TWI727543B - 釕蝕刻組合物及方法 - Google Patents
釕蝕刻組合物及方法 Download PDFInfo
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- TWI727543B TWI727543B TW108145228A TW108145228A TWI727543B TW I727543 B TWI727543 B TW I727543B TW 108145228 A TW108145228 A TW 108145228A TW 108145228 A TW108145228 A TW 108145228A TW I727543 B TWI727543 B TW I727543B
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- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 26
- 238000005530 etching Methods 0.000 title claims abstract description 24
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000872 buffer Substances 0.000 claims abstract description 5
- -1 alkylammonium hydroxide compound Chemical class 0.000 claims description 31
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 30
- 238000004377 microelectronic Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 10
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- 239000011545 carbonate/bicarbonate buffer Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 4
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 3
- PYIGXCSOLWAMGG-UHFFFAOYSA-M methyl(triphenyl)phosphanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 PYIGXCSOLWAMGG-UHFFFAOYSA-M 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
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 claims description 3
- 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
- FBYBILSNSUSRGL-UHFFFAOYSA-N 2-hydroxyethyl(methyl)azanium hydroxide Chemical compound [OH-].C[NH2+]CCO FBYBILSNSUSRGL-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 241000208340 Araliaceae Species 0.000 claims description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 2
- 229940075419 choline hydroxide Drugs 0.000 claims description 2
- SMSCVBBYKOFGCY-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SMSCVBBYKOFGCY-UHFFFAOYSA-M 0.000 claims description 2
- 235000008434 ginseng Nutrition 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- ZOMVKCHODRHQEV-UHFFFAOYSA-M tetraethylphosphanium;hydroxide Chemical compound [OH-].CC[P+](CC)(CC)CC ZOMVKCHODRHQEV-UHFFFAOYSA-M 0.000 claims description 2
- CRUVUWATNULHFA-UHFFFAOYSA-M tetramethylphosphanium;hydroxide Chemical compound [OH-].C[P+](C)(C)C CRUVUWATNULHFA-UHFFFAOYSA-M 0.000 claims description 2
- SGKOGTXWLOGBID-UHFFFAOYSA-M triphenyl(propyl)phosphanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 SGKOGTXWLOGBID-UHFFFAOYSA-M 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- QYJPISSGHXGBGH-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 QYJPISSGHXGBGH-UHFFFAOYSA-M 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 claims 1
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims 1
- OORMKVJAUGZYKP-UHFFFAOYSA-M tetrapropylphosphanium;hydroxide Chemical compound [OH-].CCC[P+](CCC)(CCC)CCC OORMKVJAUGZYKP-UHFFFAOYSA-M 0.000 claims 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical class OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 abstract description 23
- 125000005210 alkyl ammonium group Chemical group 0.000 abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003989 dielectric material Substances 0.000 abstract description 2
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- TWLXDPFBEPBAQB-UHFFFAOYSA-N orthoperiodic acid Chemical compound OI(O)(O)(O)(O)=O TWLXDPFBEPBAQB-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 description 2
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 description 2
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 2
- WXSBVEKBZGNSDY-UHFFFAOYSA-N 5-phenyl-2h-benzotriazole Chemical compound C1=CC=CC=C1C1=CC2=NNN=C2C=C1 WXSBVEKBZGNSDY-UHFFFAOYSA-N 0.000 description 2
- 229930024421 Adenine Natural products 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- CWRVKFFCRWGWCS-UHFFFAOYSA-N Pentrazole Chemical compound C1CCCCC2=NN=NN21 CWRVKFFCRWGWCS-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 229960000643 adenine Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 2
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 2
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- SIYLLGKDQZGJHK-UHFFFAOYSA-N dimethyl-(phenylmethyl)-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]ammonium Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 SIYLLGKDQZGJHK-UHFFFAOYSA-N 0.000 description 2
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229960005152 pentetrazol Drugs 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 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 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- NHAZGSRLKBTDBF-UHFFFAOYSA-N 1,2,4-triazol-1-amine Chemical compound NN1C=NC=N1 NHAZGSRLKBTDBF-UHFFFAOYSA-N 0.000 description 1
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- NXRIDTLKJCKPOG-UHFFFAOYSA-N 1,4-dihydroimidazole-5-thione Chemical compound S=C1CN=CN1 NXRIDTLKJCKPOG-UHFFFAOYSA-N 0.000 description 1
- HTZVLLVRJHAJJF-UHFFFAOYSA-M 1-decyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCCCCCN1C=C[N+](C)=C1 HTZVLLVRJHAJJF-UHFFFAOYSA-M 0.000 description 1
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- NDCSFKSWMDSVBX-UHFFFAOYSA-N 2-(2-chloropropan-2-yl)dodecylbenzene Chemical compound CCCCCCCCCCC(C(C)(C)Cl)CC1=CC=CC=C1 NDCSFKSWMDSVBX-UHFFFAOYSA-N 0.000 description 1
- JUNAPQMUUHSYOV-UHFFFAOYSA-N 2-(2h-tetrazol-5-yl)acetic acid Chemical compound OC(=O)CC=1N=NNN=1 JUNAPQMUUHSYOV-UHFFFAOYSA-N 0.000 description 1
- BMYCCWYAFNPAQC-UHFFFAOYSA-N 2-[dodecyl(methyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCN(C)CC(O)=O BMYCCWYAFNPAQC-UHFFFAOYSA-N 0.000 description 1
- PCFUWBOSXMKGIP-UHFFFAOYSA-N 2-benzylpyridine Chemical compound C=1C=CC=NC=1CC1=CC=CC=C1 PCFUWBOSXMKGIP-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- DVGVMQVOCJNXNJ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;4-methylbenzenesulfonate Chemical compound C[N+](C)(C)CCO.CC1=CC=C(S([O-])(=O)=O)C=C1 DVGVMQVOCJNXNJ-UHFFFAOYSA-M 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- QXPWKLBWUZALNM-UHFFFAOYSA-N 2h-benzotriazole;1h-imidazole Chemical compound C1=CNC=N1.C1=CC=CC2=NNN=C21 QXPWKLBWUZALNM-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- MVVJINIUPYKZHR-UHFFFAOYSA-N 3-[[4-[5-(methoxymethyl)-2-oxo-1,3-oxazolidin-3-yl]phenoxy]methyl]benzonitrile Chemical compound O=C1OC(COC)CN1C(C=C1)=CC=C1OCC1=CC=CC(C#N)=C1 MVVJINIUPYKZHR-UHFFFAOYSA-N 0.000 description 1
- XGWWZKBCQLBJNH-UHFFFAOYSA-N 3-methylsulfanyl-1h-1,2,4-triazol-5-amine Chemical compound CSC1=NN=C(N)N1 XGWWZKBCQLBJNH-UHFFFAOYSA-N 0.000 description 1
- AGWWTUWTOBEQFE-UHFFFAOYSA-N 4-methyl-1h-1,2,4-triazole-5-thione Chemical compound CN1C=NN=C1S AGWWTUWTOBEQFE-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-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
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- XDUVTZGINNGNAG-UHFFFAOYSA-M tridodecyl(methyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC XDUVTZGINNGNAG-UHFFFAOYSA-M 0.000 description 1
- GPQCSCQDQNXQSV-UHFFFAOYSA-N tridodecylazanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC GPQCSCQDQNXQSV-UHFFFAOYSA-N 0.000 description 1
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/34—Alkaline compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- 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
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/40—Alkaline compositions for etching other metallic material
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- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
-
- H—ELECTRICITY
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Abstract
本發明提供適用於選擇性地蝕刻釕及/或銅之組合物。該等組合物包含某些過碘酸鹽化合物、氫氧化烷基銨或烷基鏻、碳酸鹽或碳酸氫鹽緩衝劑及水，其中該組合物之pH為約9至約12.5。本發明之組合物有效用於本發明之方法中且已發現能夠以類似速率，亦即＞20 Å/min蝕刻Cu及Ru，同時將介電質之蝕刻速率降至最低(＜2 Å/min)。
Description
本發明屬於電子化學品之領域。特定言之，其係關於用於選擇性地蝕刻釕及/或銅之組合物及方法。
在動態隨機存取(DRAM)記憶體裝置中，金屬-絕緣體-金屬(metal-insulator-metal，MIM)電容器具有使用諸如釕之貴金屬製造的底部電極。鑒於其電學效能，亦已發現釕充當銅互連之銅擴散障壁材料。
但是釕之分離及平坦化存在問題，因為其一般自塗佈有難以蝕刻的RuO2
氧化膜。其蝕刻需要強氧化劑，然而這往往會將Ru及RuO2
轉化成揮發性及毒性氧化物RuO4
。如此形成之RuO4
蒸氣與有機材料反應且生成RuO2
粒子。此等特性將可安全地蝕刻釕之pH的範圍限於≥9，且較佳地限於≥10，以便僅形成釕之非揮發性氧陰離子。
本發明如隨附申請專利範圍中所闡述。在第一態樣中，本發明提供一種組合物，其包含
(i)一或多種選自原過碘酸(H5
IO6
)或偏過碘酸(HIO4
)之七價碘含氧酸或其鹽；
(ii)氫氧化烷基銨化合物或氫氧化烷基鏻化合物；及
(iii)水；
其中該組合物之pH為約9至約12.5。在本發明之組合物中，將過碘酸用作氧化劑。存在兩種主要形式之過碘酸，原過碘酸(H5
IO6
)及偏過碘酸(HIO4
)，且預期兩種形式適用作以上組分(i)。另外，其他遇到之含氧酸可包括H3
IO5
、H4
I2
O9
及H7
I3
O14
或其鹽。在以下實例中利用原過碘酸。在另一實施例中，組合物進一步包含(iv)碳酸鹽/碳酸氫鹽緩衝化合物。本發明之組合物有效用於本發明之方法中且已發現能夠以類似速率，亦即＞20 Å/min蝕刻Cu及Ru，同時將介電質之蝕刻速率降至最低(＜2 Å/min)。
如本文所使用，「微電子裝置」對應於半導體基板，包括DRAM 3D NAND結構、平板顯示器及微機電系統(microelectromechanical system，MEMS)，其經製造用於微電子、積體電路或電腦芯片應用中。應理解，術語「微電子裝置」不意謂以任何方式為限制性的，且包括包括負通道金屬氧化物半導體(negative channel metal oxide semiconductor，nMOS)及/或正通道金屬氧化物半導體(positive channel metal oxide semiconductor，pMOS)電晶體之任何基板，且將最終成為微電子裝置或微電子總成。
如本文中所使用，「約」意欲對應於所陳述值之+/-5%。
如下文更充分地描述，本發明之組合物可實施於廣泛多種特定調配物中。
在組合物之某些實施例中，組分(i)以約0.01至20重量%之量存在；組分(ii)以約0.02至40重量%之量存在；其中(i)、(ii)組分(iii)之總和為100%。
在組合物之某些實施例中，組分(i)以約0.5至10重量%之量存在；且組分(ii)以約1至20重量%之量存在；其中(i)、(ii)組分(iii)之總和為100%。
在組合物之某些實施例中，組分(i)以約1至5重量%之量存在且組分(ii)以約2至10重量%之量存在；其中(i)、(ii)組分(iii)之總和為100%。
在某些實施例中，組合物進一步包含
(iv)碳酸鹽/碳酸氫鹽緩衝化合物，其量為約0.01至5重量%、0.1至2重量%或0.2至1重量%，其中(i)、(ii)、(iii)及(iv)之總和為100%。
除非上下文另外明確指示，否則如本說明書及隨附申請專利範圍中所使用，單數形式「一(a/an)」及「該(the)」包括複數個參考物。除非在申請專利範圍中明確排除，否則術語「含有」或「包括」意欲與術語「包含」同義，意謂至少所命名化合物、元素、粒子或方法步驟等存在於組合物或製品或方法中，但並不排除其他化合物、材料、粒子、方法步驟等之存在，即使其他此類化合物、材料、粒子、方法步驟等具有與所命名之物相同的功能。
在本發明之組合物中，烷基銨(或烷基鏻)過碘酸鹽物種通常原位形成，同時使用過量之氫氧化烷基銨或氫氧化烷基鏻以及過碘酸(組分(i))，因為pH調節至所需水準。或者，在本發明之另一實施例中，可添加以純形式或以由過碘酸、水及鹼(諸如氫氧化烷基銨)製成之溶液形式的過碘酸鹽以便將pH調節至所需水準。適宜地，碳酸鹽/碳酸氫鹽緩衝系統可用於穩定水性組合物，同時用CO2
鼓泡溶液；或者，可一次添加所需濃度之含有溶解CO2
的水。使用碳酸鹽緩衝劑有利地避免與(可氧化)胺緩衝劑之潛在不相容性。或者，可利用氫氧化烷基銨或氫氧化烷基鏻之碳酸鹽及/或碳酸氫鹽且將此類物種添加至呈固體或液體狀之組合物中。氫氧化烷基鏻化合物可具有式HxN(P)Ry，其中x + y = 4，其中y＞0。
在一個實施例中，組合物包含(作為起始物質成分)約93.923%水、3.494%氫氧化四甲基銨、2.108% H5
IO6
、0.475% CO2
且具有約10.8之pH。在另一實施例中，組合物包含大致94重量%水、3.5重量%氫氧化四甲基銨及約0.5重量%碳酸鹽/碳酸氫鹽緩衝化合物。
吾等已發現，此類組合物具有足夠鹼性以避免形成毒性及揮發性RuO4
蒸氣且亦趨於使Cu以其與過碘酸鹽之Cu3+
可溶性錯合物形式溶解，同時仍具足夠活性從而以＞20 Å/min將釕氧化(Ru蝕刻速率隨著pH提高而降低)。在本發明之方法之實踐中，吾人可選擇藉由在以上所述範圍內改變pH來改變Ru與Cu之間的蝕刻速率，其中Ru在較低pH (接近9)下優先蝕刻，且其中Cu在較高pH (接近11)下優先蝕刻。此外，吾等已發現組合物之pH足夠低以使得PETEOS蝕刻速率＜1 Å/min，且OSG蝕刻速率相當低(約6 Å/min)。
在蝕刻應用中，以任何適合之方式將組合物施加至上面具有釕及/或銅材料之微電子裝置的表面，例如藉由將組合物噴塗於裝置之表面上，藉由浸漬(在移除組合物之靜態或動態體積中)包括釕及銅之裝置。在一個實施例中，將移除組合物施加至微電子裝置之表面為受控攪動，藉此組合物循環通過容納該組合物之容器。
如本文所定義，術語「障壁材料」對應於此項技術中用以密封金屬線(例如，銅互連線)以將該金屬(例如，銅)至介電材料中之擴散降至最低的任何材料。較佳之障壁層材料包括鉭、鈦、釕、鉿、鎢及其他耐火金屬及其氮化物及矽化物。
在使用本發明之組合物以自上面具有釕及/或銅材料之微電子裝置結構移除釕及/或銅材料時，該組合物典型地與微電子裝置結構在包括但不限於，在一個實施例中，在約20℃至約90℃範圍內之溫度下(在用於分批蝕刻之情況下)，或在另一實施例中，在約50℃至約90℃範圍內之溫度下(用於單晶圓工具蝕刻)的充足條件下接觸持續1分鐘至約200分鐘之充足時間，在一個實施例中，約15分鐘至約100分鐘，或約1分鐘至約2分鐘(用於單晶圓工具)。此類接觸時間及溫度為說明性的，且可採用在本發明之實踐內有效地自裝置結構至少部分移除釕及/或銅材料之任何其他適合之時間及溫度條件。
為達成約9至約12.5之pH，添加過量之組合物之組分(ii)且該組分(ii)可為具有式NR4
R5
R6
R7
OH之氫氧化烷基銨化合物，其中R4
、R5
、R6
及R7
可彼此相同或不同，且選自氫、直鏈或支鏈C1
-C6
烷基(例如，甲基、乙基、丙基、丁基、戊基及己基)基團、C1-
C6
羥烷基(例如，羥甲基、羥乙基、羥丙基、羥丁基、羥戊基及羥己基)基團及經取代或未經取代的C6
-C10
芳基(例如，苯甲基)。可商購之氫氧化烷基銨包括氫氧化四甲基銨(TMAH)、氫氧化四乙基銨(TEAH)、氫氧化四丙基銨(TPAH)、氫氧化四丁基銨(TBAH)、氫氧化三丁基甲基銨(TBMAH)、氫氧化苯甲基三甲基銨(BTMAH)、氫氧化膽鹼、氫氧化乙基三甲基胺、氫氧化參(2-羥乙基)甲基銨、氫氧化二乙基二甲基胺及其組合，其可經使用。或者或另外，組合物之組分(ii)可為具有式(PR8
R9
R10
R11
)OH之鏻鹼，其中R8
、R9
、R10
及R11
可彼此相同或不同，且選自由以下組成之群：氫、直鏈C1
-C6
烷基(例如，甲基、乙基、丙基、丁基、戊基及己基)基團、直鏈C1
-C6
烷基、C1
-C6
羥烷基(例如，羥甲基、羥乙基、羥丙基、羥丁基、羥戊基及羥己基)基團、經取代之C6
-C10
芳基、未經取代之C6
-C10
芳基(例如，苯甲基)及其任何組合，諸如氫氧化四丁基鏻(TBPH)、氫氧化四甲基鏻、氫氧化四乙基鏻、氫氧化四丙基鏻、氫氧化苯甲基三苯基鏻、氫氧化甲基三苯基鏻、氫氧化乙基三苯基鏻、氫氧化正丙基三苯基鏻。
在其他實施例中，本發明之組合物進一步包含一或多種腐蝕抑制劑。在本發明之上下文中，此類腐蝕抑制劑降低金屬之腐蝕速率；腐蝕抑制劑之類別可包括但不限於：1.結合、吸附、塗佈至金屬表面/或與金屬表面反應，且為氧氣或水輸送至金屬表面提供障壁或防止氧化金屬陽離子自表面傳播出之分子；2.改變金屬之電化學表面電位且使其更貴重之分子；及3.犧牲地清除提高腐蝕速率之氧或酸之分子。例示性腐蝕抑制劑包括化合物，諸如三唑及其衍生物、苯并三唑及其衍生物、甲苯基三唑、噻唑及其衍生物、四唑及其衍生物、咪唑及其衍生物以及吖嗪及其衍生物。例示性腐蝕抑制劑包括5-胺基四唑、5-苯基-苯并三唑、1H-四唑-5-乙酸、1-苯基-2-四唑啉-5-硫酮、苯并咪唑、甲基四唑、試鉍硫醇I (Bismuthiol I)、胞嘧啶、鳥嘌呤、胸嘧啶、吡唑、亞胺基二乙酸(IDA)、丙硫醇、苯并異羥肟酸、檸檬酸、抗壞血酸、5-胺基-1,3,4-噻二唑-2-硫醇(ATDT)、苯并三唑(BTA)、1,2,4-三唑(TAZ)、甲苯基三唑、5-甲基-苯并三唑(mBTA)、5-苯基-苯并三唑、5-硝基-苯并三唑、苯并三唑甲酸、3-胺基-5-巰基-1,2,4-三唑、1-胺基-1,2,4-三唑、羥基苯并三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-1,2,3-三唑、1-胺基-5-甲基-1,2,3-三唑、3-胺基-1,2,4-三唑(3-ATA)、3-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯硫醇-苯并三唑、鹵基-苯并三唑(鹵基=F、Cl、Br或I)、萘三唑、2-巰基苯并咪唑(MBI)、2-巰基苯并噻唑、4-甲基-2-苯基咪唑、2-巰基噻唑啉、5-胺基-1,2,4-三唑(5-ATA)、十二烷基硫酸鈉(SDS)、ATA-SDS、3-胺基-5-巰基-1,2,4-三唑、伸戊基四唑、5-苯基-1H-四唑、5-苯甲基-1H-四唑、Ablumine O、2-苯甲基吡啶、丁二醯亞胺、2,4-二胺基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑啶酮、1,5-五亞甲基四唑、1-苯基-5-巰基四唑、二胺基甲基三嗪、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、4-胺基-4H-1,2,4-三唑、3-胺基-5-甲基硫基-1H-1,2,4-三唑、苯并噻唑、咪唑、吲二唑、腺嘌呤、丁二醯亞胺、腺苷、咔唑、鄰磺醯苯甲醯亞胺、尿酸、苯偶姻肟(benzoinoxime)、陽離子四級鹽(例如，氯化苯甲烴銨、氯化苯甲基二甲基十二烷基銨、溴化肉豆蔻基三甲基銨、溴化十二烷基三甲基銨、氯化十六基吡錠、Aliquot 336 (Cognis)、氯化苯甲基二甲基苯基銨、Crodaquat TES (Croda. Inc.)、Rewoquat CPEM (Witco)、對甲苯磺酸十六基三甲基銨、氫氧化十六基三甲基銨、二氯化1-甲基-1'-十四基-4,4'-二吡錠、溴化烷基三甲基銨、鹽酸氨丙林(amprolium hydrochloride)、氫氧化苄索銨、氯化苄索銨(benzethonium chloride)、氯化苯甲基二甲基十六基銨、氯化苯甲基二甲基十四基銨、溴化苯甲基十二烷基二甲基銨、氯化苯甲基十二烷基二甲基銨、氯化十六基吡錠、對甲苯磺酸膽鹼、溴化二甲基二十八基銨、溴化十二烷基乙基二甲基銨、氯化十二烷基三甲基銨、溴化乙基十六基二甲基銨、吉拉德氏試劑(Girard's reagent)、磷酸二氫十六基(2-羥乙基)二甲基銨、溴化十六基吡錠、溴化十六基三甲基銨、氯化十六基三甲基銨、氯化甲基苄索銨、Hyamine® 1622、Luviquat™、N,N',N'-聚氧化乙烯(10)-N-動物脂-1,3-二胺基丙烷液體、奧芬溴銨(oxyphenonium bromide)、溴化四庚基銨、溴化肆(癸基)銨、通佐溴銨(thonzonium bromide)、氯化三十二烷基銨、溴化三甲基十八基銨、四氟硼酸1-甲基-3-正辛基咪唑鎓、四氟硼酸1-癸基-3-甲基咪唑鎓、氯化1-癸基-3-甲基咪唑鎓、溴化三十二烷基甲基銨、氯化二甲基二硬脂基銨、溴化十六基三甲基銨、溴化肉豆蔻基三甲基銨及氯化六羥季銨)、陰離子界面活性劑(例如，十二烷基苯磺酸、十二烷基苯磺酸鈉、十二烷基膦酸(DDPA)、硬脂醯基肌胺酸、月桂基肌胺酸、Surfynol® 104 (四甲基癸炔二醇，Evonik)、炔丙醇、雙氰胺、二甲基炔丙醇、糖精二乙基羥胺、羥胺、2-巰基-2-噻唑啉、巰基噻二唑、胺基巰基噻二唑、二巰基噻二唑、3-甲基吡唑啉-5-酮及其組合。
在實現所需移除操作之後，蝕刻劑組合物易於自先前已經施加該組合物的微電子裝置移除，例如藉由沖洗、洗滌或其他一或多種移除步驟，如在本發明之組合物之給定最終用途應用中可能為所需的且有效的。舉例而言，可藉由包括去離子水之沖洗溶液來沖洗裝置及/或乾燥(例如，旋塗乾燥、N2
、蒸氣-乾燥等)。因此，在其他實施例中，本發明提供一種用於自微電子裝置移除釕及/或銅之方法，該方法包含使電子裝置與如本文所闡述之組合物在足以自微電子裝置至少部分地移除該釕及/或銅的條件下接觸持續足以自微電子裝置至少部分地移除該釕及/或銅的時間。
本發明之又其他態樣係關於製造包含微電子裝置之製品的方法，該方法包含使微電子裝置與本發明之組合物接觸持續足以自上面具有釕及/或銅材料之微電子裝置的表面以蝕刻方式移除釕及/或銅材料的時間，及將該微電子裝置併入至該製品中。
藉由簡單添加各別成分且混合至均質狀況，易於調配出本文所描述之組合物。
本發明已尤其參考其實施例來詳細描述，但應理解，可在本發明之精神及範疇內實現變化及修改。
實例
藉由在攪拌及冷卻之情況下添加50%原過碘酸溶液至所計算量之水中，隨後添加指定量之20-25%特定鹼(每莫耳過碘酸＞2莫耳鹼)溶液來製備列表於下文中之調配物。對於含CO2
的溶液(6-8號)，碳酸-碳酸氫四甲基銨緩衝劑藉由緩慢鼓泡CO2
通過25% TMAH溶液直至pH降低到約11.5來製備，其後將所計算量之緩衝劑添加至水、過碘酸及TMAH之混合物中。
在攪拌下在60℃下進行毯覆式膜試片之蝕刻。未嘗試預處理釕；用5%乙酸(HAc)預處理銅顯示蝕刻速率提高，但僅稍微提高。在無HAc預處理之情況下獲得列表之Cu結果，而使用經HAc-預處理之銅獲得下文進一步繪製之結果。用去離子水沖洗蝕刻試片且在氮氣噴射中乾燥。金屬厚度變化藉由XRF測定；介電質厚度變化-藉由橢圓偏振量測法測定。
儘管基於KOH之調配物蝕刻比基於烷基銨之調配物快得多，但其對於介電質組分卻更苛刻。
*在膜完全蝕刻掉之情況下，結果-之前的「＞」-為下限。
** OSG在此情況下嚴重粗糙化，因此不能準確地量測厚度。
| 在60℃下之蝕刻速率，以Å/分鐘為單位 | ||||||||||||||||||
| 膜 à | Ru | Cu | PETEOS | OSG | TaN | |||||||||||||
| 調配物 | 化合物，以mol/kg為單位 | pH â 運行長度 à | 0.5' | 1' | 3' | 5' | 10' | 1' | 3' | 20' | 10' | 20' | 3' | 10' | 20' | 10' | 20' | |
| 1 | 0.2 PIA + 0.44 KOH | 11.75 | ＞450* | ＞225 | ||||||||||||||
| 2 | 12.13 | (＞176) | 9.9 (高)** | ? (高)* | ＜1 | |||||||||||||
| 3 | 0.2 PIA + 0.44 MTEAH | 11.97 | 7.3 | |||||||||||||||
| 4 | 0.2 PIA + 0.44 TMAH | 12.22 | 6.85 | |||||||||||||||
| 5 | 0.2 PIA + 0.4025 TMAH | 11.37 | 66 | 0.55 | 4.8 | 0 | ||||||||||||
| 6 | 0.2 PIA + 0.66 TMAH + 0.13 CO2 | 12.2 | 13.2 | 15.4 | 97.4 | |||||||||||||
| 7 | 0.2 PIA + 0.705 TMAH + 0.177 CO2 | 10.51 | ＞223 | (＞45) | 153.7 | 0.82 | 6.6 | 0.07 | ||||||||||
| 8 | .0925 PIA + 0.3834 TMAH + 0.1079 CO2 | 10.79 | 4 | 20 | 30 | 53 | 28 | 0.3 | 6.1 | 7.4 | -0.17 | 0.09 | ||||||
| 2.108% PIA, 3.494% TMAH, 0.475% CO2 |
縮寫說明：
PIA=過碘酸，H5
IO6
.
MTEAH=氫氧化甲基三乙銨
PETEOS=電漿增強之正矽酸四乙酯
OSG=有機矽酸鹽玻璃
圖1為如藉由XRF(x射線螢光)所測定之以埃為單位之Cu厚度損失相對於以分鐘為單位之運行時間的曲線圖。所測試之組合物為2.108%過碘酸(H5
IO6
)、3.494%氫氧化四甲基銨及0.475% CO2
(下文調配物實例8)。
Claims (10)
- 一種蝕刻組合物，其包含(i)一或多種選自H5IO6或HIO4之七價氧化劑；(ii)氫氧化烷基銨化合物或氫氧化烷基鏻化合物，其相對於該一或多種七價氧化劑為過量；(iii)水；其中該蝕刻組合物之pH為約9至約12.5。
- 如請求項1之蝕刻組合物，其中該氫氧化烷基銨化合物係選自氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化三丁基甲基銨、氫氧化苯甲基三甲基銨、氫氧化膽鹼、氫氧化乙基三甲基銨、氫氧化參(2-羥乙基)甲基銨、氫氧化二乙基二甲基銨及其組合。
- 如請求項2之蝕刻組合物，其中該氫氧化烷基銨化合物為氫氧化四甲基銨。
- 如請求項1之蝕刻組合物，其中該氫氧化烷基鏻化合物係選自氫氧化四丁基鏻、氫氧化四甲基鏻、氫氧化四乙基鏻、氫氧化四丙基鏻、氫氧化苯甲基三苯基鏻、氫氧化甲基三苯基鏻、氫氧化乙基三苯基鏻及氫氧化正丙基三苯基鏻及其組合。
- 如請求項1之蝕刻組合物，其進一步包含 (iv)碳酸鹽/碳酸氫鹽緩衝化合物。
- 如請求項5之蝕刻組合物，其中該緩衝化合物藉由用二氧化碳鼓泡該蝕刻組合物而原位形成。
- 如請求項1之蝕刻組合物，其中組分(i)以約0.01至20重量%之量存在；組分(ii)以約0.02至40重量%之量存在；其中(i)、(ii)組分(iii)之總和為100%。
- 如請求項1之蝕刻組合物，其中組分(i)以約0.5至10重量%之量存在；組分(ii)以約1至20重量%之量存在；其中(i)、(ii)組分(iii)之總和為100%。
- 如請求項1之蝕刻組合物，其中組分(i)以約1至5重量%之量存在；組分(ii)以約2至10重量%之量存在；其中(i)、(ii)組分(iii)之總和為100%。
- 一種用於自微電子裝置移除釕及/或銅之方法，該方法包含使電子裝置與如請求項1之蝕刻組合物在充足條件下接觸持續充足時間以自該微電子裝置至少部分地移除該釕及/或銅。
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| JP7219061B2 (ja) * | 2018-11-14 | 2023-02-07 | 関東化学株式会社 | ルテニウム除去用組成物 |
| US11898081B2 (en) * | 2019-11-21 | 2024-02-13 | Tokyo Ohka Kogyo Co., Ltd. | Ruthenium-etching solution, method for manufacturing ruthenium-etching solution, method for processing object to be processed, and method for manufacturing ruthenium-containing wiring |
-
2019
- 2019-11-22 US US16/692,834 patent/US11346008B2/en active Active
- 2019-11-22 CN CN201980081808.8A patent/CN113195681A/zh active Pending
- 2019-11-22 WO PCT/US2019/062835 patent/WO2020123126A1/en unknown
- 2019-11-22 EP EP19896272.2A patent/EP3894512A4/en active Pending
- 2019-11-22 JP JP2021533484A patent/JP7269348B2/ja active Active
- 2019-11-22 KR KR1020217021563A patent/KR102646575B1/ko active IP Right Grant
- 2019-11-22 SG SG11202105495VA patent/SG11202105495VA/en unknown
- 2019-12-11 TW TW108145228A patent/TWI727543B/zh active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201144484A (en) * | 2009-12-17 | 2011-12-16 | Showa Denko Kk | Composition for etching ruthenium-based metal and method for preparing same |
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| WO2020123126A1 (en) | 2020-06-18 |
| EP3894512A1 (en) | 2021-10-20 |
| EP3894512A4 (en) | 2022-08-24 |
| US11346008B2 (en) | 2022-05-31 |
| KR20210092311A (ko) | 2021-07-23 |
| SG11202105495VA (en) | 2021-06-29 |
| JP2022512386A (ja) | 2022-02-03 |
| CN113195681A (zh) | 2021-07-30 |
| TW202030368A (zh) | 2020-08-16 |
| KR102646575B1 (ko) | 2024-03-13 |
| JP7269348B2 (ja) | 2023-05-08 |
| US20200190673A1 (en) | 2020-06-18 |
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