TW202235584A - 選擇性移除金屬氧化物硬遮罩 - Google Patents
選擇性移除金屬氧化物硬遮罩 Download PDFInfo
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- TW202235584A TW202235584A TW110149283A TW110149283A TW202235584A TW 202235584 A TW202235584 A TW 202235584A TW 110149283 A TW110149283 A TW 110149283A TW 110149283 A TW110149283 A TW 110149283A TW 202235584 A TW202235584 A TW 202235584A
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- ammonium
- water
- acid
- fluoride
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- 229910044991 metal oxide Inorganic materials 0.000 title abstract description 6
- 150000004706 metal oxides Chemical class 0.000 title abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 63
- 238000004377 microelectronic Methods 0.000 claims abstract description 14
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 8
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 hexafluorosilicic acid Chemical compound 0.000 claims description 46
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 26
- 239000003112 inhibitor Substances 0.000 claims description 18
- 238000005260 corrosion Methods 0.000 claims description 16
- 230000007797 corrosion Effects 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 6
- 150000002222 fluorine compounds Chemical class 0.000 claims description 6
- 150000002334 glycols Chemical class 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- JTXUAHIMULPXKY-UHFFFAOYSA-N 3-trihydroxysilylpropan-1-amine Chemical compound NCCC[Si](O)(O)O JTXUAHIMULPXKY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- DAUXGBNWCNJACU-UHFFFAOYSA-N (amino-hydroxy-methylsilyl)methane Chemical compound C[Si](C)(N)O DAUXGBNWCNJACU-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical group CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- ZRBPLFDXISTAAG-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]propan-1-amine Chemical compound NCCC[Si](OC)(CCCN)OC ZRBPLFDXISTAAG-UHFFFAOYSA-N 0.000 claims description 2
- BEMQMQUNCRGREM-UHFFFAOYSA-N 3-di(propan-2-yl)silylpropan-1-amine Chemical compound CC(C)[SiH](C(C)C)CCCN BEMQMQUNCRGREM-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-O dodecylazanium Chemical compound CCCCCCCCCCCC[NH3+] JRBPAEWTRLWTQC-UHFFFAOYSA-O 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 claims description 2
- HLDBBQREZCVBMA-UHFFFAOYSA-N hydroxy-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](O)(OC(C)(C)C)OC(C)(C)C HLDBBQREZCVBMA-UHFFFAOYSA-N 0.000 claims description 2
- QNHNSPNFZFBEQR-UHFFFAOYSA-N n'-(3-trihydroxysilylpropyl)ethane-1,2-diamine Chemical compound NCCNCCC[Si](O)(O)O QNHNSPNFZFBEQR-UHFFFAOYSA-N 0.000 claims description 2
- AMVXVPUHCLLJRE-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)hexane-1,6-diamine Chemical compound CO[Si](OC)(OC)CCCNCCCCCCN AMVXVPUHCLLJRE-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000036961 partial effect Effects 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 claims description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 27
- 238000005530 etching Methods 0.000 abstract description 23
- 239000000377 silicon dioxide Substances 0.000 abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 13
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 11
- 229920005591 polysilicon Polymers 0.000 abstract description 11
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010937 tungsten Substances 0.000 abstract description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- HHDRWGJJZGJSGZ-UHFFFAOYSA-N 5-benzyl-2h-tetrazole Chemical compound C=1C=CC=CC=1CC=1N=NNN=1 HHDRWGJJZGJSGZ-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-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
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RNDVWASRPMZYLW-UHFFFAOYSA-N [Cl-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[NH4+].[NH4+].[NH4+] Chemical compound [Cl-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[NH4+].[NH4+].[NH4+] RNDVWASRPMZYLW-UHFFFAOYSA-N 0.000 description 2
- 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 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
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 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
- 230000000295 complement effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- MZMRZONIDDFOGF-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CCCCCCCCCCCCCCCC[N+](C)(C)C MZMRZONIDDFOGF-UHFFFAOYSA-M 0.000 description 2
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 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
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- WEGOLYBUWCMMMY-UHFFFAOYSA-N 1-bromo-2-propanol Chemical compound CC(O)CBr WEGOLYBUWCMMMY-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- YYTSGNJTASLUOY-UHFFFAOYSA-N 1-chloropropan-2-ol Chemical compound CC(O)CCl YYTSGNJTASLUOY-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
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-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
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-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
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- BJFOBOGTLULXEZ-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol 2-(2-propoxypropoxy)propan-1-ol Chemical compound C(CC)OC(C)COC(C)CO.C(C)OC(C)COC(C)CO BJFOBOGTLULXEZ-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical group COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- FYYLCPPEQLPTIQ-UHFFFAOYSA-N 2-[2-(2-propoxypropoxy)propoxy]propan-1-ol Chemical compound CCCOC(C)COC(C)COC(C)CO FYYLCPPEQLPTIQ-UHFFFAOYSA-N 0.000 description 1
- LSRXVFLSSBNNJC-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-phenoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound OCCOCCOCCOCCOCCOCCOC1=CC=CC=C1 LSRXVFLSSBNNJC-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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 238000012369 In process control Methods 0.000 description 1
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- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 1
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- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- VZXFEELLBDNLAL-UHFFFAOYSA-N dodecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCC[NH3+] VZXFEELLBDNLAL-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- FFGSPQDSOUPWGY-UHFFFAOYSA-M dodecyl-ethyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC FFGSPQDSOUPWGY-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 description 1
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- 230000005669 field effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
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- 239000004700 high-density polyethylene Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 238000007654 immersion Methods 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
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- 229960005152 pentetrazol Drugs 0.000 description 1
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- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical compound O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 1
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- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- AHNISXOXSNAHBZ-UHFFFAOYSA-M tetrakis-decylazanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC AHNISXOXSNAHBZ-UHFFFAOYSA-M 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 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 description 1
- 229940051002 thonzonium bromide Drugs 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- LDGFRUUNCRYSQK-UHFFFAOYSA-N triazin-4-ylmethanediamine Chemical compound NC(N)C1=CC=NN=N1 LDGFRUUNCRYSQK-UHFFFAOYSA-N 0.000 description 1
- MPSUGQWRVNRJEE-UHFFFAOYSA-N triazol-1-amine Chemical compound NN1C=CN=N1 MPSUGQWRVNRJEE-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910052905 tridymite Inorganic materials 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- OJYBUGUSFDKJEX-UHFFFAOYSA-N tungsten zirconium Chemical compound [Zr].[W].[W] OJYBUGUSFDKJEX-UHFFFAOYSA-N 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
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Abstract
本發明提供在其他材料(諸如多晶矽、二氧化矽、氮化矽及鎢)存在下可用於選擇性蝕刻(即移除)金屬氧化物硬遮罩(諸如氧化鋯及氧化鉿)之組合物,該硬遮罩通常用作微電子裝置中之硬遮罩。
Description
本發明大體上係關於移除或蝕刻某些高k介電材料,包括金屬氧化物硬遮罩諸如氧化鋯及氧化鉿。
習知半導體裝置可包括大量之金屬氧化物半導體場效電晶體(「MOSFET」),各包含至少一個源極區、汲極區及閘極區。互補金屬氧化物半導體(「CMOS」)使用互補且對稱之p型及n型MOSFETs對,允許邏輯功能於晶片上之較高密度。
MOS或CMOS電晶體之閘極區一般由放置於氧化物絕緣子/介電(例如SiO
2)之頂部之上或上之閘極材料(例如多晶矽)製成,氧化物絕緣子/介電繼而覆蓋半導體材料或於半導體材料上,此組合通常稱為「閘極堆疊」。儘管在金屬閘極及金屬氧化物半導體中提及「金屬」,但多晶矽係習知閘極製造中之最常見的閘極材料。多晶矽因其容易沉積、在後續製造步驟(例如退火)中其對極高溫度(超過900℃至1000℃)之耐受性、及其形成自配向閘極之能力而成為製造閘極電極中之較佳材料。用金屬製造閘極受到多晶矽避免的許多問題的困擾。
在先前技術中選擇的閘極介電一直是二氧化矽。隨著電晶體尺寸減小,二氧化矽介電之厚度亦已經縮小以改良閘極電容,由此提高電流及裝置性能。二氧化矽閘極厚度減小小於約2 nm已導致由於隧道化而顯著增加之漏電流,此導致不堪重負之功率消耗及降低之裝置可靠性。解決辦法是用高-k介電材料(諸如氧化鋯)替換二氧化矽閘極閘極介電,此將使閘電容增加而沒有伴隨洩漏效應。
另外,利用高縱橫比矽溝渠產生在存在二氧化矽及其他材料下選擇性蝕刻氧化鋯層或「硬遮罩」的挑戰。
已知,可使用包含酸、氧化劑及氟化合物(諸如氫氟酸、氟硫酸、氟化銨或二氟化銨)之水性溶液移除高k介電質諸如氧化鋯。(參見例如美國專利第6,656,852號)。然而,此類組合物不僅傾向於蝕刻高k介電質諸如氧化鋯,而且蝕刻或降解可存在的其他材料,諸如多晶矽、二氧化矽、氮化矽及鎢。
因此,仍需要用於在存在其他材料(諸如多晶矽、二氧化矽、氮化矽及鎢)下蝕刻高k介電材料(諸如氧化鋯)之經改良方法。
總而言之,本揭示提供一種預期在存在其他材料(諸如多晶矽、二氧化矽、氮化矽及鎢)下可用於選擇性蝕刻
(亦即移除)金屬氧化物硬遮罩(諸如氧化鋯及氧化鉿)之組合物,該硬遮罩通常用作微電子裝置中之硬遮罩。就此而言,某些氟化物化合物經描述為在規定pH範圍內之組合物中之用於促進在存在其他材料下選擇性移除氧化鋯之蝕刻劑。該組合物包含:
a. 水;
b. 選自氟化銨、二氟化銨及六氟矽酸之氟化物化合物;
c. 一或多種酸;
d. 一或多種腐蝕抑制劑;
e. 選自醇、二醇、二醇醚、鹵化銨及胺之水可混溶組分;
其中該組合物具有約-2至6之pH。
如本說明書及隨附申請專利範圍中所用,除非本文清楚地另作指明,否則單數形式「一」、「一個」及「該」包括複數個指示物。如本說明書及隨附申請專利範圍中所用,除非本文清楚地另作指明,否則術語「或」一般在其包括「及/或」的意義上使用。
術語「約」一般係指被認為等同於所列舉值(例如,具有相同功能或結果)之一系列數值。在許多情況下,術語「約」可包括四捨五入至最接近有效數字之數值。
使用端點表示的數值範圍包括包含在該範圍內的所有數值(例如,1至5包括1、1.5、2、2.75、3、3.80、4及5)。
在第一態樣中,本發明提供一種組合物,其包含:
a. 水;
b. 選自氟化銨、二氟化銨及六氟矽酸之氟化物化合物;
c. 一或多種酸;
d. 一或多種腐蝕抑制劑;及
e. 選自醇、二醇、二醇醚、鹵化銨及胺之水可混溶組分;
其中該組合物具有約-2至6之pH。在某些實施例中,該組合物之pH將為約0至約4,且在其他實施例中,為約1至約2。
在一個實施例中,該氟化物化合物為六氟矽酸。
在一個實施例中,組分(c)之該等酸可選自鹽酸、硝酸、丙酸、檸檬酸、酒石酸及硫酸,且以使得連同組合物之其他組分一起提供所需pH的量使用。
在一個實施例中,該醇係選自甲醇、乙醇、異丙醇、丁醇、四氫呋喃醇(THFA)、鹵化醇(諸如3-氯-1,2-丙二醇、3-氯-1-丙二醇、1-氯-2-丙醇、2-氯-1-丙醇、3-氯-1-丙醇、3-溴-1,2-丙二醇、1-溴-2-丙醇、3-溴-1-丙醇、3-碘-1-丙醇、4-氯-1-丁醇及2-氯乙醇)。
在一個實施例中,該醇為C
1-C
4烷醇且係選自甲醇、乙醇、丙醇、正丁醇、異丙醇、第二丁醇及第三丁基醇乙醇。在一個實施例中,該醇為乙醇。
在一個實施例中,該二醇係選自C
2-C
4二醇及C
2-C
4三醇,諸如乙二醇、丙二醇(PG)、1,3-丙二醇及三甲基丙烷。
在一個實施例中,該二醇醚係選自二乙二醇單甲基醚、三乙二醇單甲基醚、二乙二醇單乙基醚、三乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、二乙二醇單丁基醚(亦即丁基卡必醇(carbitol))、三乙二醇單丁基醚、乙二醇單己基醚、二乙二醇單己基醚、乙二醇苯基醚、丙二醇甲基醚、二丙二醇甲基醚(DPGME)、三丙二醇甲基醚(TPGME)、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、乙二醇單苯基醚、二乙二醇單苯基醚、六乙二醇單苯基醚、二丙二醇甲基醚乙酸酯及四乙二醇二甲基醚(TEGDE)。
在一個實施例中,鹵化銨為氯化銨或溴化銨。
在一個實施例中,胺為三乙胺。在另一個實施例中,胺為二級胺。在另一個實施例中,胺係選自二乙胺、二異丙胺、乙基甲胺、二乙醇胺、
N,
N-二甲胺及
N-甲基二乙醇胺。
在一個實施例中,該等腐蝕抑制劑係選自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、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-胺基苯基)-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-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯基硫醇基-苯并三唑、鹵基-苯并三唑(鹵基=F、Cl、Br或I)、萘并三唑、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-胺基四唑、戊烯四唑、5-苯基-1
H-四唑、5-苄基-1
H-四唑、2-苄基吡啶、琥珀醯亞胺、馬來醯亞胺、鄰苯二甲醯亞胺、戊二醯亞胺、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-4
H-1,2,4-三唑-3-硫醇、苯并噻唑、咪唑、吡唑、吲唑、腺苷、咔唑、醣精及安息香肟。另外腐蝕抑制劑包括陽離子性四級表面活性劑鹽,諸如氯化苯二甲烴銨、氯化苄基二甲基十二基銨、溴化肉豆蔻基三甲基銨、溴化十二基三甲基銨、氯化十六基吡啶鎓、Aliquat 336 (Cognis)、氯化苄基二甲基苯基銨、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'-二吡啶鎓、溴化烷基三甲基銨、胺丙啉(amprolium)鹽酸鹽、氫氧化苯索寧(benzethonium)、氯化苯索寧、氯化苄基二甲基十六基銨、氯化苄基二甲基十四基銨、溴化苄基十二基二甲基銨、氯化苄基十二基二甲基銨、氯化鯨蠟基吡啶鎓、膽鹼對甲苯磺酸鹽、溴化二甲基二(十八基)銨、溴化十二基乙基二甲基銨、氯化十二基三甲基銨、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-羥基乙基)二甲基銨、溴化十六基吡啶鎓、溴化十六基三甲基銨、氯化十六基三甲基銨、氯化甲基苯索寧、Hyamine® 1622、Luviquat™、
N,
N',
N'-聚氧伸乙基(10)-
N-牛脂-1,3-二胺基丙烷液體、溴化氧基苯鎓、溴化四庚基銨、溴化肆(癸基)銨、通佐溴銨(thonzonium bromide)、氯化三(十二基)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(十二基)甲基銨、氯化二甲基二硬脂基銨及氯化六羥季銨。其他腐蝕抑制劑包括非離子性表面活性劑,諸如PolyFox PF-159 (OMNOVA Solutions)、聚(乙二醇) (「PEG」)、聚(丙二醇) (「PPG」)、PEG-PPG共聚物(諸如Pluronic F-127 (BASF))、陰離子性表面活性劑(諸如十二基苯磺酸、十二基苯磺酸鈉及其組合。四級鹽可作用為腐蝕抑制劑及潤濕劑。應瞭解,雖然四級鹽最常以氯化物或溴化物的形式購買獲得,但其易於用非鹵化物陰離子(諸如硫酸鹽、甲磺酸鹽、硝酸鹽、氫氧化物及類似鹽)離子交換鹵化物陰離子。本文亦涵蓋此類轉化之四級鹽。在一個特佳實施例中,已知5-甲基-1H-苯并三唑阻斷氧化劑針對銅之氧化活性。或者或除了5-甲基-1
H-苯并三唑(mBTA)之外,腐蝕抑制劑包括吡唑、苯并三唑、陽離子性四級表面活性劑鹽,更佳為溴化肉豆蔻基三甲基銨、氯化苯二甲烴銨、對甲苯磺酸十六基三甲基銨及氫氧化十六基三甲基銨、四唑(諸如5-苄基-1
H-四唑)及其組合。
在另一個實施例中,腐蝕抑制劑係選自溴化肉豆蔻基三甲基銨、氯化苯二甲烴銨、對甲苯磺酸十六基三甲基銨、氫氧化十六基三甲基銨、5-苄基-1
H-四唑及其組合。
在一個實施例中,腐蝕抑制劑係選自氯化苯二甲烴銨;氯化十二基苯二甲烴銨;烷基苯磺酸酯;及選自二苯基矽醇;三乙基矽醇;三-第三丁氧基矽醇;胺基(二甲基)矽醇;胺基丙基二異丙基矽烷;胺基丙基矽烷三醇;(3-胺基丙基)三乙氧基矽烷;
N-(2-胺基乙基)-3-胺基丙基矽烷三醇;
N 1-(3-三甲氧基矽基丙基)二伸乙三胺);
3,3'-(二甲氧基亞矽基)雙-(1-丙胺);1,3-雙(3-胺基丙基)-1,1,3,3-四乙氧基二矽氧烷;及
N-(6-胺基己基)胺基丙基三甲氧基矽烷及其組合之化合物。
在另一個實施例中,腐蝕抑制劑係以約0.001重量%至約2重量%之量存在。
在一個實施例中,腐蝕抑制劑為胺基丙基矽烷三醇及至少一種烷基苯磺酸酯之混合物。
在上述組合物中,組分之相對比例如下:
a. 約65至約80重量%之水;
b. 約4至約10重量%之選自氟化銨、二氟化銨及六氟矽酸之氟化物化合物;
c. 酸,其量足以達成約-2至約6之規定pH;
d. 約1至約5重量%之腐蝕抑制劑;及
e. 選自醇、二醇、二醇醚、鹵化銨及胺之水可混溶組分。
在一個實施例中,氟化物化合物為六氟矽酸。
雖然已觀測到六氟矽酸經水解成氫氟酸及各種形式之非晶型且水合化之矽石(亦即SiO
2),但本發明提供在某些水可混溶組分存在下在約1至約2之pH下利用含在水性組合物中之六氟矽酸以在其他材料(諸如多晶矽、二氧化矽、氮化矽及鎢)存在下選擇性蝕刻(亦即移除)氧化鋯。因此,該等組合物特別可用於製造包含此等材料之高縱橫比結構。
如本文所用,「微電子裝置」為包括形成於其上的極小(例如微米規模或更小)尺寸之電路及相關結構之裝置。示例性微電子裝置包括平板顯示器、積體電路、記憶裝置、太陽能面板、光伏打及微機電系統(MEMS)。微電子裝置基板為處於準備好以形成最終微電子裝置之狀態中的包括一或多個微電子裝置或其前驅物之結構諸如晶圓(例如半導體晶圓)。
在第二態樣中,本發明提供一種自微電子裝置移除氧化鋯或氧化鉿硬遮罩之方法,該方法包括使該微電子裝置與包含以下之組合物在實施該硬遮罩之至少部分移除所必需的時間及溫度下接觸:
a. 水;
b. 選自氟化銨、二氟化銨及六氟矽酸之氟化物化合物;
c. 一或多種酸;
d. 一或多種腐蝕抑制劑;及
e. 選自醇、二醇、二醇醚、鹵化銨及胺之水溶性組分;
其中該組合物具有約-2至6之pH。
在其他實施例中,該等組合物如上文在各種實施例中所述。
應瞭解,常見的實務是在使用之前製備待稀釋的組合物之濃縮形式。例如,該組合物可以更濃縮形式製造且此後在製造商處、在使用之前及/或在製造廠(fab)處使用期間用至少一種溶劑稀釋。稀釋比可在約0.1份稀釋劑:1份組合物濃縮物至約100份稀釋劑:1份組合物濃縮物之範圍內。本文所述的組合物可容易地藉由簡單添加各別組分且混合至均勻條件來調配。此外,該等組合物可容易地調配為單包裝調配物或在應需使用時或之前混合的多部分調配物,較佳為多部分調配物。多部分調配物之個別部分可在工具處或在混合區域(region/area) (諸如線內混合器)中或在工具上游的儲存槽中進行混合。經考慮,多部分調配物之各個部分可含有當混合在一起時形成所需組合物之組分/成分之任何組合。各別組分之濃度可以半水性組合物之特定倍數(亦即更稀或更濃)而廣泛地變化,且應瞭解,半水性組合物可不同地且替代地包含與本文揭示內容一致之組分之任何組合,由其組成或基本上由其組成。
因此,在第三態樣中,本發明提供一種套組,該套組包含適合於形成本文所述的組合物之兩種或更多種組分於一或多個容器中。套組之容器必須適合於儲存及運輸該等組合物組分,例如NOWPak®容器(Advanced Technology Materials, Inc., Danbury, Conn., USA)。兩個或更多個含有該組合物之組分之容器較佳包括用於使該一或多個容器中之組分成流體連通以供摻合及分配之構件。例如,參考NOWPak®容器,可將氣體壓力施加至該一或多個容器中之內襯的外部以引起該內襯之內含物之至少一部分被排出且因此啟動流體連通以供摻合及分配。或者,可將氣體壓力施加至習知可加壓之容器之頭部空間或可使用泵以啟動流體連通。此外,該系統較佳包括用於將經摻合組合物分配至加工工具之分配埠。
可使用實質上化學惰性、無雜質、撓性且彈性聚合物膜材料(諸如高密度聚乙烯)製造該一或多個容器的內襯。期望內襯材料一般在不需要共擠出或障壁層下,且在沒有可不利影響待配置於內襯中的組分之純度要求之任何顏料、UV抑制劑或加工劑下進行加工。期望內襯材料之清單包括包含純(無添加劑)聚乙烯、純聚四氟乙烯(PTFE)、聚丙烯、聚胺甲酸酯、聚偏二氯乙烯、聚氯乙烯、聚縮醛、聚苯乙烯、聚丙烯腈、聚丁烯及類似內襯材料之膜。此類內襯材料之示例性厚度在約5密耳(0.005英寸)至約30密耳(0.030英寸)之範圍內,如例如20密耳(0.020英寸)之厚度。
關於套組之容器,以下專利及專利申請案之揭示內容係以其各別全文引用方式併入本文中:美國專利第7,188,644號,題為「APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS」;及美國專利第6,698,619號,題為「RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM」。
如所述的組合物可用於在材料(諸如多晶矽、二氧化矽、氮化矽及鎢)存在下移除高k硬遮罩材料(諸如氧化鋯及氧化鉿)之方法。
在使用中,本發明之組合物可提供基於商業性能需要及期望有用的蝕刻(亦即移除)性能,且與比較蝕刻組合物相比,可提供關於高k材料(諸如氧化鋯及氧化鉿)相對材料(諸如多晶矽、二氧化矽、氮化矽及鎢)之蝕刻速率及選擇性改良之性能。
蝕刻微電子裝置基板之方法係半導體製造技術中已知的且可在已知及市售設備上進行。一般而言,為了蝕刻基板以選擇性移除基板之表面處的材料,可將蝕刻組合物施覆至表面且允許接觸表面結構以化學地選擇性移除某些結構。
在一個蝕刻步驟中,組合物可以任何適宜方式施覆至表面,諸如藉由將蝕刻組合物噴灑至表面上;藉由將基板浸漬(在靜態或動態體積之組合物中)至蝕刻組合物中;藉由使表面與具有吸收於其上之蝕刻組合物之另一材料(例如墊或纖維吸附劑施覆器元件)接觸;藉由使基板與一定量之蝕刻組合物在循環池中接觸;或藉由使蝕刻組合物與含有高k硬遮罩材料(諸如氧化鋯或氧化鉿)之微電子基板之表面進行移除接觸之任何其他適宜手段、方式或技術。該施覆可為在分批或單晶圓設備中,以用於動態或靜態清潔。
有用之蝕刻製程之條件(例如時間及溫度)可為經發現是有效或有利之任何條件。一般而言,使蝕刻組合物與表面接觸,諸如藉由浸沒於蝕刻組合物浴中一段足以選擇性移除所需硬遮罩材料之時間。暴露於蝕刻組合物之時間及蝕刻組合物之溫度可有效地自基板之表面移除所需量之硬遮罩。蝕刻步驟之時間應不過於短,因為此意指硬遮罩之蝕刻速率可過於高,此可導致製程控制困難且在蝕刻步驟結束時微電子裝置之品質降低。當然,蝕刻步驟所需的時間有利地不是過度長的,以允許蝕刻製程及半導體製造線之良好效率及生產量。在於約30℃至約60℃之範圍內之溫度下,蝕刻步驟之有用時間之實例可在約0.5分鐘至約3分鐘、或約1分鐘至約2分鐘之範圍內。此種接觸時間及溫度係例示性的,且可利用可有效達成所需要移除選擇性之任何其他適宜時間及溫度條件。
已因此描述本揭示之幾個例示性實施例,熟習此項技術者將輕易瞭解,可在本揭示隨附申請專利範圍之範疇內製作及使用又其他實施例。本文件涵蓋的揭示之許多優勢已在前述描述中進行闡述。然而,應理解,在很多方面,本揭示僅係例示性的。當然,本揭示的範疇以表現隨附申請專利範圍的語言限定。
Claims (10)
- 一種組合物,其包含: a. 水; b. 選自氟化銨、二氟化銨及六氟矽酸之氟化物化合物; c. 一或多種酸; d. 一或多種腐蝕抑制劑;及 e. 選自醇、二醇、二醇醚、鹵化銨及胺之水溶性組分; 其中該組合物具有約-2至6之pH。
- 如請求項1之組合物,其中該pH為約0至約4。
- 如請求項1之組合物,其中該醇為C 1-C 4烷醇。
- 如請求項1之組合物,其中該一或多種酸係選自鹽酸、硫酸及硝酸。
- 如請求項1之組合物,其中該氟化物化合物為六氟矽酸。
- 如請求項1之組合物,其中該一或多種抑制劑係選自氯化苯二甲烴銨;氯化十二基苯二甲烴銨;烷基苯磺酸酯;及選自二苯基矽醇;三乙基矽醇;三-第三丁氧基矽醇;胺基(二甲基)矽醇;胺基丙基二異丙基矽烷;胺基丙基矽烷三醇;(3-胺基丙基)三乙氧基矽烷; N-(2-胺基乙基)-3-胺基丙基矽烷三醇; N 1-(3-三甲氧基矽基丙基)二伸乙三胺);3,3'-(二甲氧基亞矽基)雙-(1-丙胺);1,3-雙(3-胺基丙基)-1,1,3,3-四乙氧基二矽氧烷;及 N-(6-胺基己基)胺基丙基三甲氧基矽烷或其混合物之化合物。
- 如請求項1之組合物,其中該水溶性組分係選自C 1-C 4烷醇。
- 如請求項1之組合物,其中該水溶性組分係選自乙二醇、丙二醇、1,3-丙二醇及三羥甲基丙烷。
- 如請求項1之組成物,其中該腐蝕抑制劑係選自十二基苯磺酸及胺基丙基矽烷三醇或其混合物。
- 一種自微電子裝置移除氧化鋯或氧化鉿硬遮罩之方法,該方法包括使該微電子裝置與包含以下組分之組合物在實現該硬遮罩之至少部分移除所必需的時間及溫度下接觸: a. 水; b. 選自氟化銨、二氟化銨及六氟矽酸之氟化物化合物; c. 一或多種酸; d. 一或多種腐蝕抑制劑;及 e. 選自醇、二醇、二醇醚、鹵化銨及胺之水溶性組分; 其中該組合物具有約-2至6之pH。
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