CN116096837A - 氮化物蚀刻剂组合物和方法 - Google Patents
氮化物蚀刻剂组合物和方法 Download PDFInfo
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- CN116096837A CN116096837A CN202180050131.9A CN202180050131A CN116096837A CN 116096837 A CN116096837 A CN 116096837A CN 202180050131 A CN202180050131 A CN 202180050131A CN 116096837 A CN116096837 A CN 116096837A
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- Prior art keywords
- composition
- microelectronic device
- ammonium
- acid
- titanium nitride
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- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 43
- 150000004767 nitrides Chemical class 0.000 title description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical group [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 42
- -1 Titanium nitride Chemical class 0.000 claims abstract description 39
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 23
- 239000011733 molybdenum Substances 0.000 claims abstract description 23
- 238000005530 etching Methods 0.000 claims abstract description 17
- 238000004377 microelectronic Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003112 inhibitor Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 21
- 238000005260 corrosion Methods 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 11
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical group OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001039 wet etching Methods 0.000 claims description 8
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 7
- 238000001312 dry etching Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- AQIIVEISJBBUCR-UHFFFAOYSA-N 4-(3-phenylpropyl)pyridine Chemical compound C=1C=NC=CC=1CCCC1=CC=CC=C1 AQIIVEISJBBUCR-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 238000005406 washing Methods 0.000 claims description 5
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 2
- 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 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 5
- 229920005591 polysilicon Polymers 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 28
- 238000009472 formulation Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 13
- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000008139 complexing agent Substances 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- 239000004020 conductor Substances 0.000 description 7
- 239000003989 dielectric material Substances 0.000 description 7
- 150000003839 salts Chemical group 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 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
- 239000012141 concentrate Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
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- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 2
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- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
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- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
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- 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 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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AENSXLNDMRQIEX-UHFFFAOYSA-L oxido sulfate;tetrabutylazanium Chemical compound [O-]OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC AENSXLNDMRQIEX-UHFFFAOYSA-L 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
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- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 description 1
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical class [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
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- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 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
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 description 1
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 description 1
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 description 1
- APSPVJKFJYTCTN-UHFFFAOYSA-N tetramethylazanium;silicate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-][Si]([O-])([O-])[O-] APSPVJKFJYTCTN-UHFFFAOYSA-N 0.000 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
- 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
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 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
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 235000014393 valine Nutrition 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- 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
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- C23F1/00—Etching metallic material by chemical means
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- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
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- 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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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- C23F4/00—Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00
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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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- 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
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- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
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- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Weting (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
技术领域
本发明大体上涉及半导体制造的领域。确切地说,其涉及一种用于蚀刻微电子装置上的氮化钛膜的方法。
背景技术
光阻掩模常用于半导体行业中以图案化如半导体或介电质的材料。在一种应用中,在双金属镶嵌工艺中使用光阻掩模以在微电子装置的后段金属工艺中形成互连件。双金属镶嵌工艺涉及在上覆金属导体层(如铜层)的低k介电层上形成光阻掩模。随后根据光阻掩模蚀刻低k介电层以形成暴露金属导体层的通孔和/或沟槽。通常称为双金属镶嵌结构的通孔和沟槽通常使用两个光刻步骤来界定。随后从低k介电层去除光阻掩模,之后将导电材料沉积到通孔和/或沟槽中以形成互连件。
随着微电子装置的尺寸减小,实现通孔和沟槽的临界尺寸变得愈加困难。因此,使用金属硬式掩模来提供对通孔和沟槽的优选轮廓控制。金属硬式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/或沟槽之后通过湿式蚀刻工艺去除。湿式蚀刻工艺必需使用有效地去除金属硬式掩模和/或光阻蚀刻残留物,而不影响底层的金属导体层和低k介电材料或微电子装置上的其它材料的去除化学物质。确切地说,需要可用于湿式蚀刻工艺的组合物,所述组合物选择性地去除如氮化钛的物质,同时与亦可存在于微电子装置上的如钼、AlOx、SiOx和多晶硅的金属导电层相容。
发明内容
本发明大体上提供用于在例如3D与非(NAND)闪存器装置的微电子装置结构中产生钼凹部的组合物的方法。在此方法中,第一步骤涉及使用高选择率钼蚀刻剂去除钼层,所述高选择率钼蚀刻剂展现出的对钼的选择率高于亦存在于微电子装置上的氮化钛。此第一步骤为已知的并且可表征为干式或湿式蚀刻工艺(参见例如IEEE电子装置的交易(Transactions on Electronic Devices),第51卷,第12期,2004年12月)。在第二步骤中,在本发明的一个实施例中,选择性地蚀刻氮化钛层,通常使存在的钼以及可能存在于装置上的任何氧化铝、二氧化硅和多晶硅不受所述工艺影响。本发明组合物通常能够实现超过的氮化钛蚀刻速率,由此在图案中提供均匀的凹部顶层和底层。另外,组合物非常稳定,例如浴寿命超过24小时并且存放期超过6个月。
因此,在第一方面,本发明提供一种组合物,其包含:
a.水;
b.至少一种氧化剂;
c.至少一种含氟化物的蚀刻剂;
d.至少一种金属腐蚀抑制剂;
e.至少一种pH调节剂;和任选的
f.至少一种可与水混溶的溶剂。
所述组合物适用于选择性地蚀刻氮化钛。组合物的选择率视工艺温度和时间(即暴露)而定。在一个实施例中,当在约50℃下测量5分钟时,氮化钛蚀刻相对于钼的选择率为约5至25。
附图说明
图1为本发明方法的流程图。以具有包含钨和钼的栅极材料的装置结构开始,使所述装置结构经历例如干式蚀刻(或湿式蚀刻)技术以提供栅极金属凹部。随后,蚀刻例如氮化钛和/或氮化钽的障壁金属。用于去除氮化钛和氮化钽的此选择率与现存栅极材料(如钨或钼)和高k材料(如AlOx或ZrOx)相容。
具体实施方式
在第一方面,本发明提供一种组合物,其包含:
a.水;
b.至少一种氧化剂;
c.至少一种含氟化物的蚀刻剂;
d.至少一种金属腐蚀抑制剂;
e.至少一种pH调节剂;和任选的
f.至少一种可与水混溶的溶剂。
如本文所用,术语“微电子装置”对应于制造用于微电子、集成电路、能量收集或计算机芯片应用中的半导体衬底、平板显示器、相变存储器装置、太阳能电池板和其它产品(包括太阳能电池装置、光伏装置和微机电系统(MEMS))。应了解,术语“微电子装置”、“微电子衬底”和“微电子装置结构”并不意谓以任何方式为限制性的并且包括最终将变成微电子装置或微电子组合件的任何衬底或结构。微电子装置可经图案化、经覆盖、为控制件和/或为测试装置。
如本文所用,术语“氮化钛”和“TiNx”对应于纯氮化钛以及包括不同化学计量和氧含量的非纯氮化钛(即TiOxNy)。
如本文所用,“约”意谓对应于陈述值的+或-0.5%。
如本文所用,术语“低k介电材料”对应于用作分层微电子装置中的介电材料的任何材料,其中所述材料具有小于约3.5的介电常数。在某些实施例中,所述低k介电材料包括低极性材料,如含硅有机聚合物、含硅有机/无机混合材料、有机硅酸盐玻璃(OSG)、TEOS、氟化硅酸盐玻璃(FSG)、二氧化硅、氧化铝(AlOx)、氧化锆(ZrOx)和掺碳氧化物(CDO)玻璃。亦应了解,低k介电材料可能具有不同密度和不同孔隙率。
如本文所用,术语“金属导体层”包含铜、钨、钴、钼、铝、钌、包含其的合金和其组合。
如本文所用,“氟化物”物种对应于包括氟离子(F-)或共价键合的氟的物种。应了解氟化物物种可以氟化物物种包括在内或原位产生。
如下文更充分地描述,本发明组合物可体现于广泛多种特定调配物中。
在所有此类组合物中,其中参考重量百分比范围(包括零下限)论述组合物的特定组分,应了解此类组分可存在或不存在于组合物的各种特定实施例中,并且在存在此类组分的情况下,按采用此类组分的组合物的总重量计,所述组分可以低至0.0001重量%的浓度存在。
添加蚀刻剂以增加氮化钛的蚀刻速率。所考虑的蚀刻剂包括(但不限于)氟化物源,如HF、氟化铵、四氟硼酸、六氟硅酸、其它含有B--F或Si--F键的化合物、四丁基四氟硼酸铵(TBA-BF4)、四烷基氟化铵(NR1R2R3R4F);强碱,如四烷基氢氧化铵(NR1R2R3R4OH),其中R1、R2、R3、R4可彼此相同或不同并且选自氢、直链或分支链C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)、C1-C6烷氧基(例如羟乙基、羟丙基)、经取代或未经取代的芳基(例如,苯甲基);弱碱;和其组合。在一个实施例中,氟化物源包含HF、四氟硼酸、六氟硅酸、H2ZrF6、H2TiF6、HPF6、氟化铵、四甲基氟化铵、四甲基氢氧化铵、六氟硅酸铵、六氟钛酸铵,或氟化铵与四甲基氟化铵的组合。在另一实施例中,蚀刻剂包含HF、六氟硅酸或四氟硼酸。在又一实施例中,蚀刻剂为HF。
氧化剂包括在其中以蚀刻或氧化TiNx膜中的Ti3+。本文中所考虑的氧化剂包括(但不限于)过氧化氢(H2O2)、FeCl3、FeF3、Fe(NO3)3、Sr(NO3)2、CoF3、MnF3、(2KHSO5·KHSO4·K2SO4-CAS编号70693-62-8)、过碘酸、碘酸、氢过氧化叔丁基、氧化钒(V)、氧化钒(IV,V)、钒酸铵、多原子铵盐(例如,过氧单硫酸铵、亚氯酸铵(NH4ClO2)、氯酸铵(NH4ClO3)、碘酸铵(NH4IO3)、硝酸铵(NH4NO3)、过硼酸铵(NH4BO3)、过氯酸铵(NH4ClO4)、过碘酸铵(NH4IO4)、过硫酸铵((NH4)2S2O8)、次氯酸铵(NH4ClO))、钨酸铵((NH4)10H2(W2O7))、多原子钠盐(例如,过硫酸钠(Na2S2O8)、次氯酸钠(NaClO)、过硼酸钠)、多原子钾盐(例如,碘酸钾(KIO3)、过锰酸钾(KMnO4)、过硫酸钾、硝酸(HNO3)、过硫酸钾(K2S2O8)、次氯酸钾(KClO))、多原子四甲基铵盐(例如,四甲基亚氯酸铵((N(CH3)4)ClO2)、四甲基氯酸铵((N(CH3)4)ClO3)、四甲基碘酸铵((N(CH3)4)IO3)、四甲基过硼酸铵((N(CH3)4)BO3)、四甲基过氯酸铵((N(CH3)4)ClO4)、四甲基过碘酸铵((N(CH3)4)IO4)、四甲基过硫酸铵((N(CH3)4)S2O8))、多原子四丁基铵盐(例如,四丁基过氧单硫酸铵)、过氧单硫酸、硝酸铁(Fe(NO3)3)、过氧化脲((CO(NH2)2)H2O2)、过氧乙酸(CH3(CO)OOH)、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯醌(chloranil)、四氧嘧啶(alloxan)和其组合。当氧化剂为盐时,其可为水合的或无水的。氧化剂可在制造商处,在将组合物引入装置晶片之前,或替代地在装置晶片(即原位)处引入到组合物中。在一个实施例中,氧化剂包含过碘酸。
添加金属腐蚀抑制剂以阻断氧化剂的氧化活性。本文中所考虑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(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-苯硫醇-苯并三唑、卤代-苯并三唑(卤素=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、戊烯四唑、5-苯基-1H-四唑、5-苯甲基-1H-四唑、丁二酰亚胺、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、吲二唑(indiazole)、腺苷、咔唑、邻磺酰苯甲酰亚胺、安息香肟和其组合。另外腐蚀抑制剂包括阳离子季盐,如苯扎氯铵、苯甲基二甲基十二烷基氯化铵、肉豆蔻基三甲基溴化铵、十二烷基三甲基溴化铵、十六烷基氯化吡锭、Aliquat 336(科宁(Cognis))、苯甲基二甲基苯基氯化铵、克罗拉夸(Crodaquat)TES(禾大公司(Croda Inc.))、Rewoquat CPEM(威科(Witco))、十六烷基三甲基对甲苯磺酸铵、十六烷基三甲基氢氧化铵、二氯化1-甲基-1′-十四烷基-4,4′-联吡锭、烷基三甲基溴化铵、盐酸安普罗铵(amproliumhydrochloride)、氢氧化苄索铵(benzethonium hydroxide)、苄索氯铵、苯甲基二甲基十六烷基氯化铵、苯甲基二甲基十四烷基氯化铵、苯甲基十二烷基二甲基溴化铵、苯甲基十二烷基二甲基氯化铵、鲸蜡基氯化吡锭、胆碱对甲苯磺酸盐、二甲基二(十八烷基)溴化铵、十二烷基乙基二甲基溴化铵、十二烷基三甲基氯化铵(DTAC)、乙基十六烷基二甲基溴化铵、十二烷基(2-羟乙基)二甲基溴化铵、十六烷基(2-羟乙基)二甲基氯化铵、鲸蜡基三甲基对甲苯磺酸铵、十二烷基氯化吡锭(月桂基氯化吡锭)、十二烷基三甲基甲磺酸铵、十二烷基三甲基对甲苯磺酸铵、[9-(2-羧苯基)-6-二乙氨基-3-亚呫吨基]-二乙基氯化铵(若丹明B(Rhodamine B))吉拉德试剂(Girard′s reagent)、十六烷基(2-羟乙基)二甲基磷酸二氢铵、十六烷基溴化吡锭、十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、甲基苄索氯铵、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(oxyphenonium bromide)、四庚基溴化铵、四(癸基)溴化铵、通佐溴铵(thonzoniumbromide)、三(十二烷基)氯化铵、三甲基十八烷基溴化铵、1-甲基-3-正辛基四氟硼酸咪唑鎓、1-癸基-3-甲基四氟硼酸咪唑鎓、1-癸基-3-甲基氯化咪唑鎓、三(十二烷基)甲基溴化铵、二甲基二硬脂基氯化铵和氯化六羟季铵。其它腐蚀抑制剂包括非离子表面活性剂(如PolyFox PF-159(欧诺瓦解决方案公司(OMNOVA Solutions))、聚(乙二醇)(“PEG”)、聚(丙二醇)(“PPG”)、PEG-PPG共聚物(如普洛尼克(Pluronic)F-127(巴斯夫(BASF)))、阴离子表面活性剂(如十二烷基苯磺酸、十二烷基硫酸钠、十二烷基苯磺酸钠)和其组合。季盐可充当腐蚀抑制剂(尤其对于铜和钨)和润湿剂两者。优选钨腐蚀抑制剂包括醚胺,其包括(但不限于):醚季胺(例如Q系列,如异癸氧基丙基双-(2-羟乙基)甲基氯化铵、异十三烷氧基丙基双-(2-羟乙基)甲基氯化铵、单大豆甲基氯化铵、牛脂二胺二季铵盐、椰油聚(15)氧乙烯甲基氯化铵)、氧化醚胺(例如AO系列,如双-(2-羟乙基)异癸氧基丙基氧化胺、直链烷氧基丙基氧化胺、低泡烷氧基丙基氧化胺(AO-405和AO-455)),和其组合。其它氧化胺表面活性剂亦将为适用的钨腐蚀抑制剂,包括(但不限于):十二烷基二甲基氧化胺、双-(2-羟乙基)椰子烷基氧化胺(C/12W,阿克苏诺贝尔(Azko Nobel))、二甲基椰子烷基氧化胺4-(苯甲氧基)吡啶N-氧化物、4-(3-苯丙基)吡啶N-氧化物,和其组合。其它适用的钨腐蚀抑制剂包括杂环(如吡啶、喹啉、喹唑啉、异喹啉、吡嗪、嘧啶、哒嗪、喹喔啉、吩嗪、菲啶、2,2′-吡啶、1,4′-吡啶、4,4′-吡啶和吖啶),以及包括C1-6烷基、苯基、苯甲基、苯乙基、3-苯丙基、苯甲氧基、羧基、氯基、溴基、甲氧基、硝基和氰基中的至少一个的所述杂环的衍生物,其包括(但不限于)2-苯甲基吡啶和4-(4-硝基苯甲基)吡啶。所属领域的技术人员将显而易见地,尽管季盐最通常以氯化物或溴化物形式购得,但其易于用如硫酸根、甲磺酸根、硝酸根、氢氧根等非卤阴离子与卤阴离子进行离子交换。本文中亦考虑并且首选所述经转化的季盐。在一个实施例中,腐蚀抑制剂包括阳离子季盐,更优选肉豆蔻基三甲基溴化铵、苯扎氯铵、十六烷基三甲基对甲苯磺酸铵、DTAC和十六烷基三甲基氢氧化铵,其中所述氯化物在使用之前已经离子交换。
在一个实施例中,腐蚀抑制剂选自苯甲基二甲基十二烷基氯化铵、苯甲基二甲基十四烷基氯化铵、4-(3-苯丙基)吡啶和5-甲基-苯并三唑。
本发明组合物可包含一或多种能够调节(即调整)组合物的pH的化合物(即pH调节剂)。组合物的pH可使用任何能够调节组合物的pH的适合化合物来调节。pH调节剂宜为水溶性的并且与组合物的其它组分相容。通常,组合物在使用点具有约-1至5、或0至4或2至4的pH。pH调节剂的非限制性实例包括无机酸和有机酸,其包括甲磺酸、乙磺酸、磷酸、硫酸、氯化氢等。
至少一种溶剂可包含水、至少一种可与水混溶的有机溶剂或其组合,其中所述至少一种可与水混溶的有机溶剂选自由式R1R2R3C(OH)的化合物组成的群组,其中R1、R2和R3为彼此独立的并且选自由以下组成的群组:氢、C2-C30烷基、C2-C30烯烃、环烷基、C2-C30烷氧基和其组合。举例来说,至少一种溶剂可包含至少一种选自由以下组成的群组的物种:水、甲醇、乙醇、异丙醇、丁醇和高级醇、四氢糠醇(THFA)、3-氯-1,2-丙二醇、3-氯-1-丙硫醇、1-氯-2-丙醇、2-氯-1-丙醇、3-氯-1-丙醇、3-溴-1,2-丙二醇、1-溴-2-丙醇、3-溴-1-丙醇、3-碘-1-丙醇、4-氯-1-丁醇、2-氯乙醇、二氯甲烷、三氯甲烷、乙酸、丙酸、三氟乙酸、四氢呋喃(THF)、N-甲基吡咯烷酮(NMP)、环己基吡咯烷酮、N-辛基吡咯烷酮、N-苯基吡咯烷酮、甲基二乙醇胺、甲酸甲酯、二甲基甲酰胺(DMF)、二甲亚砜(DMSO)、四亚甲基砜(环丁砜)、乙醚、苯氧基-2-丙醇(PPh)、乙基苯基酮(propriophenone)、乳酸乙酯、乙酸乙酯、苯甲酸乙酯、乙腈、丙酮、乙二醇、丙二醇(PG)、1,3-丙二醇、1,4-丙二醇、二噁烷、丁酰基内酯、碳酸亚丁酯、碳酸亚乙酯、碳酸亚丙酯、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(即丁基卡必醇)、三乙二醇单丁醚、乙二醇单己醚、二乙二醇单己醚、乙二醇苯醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二丙二醇二甲醚、二丙二醇乙醚、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、二丙二醇甲醚乙酸酯、四乙二醇二甲醚(TEGDE)、二元酯、碳酸甘油酯、N-甲酰基吗啉、磷酸三乙酯和其组合。在一个实施例中,至少一种溶剂包含水,例如去离子水。在一个实施例中,可与水混溶的溶剂选自乙二醇和丙二醇。
任选地,组合物可包含至少一种络合剂/螯合剂。然而,当氧化剂为过氧化合物(如过氧化氢)时,所述络合剂为组合物的必要组分。添加络合剂(如果存在)以减少粒子产生和生长并且改进组合物的存放期。所考虑的络合剂包括(但不限于)β-二酮化合物,如2,4-戊二酮、乙酰基丙酮酸盐、1,1,1-三氟-2,4-戊二酮和1,1,1,5,5,5-六氟-2,4-戊二酮;氨基酸,如甘氨酸、丝氨酸、脯氨酸、亮氨酸、丙氨酸、天冬酰胺、天冬氨酸、谷氨酰胺、组氨酸、谷氨酸、精氨酸、半胱氨酸、缬氨酸和赖氨酸;选自由以下组成的群组的多质子酸和氨基多羧酸:亚胺二乙酸(IDA)、丙二酸、草酸、丁二酸、硼酸、氮基三乙酸、苹果酸、柠檬酸、乙酸、顺丁烯二酸、乙二胺四乙酸(EDTA)、乙二胺四乙酸二铵盐(EDTA-2NH3)、(1,2-亚环己基二氮基)四乙酸(CDTA)、二乙烯三胺五乙酸(DTPA)、2-膦酰丁烷-1,2,4-三甲酸(PBTCA)、乙二胺二丁二酸和丙二胺四乙酸;膦酸;膦酸衍生物,如羟基亚乙基二膦酸(HEDP)(德奎斯特(Dequest)2010)、1-羟基乙烷-1,1-二膦酸、氮基-三(亚甲基膦酸)(NTMP)、氨基三(亚甲基膦酸)(德奎斯特2000)、二乙烯三胺五(亚甲基膦酸)(德奎斯特2060S)、乙二胺四(亚甲基膦酸)(EDTMPA);和其组合。替代地或另外,至少一种络合剂可包括阴离子表面活性剂,其包括(但不限于)烷基硫酸钠(如乙基己基硫酸钠)、烷基硫酸铵、烷基(C10-C18)羧酸铵盐、磺基丁二酸钠和其酯(例如磺基丁二酸钠二辛酯)、烷基(C6-C18)磺酸钠盐和二阴离子磺酸盐表面活性剂。优选阴离子表面活性剂包括氧化二苯基二磺酸盐,如购自陶氏化学(DoW Chemical)的DOWFAX系列阴离子表面活性剂,其包括DOWFAX 2A1(氧化四丙基二苯基二磺酸钠)、DOWFAX 3A2、DOWFAX 8390和DowFaxTMC6L(氧化烷二苯基二磺酸盐),以及购自罗纳-普朗克(Rhone-Poulenc)的RHODACAL DSB、购自奥林(Olin)的POLY-TERGENT 2A1、POLY-TERGENT 2EP、购自氰特(Cytec)的AEROSOL DPOS-45、购自派诺化工(Pilot Chemicals)的CALFAX DBA-40、CALFAX 16L-35等。氧化二苯基二磺酸盐表面活性剂表示一类由经二磺化的氧化烷二苯基分子组成的高度阴离子表面活性剂,其中电荷由两个磺酸根基团产生并且提供极佳的乳液稳定性。替代地或另外,至少一种络合剂可包括阻垢剂聚合物,其包括(但不限于)聚氨基酰胺(PAMAM)树枝状聚合物、聚(2-乙基-2-噁唑啉)、聚乙烯亚胺(PEI)、羟化聚乙烯亚胺、经改性的聚乙烯亚胺、聚烯丙胺盐酸盐(PALAM)、聚(丙烯酰胺)、聚(丙烯酸)、聚(二烯丙基二甲基氯化铵)、二烯丙基二甲基氯化铵、丙烯酰胺、乙酰胍胺、聚(丙烯酰胺-共-二烯丙基二甲基氯化胺)(PAMALAM),和其组合。替代地或另外,络合剂包括盐,所述盐包含铵阳离子或四烷基铵阳离子([NR 1R2R3R4]+,其中R1、R2、R3和R4可彼此相同或不同并且选自由氢和C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)组成的群组),和选自由以下组成的群组的阴离子:乙酸根、氯离子、溴离子、碘离子、硫酸根、苯甲酸根、丙酸根、柠檬酸根、甲酸根、草酸根、酒石酸根、丁二酸根、乳酸根、顺丁烯二酸根、丙二酸根、反丁烯二酸根、苹果酸根、抗坏血酸根、杏仁酸根和邻苯二甲酸根。举例来说,盐可包括溴化铵和/或氯化铵。在一个实施例中,络合剂包含氧化烷二苯基二磺酸盐、2,4-戊二酮、丝氨酸和其任何组合中的至少一种。
在另一实施例中,本发明组合物中的任一种可进一步包含氮化钛和/或光阻蚀刻材料残余物,其中所述残余物悬浮和/或溶解于水性组合物中。
在一个实施例中,第一方面的组合物包含以下、由以下组成或基本上由以下组成:至少一种氧化剂、至少一种含氟化物的蚀刻剂、至少一种pH调节剂、至少一种金属腐蚀抑制剂和任选的至少一种可与水混溶的溶剂,其中组分a至f(如果存在)以以下比例存在:
a.50至(材料的余量)重量百分比(水);
b.0.001至5重量百分比(氧化剂);
c.0.001至5重量百分比(氟化物蚀刻剂);
d.0.001至5重量百分比(金属腐蚀抑制剂);
e.0.1至10重量百分比(pH调节剂);和任选的
f.1至30重量百分比(可与水混溶的溶剂)。
在另一方面,本发明提供一种组合物,其包含:
a.水;
b.至少一种氧化剂,其选自过碘酸;过氧化氢、过氧化氢-脲、过硫酸铵、过氧乙酸、氢过氧化叔丁基和过锰酸钾;
c.至少一种蚀刻剂,其选自HF、四氟硼酸、六氟硅酸、H2ZrF6、H2TiF6、HPF6、氟化铵、四甲基氟化铵、四甲基氢氧化铵、六氟硅酸铵和六氟钛酸铵;
d.至少一种金属腐蚀抑制剂,其选自苯甲基二甲基辛基氯化铵、苯甲基二甲基十二烷基氯化铵、苯甲基二甲基十四烷基氯化铵、苯甲基二甲基十八烷基氯化铵、4-(3-苯丙基)吡啶、4-(3-苯丙基)吡啶n-氧化物、3-苯甲基吡啶N-氧化物、苯并三唑、5-甲基苯并三唑、甲苯基三唑、1,2,4-三唑,和其组合;
e.至少一种pH调节剂,其选自甲磺酸、硫酸、盐酸、硝酸、乙酸和磷酸;和任选的
f.至少一种可与水混溶的溶剂。
适用于蚀刻或去除氮化钛的某些组合物利用钝化剂,其用于减少对低k介电层的化学侵蚀并且保护晶片免受另外氧化。(参见例如以引用方式并入本文中的美国专利第10,138,117号。)在此类组合物中,有低k钝化剂,如硼酸、硼酸盐、烷氧硅烷、硅酸钠、四甲基硅酸铵、3-羟基-2-萘甲酸、丙二酸和亚胺二乙酸。已发现,本发明组合物不需要此类钝化剂即有效地选择性地去除氮化钛。因此,在另一实施例中,本发明组合物不含低k钝化剂。
应了解,在使用前制备待稀释的组合物的浓缩形式为惯例。举例来说,组合物可以更浓缩的形式制得,并且其后在制造商处、在使用之前和/或在工厂使用期间用至少一种溶剂稀释。稀释比可在约0.1份稀释剂:1份组合物浓缩物到约100份稀释剂:1份组合物浓缩物的范围内。应进一步了解,本文所描述的组合物包括随时间推移可能不稳定的氧化剂。因此,浓缩形式可大体上不含氧化剂,并且氧化剂可由制造商在使用之前和/或在工厂使用期间引入到浓缩物或经稀释的组合物中。
通过简单添加对应成分并且混合到均质条件,易于调配出本文所描述的组合物。此外,组合物可易于调配为在使用之时或之前混合的单封装调配物或多部分调配物,优选多部分调配物。多部分调配物的个别部分可在工具或在混合区/域(如内嵌混合机或在工具上游的储槽中)中混合。经考虑,多部分调配物的各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。对应成分的浓度可以组成的特定倍数广泛变化,即更稀或更浓,并且应了解,组合物可不同地并且替代地包含与本文中的公开内容一致的成分的任何组合、由与本文中的公开内容一致的成分的任何组合组成或基本上由与本文中的公开内容一致的成分的任何组合组成。
因此,另一方面,本发明提供一种试剂盒,其在一或多个容器中包含适于形成本文所描述的组合物的一或多种组分。试剂盒的容器必须适合于储存和运送所述去除组合物组分,例如容器(美国康涅狄克州丹伯里(Danbury,Conn.,USA)的美国先进科材(Advanced Technology Materials)公司)。含有组合物的各组分的一或多个容器优选地包括用于使所述一或多个容器中的组分呈流体连通以供掺合和分配的构件。举例来说,参考容器,气压可施加到所述一或多个容器中的衬里外部以使得衬里的至少一部分内含物排出并且因此实现流体连通以供掺合和分配。替代地,可向常规可加压容器的顶部空间施加气压或可使用泵来实现流体连通。另外,所述系统优选地包括用于将经掺合的组合物分配到处理工具的分配口。
大体上化学惰性、无杂质、柔性和弹性聚合膜材料(如高密度聚乙烯)可用于制造所述一或多个容器的衬里。处理合乎需要的衬料不需要共挤出层或障壁层,并且不需要任何可能对待安置于衬里中的组分的纯度要求产生不利影响的颜料、UV抑制剂或处理剂。理想衬料的列表包括包含原生(即不含添加剂)聚乙烯、原生聚四氟乙烯(PTFE)、聚丙烯、聚氨基甲酸酯、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。此类衬料的优选厚度在约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在此以分别全文引用的方式并入本文中:美国专利第7,188,644号,题为“最大限度地减少超纯液体中的粒子产生的设备的方法(APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLESIN ULTRAPURE LIQUIDS)”;美国专利第6,698,619号,题为“可回收和可再用的衬袋桶式流体储存和分配容器系统(RETURNABLE AND REUSABLE,BAG-IN-DRUM FLUID STORAGE ANDDISPENSING CONTAINER SYSTEM)”;和2008年5月9日申请的PCT/US08/63276,题为“用于材料掺合和分配的系统的方法(SYSTEMS AND METHODS FOR MATERIAL BLENDING ANDDISTRIBUTION)”,所述专利中的每一个以引用的方式并入本文中。
在另一方面,本发明提供使用本文所描述的组合物从其上具有氮化钛材料的微电子装置的表面蚀刻氮化钛材料的方法。举例来说,氮化钛材料可经去除而不大体上破坏/去除存在于微电子装置上的金属导体和绝缘体材料。因此,在另一实施例中,描述一种相对于钼、铝氧化物、二氧化硅、多晶硅,使用本文所描述的组合物从其上具有氮化钛的微电子装置的表面选择性地并且大体上去除氮化钛的方法。在另一实施例中,描述一种相对于金属导体(例如铜)、钨和绝缘体材料,使用本文所描述的组合物从其上具有氮化钛的微电子装置的表面选择性地并且大体上去除氮化钛的方法。
在蚀刻应用中,以任何适合方式将组合物涂覆到其上具有氮化钛和/或光阻蚀刻残留物材料的微电子装置的表面,例如,通过将组合物喷涂到装置的表面上;通过浸渍(在组合物的静态或动态体积中)包括氮化钛的装置;通过使装置与其上吸收有组合物的另一材料(例如衬垫或纤维吸附剂施料器元件)接触;通过使包括氮化钛和/或光阻蚀刻残留物材料的装置与循环组合物接触;或通过任何其它适合的手段、方式或技术,使组合物与氮化钛膜去除接触。涂覆可在批式或单个晶片设备中进行,以用于动态或静态清洁。有利地,本文中所描述的组合物借助于其相对于可能存在于微电子装置结构上并且暴露于组合物的其它材料(如金属和绝缘材料(即低k介电质)以及高k材料(如氧化铪、氧化锆、氧化钛))对氮化钛膜的选择性以高效和高度选择性方式实现至少部分去除氮化钛。
在使用本文中所描述的组合物从其上具有氮化钛的微电子装置结构去除氮化钛时,通常在约20℃至约100℃或约30℃至约60℃范围内的温度下使所述组合物在单晶片工具中与装置结构接触持续约0.3分钟至约30分钟或约0.5分钟至约3分钟的足够时间。此类接触时间和温度为说明性的,并且可采用有效地从装置结构至少部分去除氮化钛膜的任何其它适合的时间和温度条件。
在实现所需蚀刻/去除作用之后,所述组合物可易于从其先前所涂覆的微电子装置去除,例如通过冲洗、洗涤或其它去除步骤,如本文所描述的组合物的给定最终用途应用中可为所需并且有效的。举例来说,装置可用包括去离子水的冲洗溶液冲洗和/或脱水(例如,离心法脱水、N2、蒸气脱水等)。因此,在另一方面,本发明提供一种在钼存在下在微电子装置上选择性地蚀刻氮化钛的方法,其包含在约20℃至约70℃的温度下将所述微电子装置暴露于本发明组合物持续约30秒至约10分钟的时段,随后用去离子水洗涤所述微电子装置。
在另一方面,本发明提供根据本文所描述的方法制得的改进型微电子装置和含有此类微电子装置的产品。
在另一方面,本发明提供制造包含微电子装置的制品的方法,所述方法包含使微电子装置与组合物接触足够时间而从其上具有氮化钛的微电子装置的表面以蚀刻方式去除氮化钛,并且将所述微电子装置并入到所述制品中,其中所述组合物包含以下、由以下组成或基本上由以下组成:至少一种氧化剂、至少一种蚀刻剂、至少一种腐蚀抑制剂、任选的至少一种络合剂和任选的至少一种可与水混溶的溶剂。
涉及3D与非闪存器结构中的栅极蚀刻的某些特定微电子装置涉及经由如上文所描述的干式蚀刻工艺用高选择率蚀刻剂制得钼凹部的第一步骤。在第二步骤中,本发明的方法和组合物经实施以选择性地蚀刻钛。因此,在另一方面,本发明提供一种用于以依序步骤选择性地蚀刻钼和氮化钛的方法,其包含:
a.使用干式蚀刻方法蚀刻钼,随后
b.在钼存在下在微电子装置上选择性地蚀刻氮化钛,其包含使所述微电子装置在约20℃至约70℃的温度下暴露于根据本发明组合物持续约30秒至约10分钟的时段,随后用去离子水洗涤所述微电子装置。
在另一方面,本发明提供一种制品,其包含以下、由以下组成或基本上由以下组成:微电子装置衬底、所述衬底上的氮化钛层和本文所描述的组合物。在一个实施例中,本发明提供一种组合物,其由上文列举的组分a.至f.组成或基本上由其组成。
本发明可通过其优选实施例的以下实例进一步说明,但应了解,除非另外具体指示,否则包括这些实例仅出于说明的目的并且不意谓限制本发明的范围。
实例
符号:
MSA:甲磺酸
12C:苯甲基二甲基十二烷基氯化铵
14C:苯甲基二甲基十四烷基氯化铵
PPP:4-(3-苯丙基)吡啶
DIW:去离子水
5m-BTA.:5-甲基苯并三唑
RPM-指代用于实验中的磁搅拌棒的每分钟转数。
1.氧化剂测试(过碘酸)
1)调配物和测试条件
2)蚀刻结果:
在这些实验中,注意到过碘酸浓度越高,Mo蚀刻速率越高。此外,过碘酸浓度越高,TiN蚀刻速率越低。因此,为了提高TiN/Mo选择率,宜降低过碘酸浓度。如果调配物不具有过碘酸,那么TiN蚀刻速率为极低的。
2.另外氧化剂测试(过碘酸与过氧化氢比较)
1)调配物和测试条件
2)蚀刻速率结果
可观察到,当使用过氧化氢作为氧化剂时,Mo蚀刻速率因浓度而大幅度增加。
3.HF剖析测试(蚀刻剂)
1)调配物和测试条件
2)测试结果:
在这些实验中,注意到HF浓度越高,TiN和Mo蚀刻速率越高。在HF浓度较高的情况下,TEOS蚀刻速率亦增加,但不会达到过量程度。不含HF的调配物具有极低的TiN蚀刻速率。
4.C12浓度剖析测试(Mo抑制剂)
1)调配物和测试条件:
2)蚀刻速率结果:
在这些实验中,注意到12C(苯甲基二甲基十二烷基氯化铵)作为Mo抑制剂为有效的。另外,12C的浓度越高,钼蚀刻速率越低。12C的浓度越高,钼蚀刻速率越低。12C浓度越高,氮化钛蚀刻速率越低。最后,12C浓度似乎不影响如AlOx、TEOS和多晶Si的其它材料的蚀刻速率。
5.另外Mo抑制剂测试(12C、14C、5m-BTA、PPP、甘氨酸)
1)调配物和测试条件
2)测试结果:
在这些实验中,注意到12C展现出的TiN/Mo选择率比14C(苯甲基二甲基十四烷基氯化铵)高。另外,当12C浓度增加时,Mo和TiN蚀刻速率均降低。12C、PPP(4-(3-苯丙基)吡啶)和5m-BTA(5-甲基-苯并三唑)中的每一种充当Mo抑制剂,其有助于提高TiN/Mo选择率。最后,抑制剂组合调配物可帮助降低Mo蚀刻速率。当比较组合物15至17时,组合物17具有最低Mo蚀刻速率,其产生最高的TiN/Mo选择率。
6.pH调节剂测试
1)调配物和测试条件
2)蚀刻速率结果:
观察结果:
(1)含pH调节剂的调配物具有类似的TiN/Mo选择率。
(2)不含pH调节剂的调配物具有较低Mo蚀刻速率,其产生较高TiN/Mo选择率。但其缺点为显示出较高TEOS Mo蚀刻速率。
7.溶剂测试
1)调配物和测试条件:
2)蚀刻速率结果:
观察结果:
(1)乙二醇有助于溶解调配物中的5m-BTA。
(2)但含EG的调配物具有较低TiN/Mo选择率。
已特定参考本发明的某些实施例来详细描述本发明,但应了解,可在本发明的精神和范围内进行变化和修改。
Claims (14)
1.一种组合物,其包含:
a.水;
b.至少一种氧化剂;
c.至少一种含氟化物的蚀刻剂;
d.至少一种金属腐蚀抑制剂;
e.至少一种pH调节剂;和任选的
f.至少一种可与水混溶的溶剂。
2.根据权利要求1所述的组合物,其中pH为约-1至5。
3.根据权利要求1所述的组合物,其中pH为约0至4。
4.根据权利要求1所述的组合物,其中所述含氟化物的蚀刻剂选自HF、四氟硼酸、六氟硅酸、H2ZrF6、H2TiF6、HPF6、氟化铵、四甲基氟化铵、四甲基氢氧化铵、六氟硅酸铵、六氟钛酸铵或其组合。
5.根据权利要求1所述的组合物,其中所述含氟化物的蚀刻剂为HF。
6.根据权利要求5所述的组合物,其中所述金属腐蚀抑制剂选自十二烷基三甲基氯化铵、4-(3-苯丙基)吡啶、苯甲基二甲基十四烷基氯化铵和5-甲基苯并三唑。
7.根据权利要求1所述的组合物,其中所述组合物包含选自乙二醇和丙二醇的可与水混溶的溶剂。
8.根据权利要求1所述的组合物,其中所述氧化剂为过碘酸,所述蚀刻剂为HF,并且其中所述金属腐蚀抑制剂选自十二烷基三甲基氯化铵、4-(3-苯丙基)吡啶、苯甲基二甲基十四烷基氯化铵和5-甲基苯并三唑。
9.一种用于在钼存在下在微电子装置上选择性地蚀刻氮化钛的方法,其包含使所述微电子装置在约20℃至约70℃的温度下暴露于根据权利要求1至10中任一权利要求所述的组合物持续约30秒至约10分钟的时段,随后用去离子水洗涤所述微电子装置。
10.根据权利要求9所述的方法,其中所述微电子装置为NAND闪存器装置。
11.根据权利要求9所述的方法,其中所述干式或湿式蚀刻方法包含Cl2和O2等离子体。
12.一种用于在微电子装置上以依序步骤选择性地蚀刻钼和氮化钛的方法,其包含:
a.使用干式或湿式蚀刻方法蚀刻钼,随后
b.在钼存在下在微电子装置上选择性地蚀刻氮化钛,其包含使所述微电子装置在约20℃至约70℃的温度下暴露于根据权利要求1至10中任一权利要求所述的组合物持续约30秒至约10分钟的时段,随后用去离子水洗涤所述微电子装置。
13.根据权利要求12所述的方法,其中所述微电子装置为NAND闪存器装置。
14.根据权利要求12所述的方法,其中所述干式或湿式蚀刻方法包含Cl2和O2等离子体。
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