2-丁二醇、1,4-丁二醇、四甲基脲、二乙二醇单甲基醚、三乙二醇单甲基醚、三乙二醇单乙基醚、乙二醇单丙基醚、乙二醇单丁基醚、二乙二醇单丁基醚、三乙二醇单丁基醚、乙二醇单己基醚、二乙二醇单己基醚、乙二醇苯基醚、丙二醇甲基醚、二丙二醇二甲基醚、二丙二醇乙基醚、丙二醇正丙基醚、二丙二醇正丙基醚(DPGPE)、三丙二醇正丙基醚、丙二醇正丁基醚、二丙二醇正丁基醚、三丙二醇正丁基醚、丙二醇苯基醚、2,3-二氢十氟戊烷、乙基全氟丁基醚、甲基全氟丁基醚、碳酸烷酯、4-甲基-2-戊醇及水所组成组中的至少一者。
12.如权利要求1所述的蚀刻组合物,还包括自由基抑制剂、自由基捕获剂中的至少一者。
13.如权利要求1所述的蚀刻组合物,其特征在于,所述蚀刻组合物的pH值为介于6.5至9.5之间。
14.如权利要求2所述的蚀刻组合物,其特征在于,所述蚀刻组合物的pH值为介于6至8.5之间。
15.如权利要求1至14所述的蚀刻组合物,其于60℃条件下蚀刻氮化钛的蚀刻速率为12nm/min以上。
16.如权利要求1至14所述的蚀刻组合物,其于60℃条件下蚀刻铜的蚀刻速率为0.3nm/min以下。
17.如权利要求1至14所述的蚀刻组合物,其于60℃条件下蚀刻钴的蚀刻速率为0.4nm/min以下。
18.如权利要求1至14所述的蚀刻组合物,其蚀刻氮化钛的蚀刻速率与蚀刻铜的蚀刻速率比为85以上。
19.如权利要求1至14所述的蚀刻组合物,其蚀刻氮化钛的蚀刻速率与蚀刻钴的蚀刻速率比为100以上。
20.如权利要求1至14所述的蚀刻组合物,其用于再循环式过程,以在选择性蚀刻氮化钛后回收再利用。
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