CN105102584A - 用于选择性蚀刻氮化钛的组合物和方法 - Google Patents
用于选择性蚀刻氮化钛的组合物和方法 Download PDFInfo
- Publication number
- CN105102584A CN105102584A CN201480020454.3A CN201480020454A CN105102584A CN 105102584 A CN105102584 A CN 105102584A CN 201480020454 A CN201480020454 A CN 201480020454A CN 105102584 A CN105102584 A CN 105102584A
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- China
- Prior art keywords
- ammonium
- acid
- ether
- composition
- methyl
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 141
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000005530 etching Methods 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 28
- 239000000463 material Substances 0.000 claims abstract description 115
- 238000004377 microelectronic Methods 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005260 corrosion Methods 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 24
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 24
- 230000007797 corrosion Effects 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000010937 tungsten Substances 0.000 claims abstract description 19
- 239000011810 insulating material Substances 0.000 claims abstract description 8
- -1 hexafluorosilicic acid Chemical compound 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 27
- 239000003153 chemical reaction reagent Substances 0.000 claims description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 21
- 229910052718 tin Inorganic materials 0.000 claims description 21
- 230000031709 bromination Effects 0.000 claims description 16
- 238000005893 bromination reaction Methods 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 239000012964 benzotriazole Substances 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 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 description 9
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 claims description 9
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 9
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 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 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- HIMXGTXNXJYFGB-UHFFFAOYSA-N alloxan Chemical compound O=C1NC(=O)C(=O)C(=O)N1 HIMXGTXNXJYFGB-UHFFFAOYSA-N 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 150000003217 pyrazoles Chemical class 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 5
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 claims description 5
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 5
- 150000001412 amines Chemical class 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
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 5
- 229960002798 cetrimide Drugs 0.000 claims description 5
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 5
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 239000002516 radical scavenger Substances 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 5
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- NUUDMTGMAZJCBY-UHFFFAOYSA-N 1-decyl-3-methyl-2h-imidazole Chemical compound CCCCCCCCCCN1CN(C)C=C1 NUUDMTGMAZJCBY-UHFFFAOYSA-N 0.000 claims description 4
- HHDRWGJJZGJSGZ-UHFFFAOYSA-N 5-benzyl-2h-tetrazole Chemical compound C=1C=CC=CC=1CC=1N=NNN=1 HHDRWGJJZGJSGZ-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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-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
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- OIRDTQYFTABQOQ-KQYNXXCUSA-N adenosine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O OIRDTQYFTABQOQ-KQYNXXCUSA-N 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-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
- 229960001927 cetylpyridinium chloride Drugs 0.000 claims description 4
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 claims description 4
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 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
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 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
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 3
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- UKLQXHUGTKWPSR-UHFFFAOYSA-M oxyphenonium bromide Chemical compound [Br-].C=1C=CC=CC=1C(O)(C(=O)OCC[N+](C)(CC)CC)C1CCCCC1 UKLQXHUGTKWPSR-UHFFFAOYSA-M 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- WBWDWFZTSDZAIG-UHFFFAOYSA-M thonzonium bromide Chemical compound [Br-].N=1C=CC=NC=1N(CC[N+](C)(C)CCCCCCCCCCCCCCCC)CC1=CC=C(OC)C=C1 WBWDWFZTSDZAIG-UHFFFAOYSA-M 0.000 claims description 3
- 229940051002 thonzonium bromide Drugs 0.000 claims description 3
- 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
- OOYDTEGVMRPGRK-UHFFFAOYSA-N (9-octanoyl-8,10-dioxoheptadecan-9-yl)azanium;chloride Chemical compound [Cl-].CCCCCCCC(=O)C([NH3+])(C(=O)CCCCCCC)C(=O)CCCCCCC OOYDTEGVMRPGRK-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
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-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
- 229940058015 1,3-butylene glycol Drugs 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
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- OMAFFHIGWTVZOH-UHFFFAOYSA-O 1-methyl-2h-tetrazol-1-ium Chemical compound C[N+]1=CN=NN1 OMAFFHIGWTVZOH-UHFFFAOYSA-O 0.000 claims description 2
- KTUWFYALZIAAGE-UHFFFAOYSA-N 1-methyl-3-octyl-2h-imidazole Chemical class CCCCCCCCN1CN(C)C=C1 KTUWFYALZIAAGE-UHFFFAOYSA-N 0.000 claims description 2
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 2
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 2
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 2
- SYOANZBNGDEJFH-UHFFFAOYSA-N 2,5-dihydro-1h-triazole Chemical compound C1NNN=C1 SYOANZBNGDEJFH-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 claims description 2
- MTVLEKBQSDTQGO-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol Chemical compound CCOC(C)COC(C)CO MTVLEKBQSDTQGO-UHFFFAOYSA-N 0.000 claims description 2
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 claims description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 2
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- PCFUWBOSXMKGIP-UHFFFAOYSA-N 2-benzylpyridine Chemical compound C=1C=CC=NC=1CC1=CC=CC=C1 PCFUWBOSXMKGIP-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 claims description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 2
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 2
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- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 2
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 claims description 2
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- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 2
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- IGZNKFVYUIURCZ-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCCCl Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCCCl IGZNKFVYUIURCZ-UHFFFAOYSA-N 0.000 claims description 2
- SYZWTSVMUSDDTQ-UHFFFAOYSA-N CCONCC1=CC=CC=C1.CCl Chemical compound CCONCC1=CC=CC=C1.CCl SYZWTSVMUSDDTQ-UHFFFAOYSA-N 0.000 claims description 2
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- LNEFZUJHVAPPMQ-UHFFFAOYSA-N NC1=C(C(=O)O)C(=CC(=C1C(=O)O)N)C Chemical compound NC1=C(C(=O)O)C(=CC(=C1C(=O)O)N)C LNEFZUJHVAPPMQ-UHFFFAOYSA-N 0.000 claims description 2
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
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- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 claims description 2
- YUUVAZCKXDQEIS-UHFFFAOYSA-N azanium;chlorite Chemical compound [NH4+].[O-]Cl=O YUUVAZCKXDQEIS-UHFFFAOYSA-N 0.000 claims 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 claims description 2
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- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 claims description 2
- WAKHLWOJMHVUJC-UHFFFAOYSA-N benzoin alpha-oxime Natural products C=1C=CC=CC=1C(=NO)C(O)C1=CC=CC=C1 WAKHLWOJMHVUJC-UHFFFAOYSA-N 0.000 claims description 2
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- LUVHDTDFZLTVFM-UHFFFAOYSA-N chloric acid tetramethylazanium Chemical compound C[N+](C)(C)C.Cl(=O)(=O)O LUVHDTDFZLTVFM-UHFFFAOYSA-N 0.000 claims description 2
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- FDXKBUSUNHRUIZ-UHFFFAOYSA-N chlorous acid tetramethylazanium Chemical compound C[N+](C)(C)C.Cl(=O)O FDXKBUSUNHRUIZ-UHFFFAOYSA-N 0.000 claims description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 2
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 claims description 2
- VCAVAURZPNANDQ-UHFFFAOYSA-N ethyl-hexadecyl-dimethylazanium Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC VCAVAURZPNANDQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- UENRCAFKOCYSLM-UHFFFAOYSA-N hexadecyl-(2-hydroxyethyl)-dimethylazanium Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CCO UENRCAFKOCYSLM-UHFFFAOYSA-N 0.000 claims description 2
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- 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
- C09K13/10—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a boron compound
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
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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
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Abstract
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铜以及绝缘材料而言选择性去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的半水性组合物。所述半水性组合物含有至少一种氧化剂、至少一种蚀刻剂和至少一种有机溶剂，可含有各种腐蚀抑制剂以确保选择性。
Description
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(criticaldimension)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。
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、至少二氧化硅源、水和至少一种有机溶剂，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、至少二氧化硅源、水和至少一种有机溶剂的组合物接触，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选择性去除氮化钛材料。
根据随后的公开内容和所附权利要求书，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电介质层选择性蚀刻硬掩模层和/或光致抗蚀剂蚀刻残余物的半水性组合物和方法。更具体地，本发明涉及用于相对于铜、钨和低k电介质层选择性蚀刻氮化钛和/或光致抗蚀剂蚀刻残余物的半水性组合物和方法。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、光伏器件和微机电系统(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”或“硬掩模”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、(ii)包括胺基团的表面活性剂，和(iii)其中胺基团是取代基(例如，连接至芳基或杂环部分)的物质根据这个定义不被视为“胺”。所述胺的分子式可由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。
在本文中使用时，“氯化物”物质对应于包括氯离子(Cl-)的物质，其条件是包括氯化物阴离子的表面活性剂根据这个定义不被视为“氯化物”。
在本文中使用时，术语“半水性”是指水和有机溶剂组分的混合物。所述半水性去除组合物必须不显著破坏所存在的金属导体层和低k电介质层，同时去除硬掩模层和/或光致抗蚀剂蚀刻残余物。
如本文所定义，强碱是具有至少一种大于11的pKa的任何碱，而弱碱是具有至少一种小于11的pKa的任何碱。
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重量百分比的浓度存在。
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，半水性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，所述半水性组合物是相对于铜、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。
因此，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半水性组合物，所述组合物包括至少一种氧化剂和至少一种蚀刻剂，其中所述组合物基本上不含过氧化氢。在一个实施方式中，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去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的半水性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、水和至少一种有机溶剂，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，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去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的半水性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、水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。在另一个实施方式中，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去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的半水性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、水、至少一种二氧化硅源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。在另一个实施方式中，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去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的半水性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、水和至少一种有机溶剂，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，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去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的半水性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、至少一种二氧化硅源、水和至少一种有机溶剂，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，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去除氮化钛和/或光致抗蚀剂蚀刻残余物材料的半水性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、至少二氧化硅源、水和至少一种有机溶剂，其中所述组合物基本上不含过氧化氢。被设想包括于本文所述的半水性组合物中的其它组分包括但不限于至少一种低k钝化剂、至少一种表面活性剂、至少一种碘清除剂和其组合。有利的是，这些组合物在约45℃至约60℃范围内的温度下具有大于40:1的TiN:钨选择性和小于约的钨去除速率，甚至更优选大于50:1的TiN:钨选择性和小于约的钨去除速率。此外，这些组合物在约45℃至约60℃范围内的温度下具有大于20:1的TiN:铜选择性和小于约的铜去除速率，甚至更优选大于30:1的TiN:铜选择性和小于约的铜去除速率。这些组合物基本上不含如本文所定义的胺、化学机械抛光研磨材料、金属卤化物和其组合。所述半水性组合物具有在0至4范围内的pH值，和在30至50mN/m范围内、优选在约30mN/m至约40mN/m范围内的表面张力值。
添加蚀刻剂以增加氮化钛的蚀刻速率。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，氟化物源包括四氟硼酸、六氟硅酸、H2ZrF6、H2TiF6、HPF6、氟化铵、氟化氢铵、氟化四甲基铵、氢氧化四甲基铵、六氟硅酸铵、六氟钛酸铵，或氟化铵和氟化四甲基铵的组合。可选地，或除了氟化物源之外，所述蚀刻剂可包含强碱如氢氧化四甲基铵(TMAH)、氢氧化四乙基铵(TEAH)、氢氧化四丙基铵(TPAH)、氢氧化四丁基铵(TBAH)、氢氧化苄基三甲基铵(BTMAH)、氢氧化钾、氢氧化铵、氢氧化苄基三乙基铵(BTEAH)、氢氧化四丁基(TBPH)、氢氧化(2-羟基乙基)三甲基铵、氢氧化(2-羟基乙基)三乙基铵、氢氧化(2-羟基乙基)三丙基铵、氢氧化(1-羟基丙基)三甲基铵、氢氧化乙基三甲基铵、氢氧化二乙基二甲基铵(DEDMAH)、1,1,3,3-四甲基胍(TMG)、碳酸胍、精氨酸和其组合。最优选地，所述蚀刻剂包含六氟硅酸、四氟硼酸或其组合。
包括氧化剂来氧化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(2KHSO5·KHSO4·K2SO4)、高碘酸、碘酸、氧化钒(V)、氧化钒(IV,V)(V6O13)、钒酸铵、铵多原子盐(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))、钠多原子盐(例如，过硫酸钠(Na2S2O8)、次氯酸钠(NaClO)、过硼酸钠)、钾多原子盐(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))、四甲基铵多原子盐(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))、四丁基铵多原子盐(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(alloxan)、N-甲基吗啉N-氧化物、三甲基胺N-氧化物和其组合。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，用于第二方面的组合物的氧化剂包含过氧化氢。优选地，用于半水性组合物的氧化剂包含氧化钒、钒酸铵、碘酸铵、高碘酸铵、碘酸、高碘酸、1,4-苯醌或其组合。
所述半水性组合物包含至少一种二氧化硅源以降低蚀刻剂源的活性。在一个实施方式中，至少一种二氧化硅源包含烷氧基硅烷。设想的烷氧基硅烷具有通式SiR1R2R3R4，其中R1、R2、R3和R4彼此相同或不同并选自直链的C1-C6烷基基团(例如，甲基、乙基、丙基、丁基、戊基、己基)、支链的C1-C6烷基基团、C1-C6烷氧基基团(例如，甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基)、苯基基团和其组合。本领域技术人员应理解，为了被表征为烷氧基硅烷，R1、R2、R3或R4中的至少一个必须是C1-C6烷氧基基团。设想的烷氧基硅烷包括甲基三甲氧基硅烷、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、己基三乙氧基硅烷和其组合。可以代替烷氧基硅烷使用或除了烷氧基硅烷之外还可以使用的其它二氧化硅源包括六氟硅酸铵、硅酸钠、硅酸四甲基铵(TMAS)和其组合。优选地，含硅化合物包含TEOS、TMAS、硅酸钠或其组合。
包括蚀刻剂和二氧化硅源两者的一种替代方案是在原位产生氟硅酸。氢氟酸(优选在40％或更高浓度下)和TEOS或其它可水解烷氧基硅烷可以以适当比率组合在至少一种有机溶剂中以形成具有恰当量的在SiO2中饱和或接近饱和的氟硅酸的浓缩物。
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。
添加金属腐蚀抑制剂以阻断所述氧化剂的氧化活性。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)、苯并三唑(BTA)、1,2,4-三唑(TAZ)、甲苯基三唑、5-甲基-苯并三唑、5-苯基-苯并三唑、5-硝基-苯并三唑、苯并三唑羧酸、3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、羟基苯并三唑、2-(5-氨基-戊基)-苯并三唑、1-氨基-1,2,3-三唑、1-氨基-5-甲基-1,2,3-三唑、3-氨基-1,2,4-三唑、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、卤代-苯并三唑(卤代＝F、Cl、Br或I)、萘并三唑、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、AblumineO(台湾表面活性剂)、2-苄基吡啶、琥珀酰亚胺、马来酰亚胺、邻苯二甲酰亚胺、戊二酰亚胺、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-1,2,4-三唑-3-硫醇、苯并噻唑、咪唑、吡唑、吲唑(indiazole)、腺苷、咔唑、糖精和苯偶姻肟。另外的腐蚀抑制剂包括阳离子型季铵表面活性剂盐，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Aliquat336(Cognis)、氯化苄基二甲基苯基铵、CrodaquatTES(CrodaInc.)、RewoquatCPEM(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、溴化乙基十六烷基二甲基铵、吉拉德试剂(Girard'sreagent)、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(oxyphenoniumbromide)、溴化四庚基铵、溴化四(癸基)铵、通佐溴铵(thonzoniumbromide)、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(hexamethoniumchloride)。其它腐蚀抑制剂包括非离子型表面活性剂如PolyFoxPF-159(OMNOVA溶液)、聚(乙二醇)(“PEG”)、聚(丙二醇)(“PPG”)、PEG-PPG共聚物如PluronicF-127(BASF)，阴离子型表面活性剂如十二烷基苯磺酸、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。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，但容易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。本文中还设想了这些转化的季铵盐。在一个特别优选的实施方式中，已知5-甲基-1H-苯并三唑阻断氧化剂对铜的氧化活性。可选地，或除了5-甲基-1H-苯并三唑(mBTA)之外，优选的腐蚀抑制剂包括吡唑、苯并三唑、阳离子型季铵表面活性剂盐，更优选地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和氢氧化十六烷基三甲基铵、四唑如5-苄基-1H-四唑和其组合。
本文所述的半水性组合物可以任选地包括至少一种低k钝化剂以降低低k电介质层的化学攻击并保护晶片免受额外的氧化。优选的低k钝化剂包括但不限于硼酸、硼酸盐如五硼酸铵、四硼酸钠、3-羟基-2-萘甲酸、丙二酸和亚氨基二乙酸。当存在时，所述半水性组合物包括以所述组合物的总重量计约0.01重量％至约2重量％的低k钝化剂。优选地，使用本文所述的半水性组合物蚀刻/去除以下伏的低k材料的总重量计小于2重量％、更优选小于1重量％、最优选小于0.5重量％的下伏低k材料。
为了确保润湿，特别是当pH较低时，可以向半水性组合物添加表面活性剂，优选地抗氧化、氟化阴离子型表面活性剂。本发明的组合物中设想的阴离子型表面活性剂包括但不限于氟表面活性剂如UR和FS-62(DuPontCanadaInc.,Mississauga,Ontario,Canada)和氟烷基磺酸铵如NovecTM4300(3M)。当所用蚀刻剂包含氟化物时，设想了使用可以用作表面活性剂和蚀刻剂的长链氟化四烷基铵。
所述至少一种有机溶剂包含至少一种水混溶性有机溶剂，其中所述至少一种水混溶性有机溶剂选自式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：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、1,2-丙二醇和1,3-丙二醇、1,2-丁二醇、1,3-丁二醇和1,4-丁二醇、四氢糠醇(THFA)、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、二乙二醇单乙醚、三乙二醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、二乙二醇单丁醚、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、二丙二醇乙醚、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、2,3-二氢十氟戊烷、乙基全氟丁醚、甲基全氟丁醚、碳酸烷基酯、碳酸亚烷基酯、4-甲基-2-戊醇、四亚甲基二醇二甲醚、二甲亚砜和其组合。优选地，所述至少一种有机溶剂包含二乙二醇单乙醚、二乙二醇甲醚、丙二醇、乙二醇、四乙二醇二甲醚、三乙二醇甲醚、三乙二醇乙醚、三丙二醇单甲醚、二丙二醇单甲醚或其组合。
在另一个实施方式中，本文所述的任何半水性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/或溶解在所述半水性组合物中。
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、至少二氧化硅源、水和至少一种有机溶剂，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：
在半水性组合物的一个特别优选实施方式中，所述至少一种氧化剂包括氧化钒、钒酸铵、碘酸铵、高碘酸铵、碘酸、高碘酸、1,4-苯醌或其组合；所述至少一种蚀刻剂包括六氟硅酸、四氟硼酸或其组合；所述至少一种腐蚀抑制剂包括5-甲基-1H-苯并三唑、吡唑、苯并三唑、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、氢氧化十六烷基三甲基铵、5-苄基-1H-四唑或其组合；所述至少一种二氧化硅源包括TEOS、TMAS、硅酸钠或其组合，并且所述至少一种有机溶剂包括二乙二醇单乙醚、二乙二醇甲醚、丙二醇、乙二醇、四乙二醇二甲醚、三乙二醇甲醚、三乙二醇乙醚、三丙二醇单甲醚、二丙二醇单甲醚或其组合。
应理解，通常的做法是制造待在使用前稀释的浓缩形式的半水性组合物。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氧化剂，其可能随时间不稳定。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浓缩物或稀释的半水性组合物。
本文所述的半水性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，所述半水性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半水性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，半水性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半水性组合物的组分。所述试剂盒的容器必须适合储存和运输所述半水性组合物组分，例如，容器(AdvancedTechnologyMaterials,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，所述系统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，并且无需任何可能不利地影响有待放置在衬里中的组分的纯度要求的颜料、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(APPARATUSANDMETHODFORMINIMIZINGTHEGENERATIONOFPARTICLESINULTRAPURELIQUIDS)”的美国专利No.7,188,644；名称为“可回收和可重复使用泡包袋型流体存储和分配容器系统(RETURNABLEANDREUSABLE,BAG-IN-DRUMFLUIDSTORAGEANDDISPENSINGCONTAINERSYSTEM)”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系统和方法(SYSTEMSANDMETHODSFORMATERIALBLENDINGANDDISTRIBUTION)”的PCT/US08/63276。
在第三方面，本发明涉及使用本文所述的半水性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半水性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。在另一个优选的实施方式中，描述了使用本文所述的半水性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，通过将半水性组合物喷涂在器件表面上，通过浸渍(在静态或动态体积的半水性组合物中)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半水性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半水性组合物接触，或通过使半水性组合物与氮化钛和/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。可分批或在单晶片装置中进行施加，用于动态或静态清洁。有利的是，本文所述的半水性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而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。
在本文所述的半水性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时，所述半水性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45℃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时间和温度条件。
在一个实施方式中，所述半水性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，所述半水性组合物寿命增加。
在完成所需蚀刻动作后，所述半水性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，通过如在本文所述半水性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)。
所述半水性组合物优选相对于金属导体和绝缘(即，低k电介质)材料选择性蚀刻氮化钛材料。在一个实施方式中，氮化钛的蚀刻速率高(在50℃下以上，优选约以上)，而金属(例如，Cu和W)的蚀刻速率低(小于约优选小于约，并且在相同温度下低k电介质的蚀刻速率低(小于约优选小于约)。
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半水性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，其中所述半水性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、至少二氧化硅源、水和至少一种有机溶剂，其中所述组合物基本上不含过氧化氢。所述半水性组合物还可包含氮化钛材料，由氮化钛材料组成或基本上由氮化钛材料组成。
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。
通过下文讨论的说明性实施例更充分地示出本发明的特征和优点。
实施例1
制备包含0.003重量％高碘酸、1.2重量％H2SiF6、0.004重量％苯扎氯铵、0.3重量％TEOS和98.493重量％去离子水的基础溶液1。用基础溶液1起始，如下表1-3中所示制备制剂。将铜、钨、TiN和PETEOS试样在50℃下在每种制剂中浸没所示时间并且测定蚀刻速率。
表1：通过将所示有机溶剂与余量的基础溶液1组合而制备的制剂。
表2：通过将所示有机溶剂和腐蚀抑制剂与余量的基础溶液1组合而制备的制剂。
表3：通过将所示有机溶剂和腐蚀抑制剂mBTA与余量的基础溶液1组合而制备的制剂。
可见添加10重量％有机溶剂和0.5％mBTA对TiN蚀刻速率无显著影响，但会降低Cu和W蚀刻速率。当有机溶剂的量升高至50重量％时，TiN蚀刻速率降低。利用50重量％有机溶剂得到的结果表明，制剂可以进行调节以改变制剂的选择性。例如，通过调节溶剂浓度，TiN蚀刻速率可从改变至小于以及降低Cu和W蚀刻速率，例如在具有溶剂DPGME的制剂L和W中。在另一个方面，半水性组合物是相对于TiN和W选择性去除铜或者相对于W选择性去除Cu和TiN的制剂。
可见添加10重量％有机溶剂降低了铜的蚀刻速率，这被认为是由于有机溶剂辅助mBTA的溶解。此外，添加有机溶剂与mBTA对TiN蚀刻速率无负面影响而仍与Cu和W相容。
实施例2
制备包含0.01重量％钒酸铵、1.2重量％H2SiF6、0.004重量％溴化十四烷基三甲基铵、0.3重量％TEOS和98.486重量％去离子水的基础溶液2。用基础溶液2起始，如下表4中所示制备制剂。将铜、钨、TiN和PETEOS试样在50℃下在每种制剂中浸没所示时间并且测定蚀刻速率。
表4：通过将所示有机溶剂和腐蚀抑制剂mBTA与余量的基础溶液2组合而制备的制剂。
可见仅一种溶剂(THFA)在10重量％下显著改变TiN的蚀刻速率。
实施例3
制备包含四氟硼酸、吡唑、氧化钒(IV,V)和水的组合物并且在50℃下在每种制剂中浸没后测定PETEOS、Cu(Cu)、TiN和W的试样的蚀刻速率。表5中提供了所述组合物和结果。
表5：制剂和蚀刻速率
实施例4
如表6中所示制备包含四氟硼酸、吡唑、氧化钒(IV,V)、水、二乙二醇单丁醚(DEGBE)和其它组分的组合物。在40℃下在每种制剂中浸没后测定PETEOS、Cu(Cu)、TiN和W的试样的蚀刻速率，如表7中所提供。
表6：制剂
表7：制剂AAA-FFF的蚀刻速率
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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 (22)
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、至少一种二氧化硅源、水和至少一种有机溶剂，其中所述组合物基本上不含过氧化氢。
2.根据权利要求1所述的组合物，其中所述蚀刻剂包括选自以下的物质：H2ZrF6、H2TiF6、HPF6、HF、氟化铵、氟化氢铵、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)，其中R1、R2、R3、R4可以彼此相同或不同并选自直链或支链的C1-C6烷基基团、弱碱和其组合。
3.根据权利要求1所述的组合物，其中所述蚀刻剂包括四氟硼酸、六氟硅酸或其组合。
4.根据前述权利要求中的任一项所述的组合物，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(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、N-甲基吗啉N-氧化物、三甲基胺N-氧化物和其组合。
5.根据前述权利要求中的任一项所述的组合物，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-苯醌或其组合。
6.根据前述权利要求中的任一项所述的组合物，其中所述氧化剂包括选自钒酸铵和高碘酸的物质。
7.根据前述权利要求中的任一项所述的组合物，其中所述至少一种腐蚀抑制剂包括选自以下的物质：5-氨基-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、苯并三唑羧酸、3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、羟基苯并三唑、2-(5-氨基-戊基)-苯并三唑、1-氨基-1,2,3-三唑、1-氨基-5-甲基-1,2,3-三唑、3-氨基-1,2,4-三唑、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、卤代-苯并三唑(卤代＝F、Cl、Br或I)、萘并三唑、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、AblumineO、2-苄基吡啶、琥珀酰亚胺、马来酰亚胺、邻苯二甲酰亚胺、戊二酰亚胺、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、吡唑、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-1,2,4-三唑-3-硫醇、苯并噻唑、咪唑、吲唑、腺苷、咔唑、糖精、苯偶姻肟、PolyFoxPF-159、聚(乙二醇)、聚(丙二醇)、PEG-PPG共聚物、十二烷基苯磺酸、十二烷基苯磺酸钠、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Aliquat336、氯化苄基二甲基苯基铵、CrodaquatTES、RewoquatCPEM、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、溴化乙基十六烷基二甲基铵、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、氯化六甲双铵和其组合。
8.根据前述权利要求中的任一项所述的组合物，其中所述至少一种腐蚀抑制剂包括苯并三唑衍生物、阳离子型季铵表面活性剂或其组合。
9.根据前述权利要求中的任一项所述的组合物，其中所述至少一种腐蚀抑制剂包括甲基苯并三唑。
10.根据前述权利要求中的任一项所述的组合物，其中所述二氧化硅源包括选自以下的至少一种物质：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)和其组合，优选为TEOS、TMAS、硅酸钠或其组合。
11.根据前述权利要求中的任一项所述的组合物，其中所述至少一种有机溶剂包括选自以下的物质：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、1,2-丙二醇和1,3-丙二醇、1,2-丁二醇、1,3-丁二醇和1,4-丁二醇、四氢糠醇(THFA)、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、二乙二醇单乙醚、三乙二醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、二乙二醇单丁醚、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、二丙二醇乙醚、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、2,3-二氢十氟戊烷、乙基全氟丁醚、甲基全氟丁醚、碳酸烷基酯、碳酸亚烷基酯、4-甲基-2-戊醇、四亚甲基二醇二甲醚、二甲亚砜和其组合，优选地二乙二醇单乙醚、二乙二醇甲醚、丙二醇、乙二醇、四乙二醇二甲醚、三乙二醇甲醚、三乙二醇乙醚、三丙二醇单甲醚、二丙二醇单甲醚或其组合。
12.根据前述权利要求中的任一项所述的组合物，其中所述组合物还包含选自以下的至少一种其它组分：至少一种低k钝化剂、至少一种表面活性剂、至少一种碘清除剂和其组合。
13.根据前述权利要求中的任一项所述的组合物，其中所述组合物基本上不含胺、化学机械抛光研磨材料、金属卤化物和其组合。
14.根据前述权利要求中的任一项所述的组合物，其中所述组合物在约45℃至约60℃范围内的温度下具有大于40:1的TiN:钨选择性和小于约的钨去除速率。
15.根据前述权利要求中的任一项所述的组合物，其中所述组合物在约45℃至约60℃范围内的温度下具有大于20:1的TiN:铜选择性和小于约的铜去除速率。
16.根据前述权利要求中的任一项所述的组合物，其中所述组合物的pH在约0至约4的范围内。
17.一种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，所述方法包括使所述表面与根据权利要求1至16中的任一项所述的组合物接触，其中所述组合物从所述表面相对于金属和绝缘材料选择性去除所述氮化钛材料。
18.根据权利要求17所述的方法，其中所述接触包括在约20℃至约100℃的范围内的温度下在约0.3分钟至约30分钟范围内的时间。
19.根据权利要求17至18中的任一项所述的方法，其中在所需蚀刻动作后从所述表面冲洗所述组合物。
20.根据权利要求17至19中的任一项所述的方法，其中所述金属包含铜、钨或两者。
21.根据权利要求17至20中的任一项所述的方法，其中所述组合物在约45℃至约60℃范围内的温度下具有大于40:1的TiN:钨选择性和小于约的钨去除速率。
22.根据权利要求17至21中的任一项所述的方法，其中所述组合物在约45℃至约60℃范围内的温度下具有大于20:1的TiN:铜选择性和小于约的铜去除速率。
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| CN106919013B (zh) * | 2015-12-28 | 2021-12-07 | 安集微电子（上海）有限公司 | 一种低蚀刻的去除光阻残留物的清洗液 |
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| CN113423799A (zh) * | 2019-10-03 | 2021-09-21 | 日产化学株式会社 | 用于消除激光标记周边的隆起的包含阳离子的研磨用组合物 |
| CN113122267A (zh) * | 2019-12-31 | 2021-07-16 | 安集微电子科技（上海）股份有限公司 | 一种促进剂组合物在去除铜大马士革工艺中氮化钛的应用 |
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| CN116096837A (zh) * | 2020-08-13 | 2023-05-09 | 恩特格里斯公司 | 氮化物蚀刻剂组合物和方法 |
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Also Published As
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|---|---|
| US20160032186A1 (en) | 2016-02-04 |
| KR102294726B1 (ko) | 2021-08-30 |
| KR20150126637A (ko) | 2015-11-12 |
| EP2964725B1 (en) | 2021-06-23 |
| JP6363116B2 (ja) | 2018-07-25 |
| US10472567B2 (en) | 2019-11-12 |
| EP2964725A1 (en) | 2016-01-13 |
| EP2964725A4 (en) | 2016-11-23 |
| CN105102584B (zh) | 2018-09-21 |
| WO2014138064A1 (en) | 2014-09-12 |
| TW201439280A (zh) | 2014-10-16 |
| TWI655273B (zh) | 2019-04-01 |
| SG10201706443QA (en) | 2017-09-28 |
| SG11201507014RA (en) | 2015-10-29 |
| JP2016510175A (ja) | 2016-04-04 |
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