TW201928098A - 基材上選擇性沉積金屬薄膜之方法 - Google Patents
基材上選擇性沉積金屬薄膜之方法 Download PDFInfo
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- TW201928098A TW201928098A TW107134125A TW107134125A TW201928098A TW 201928098 A TW201928098 A TW 201928098A TW 107134125 A TW107134125 A TW 107134125A TW 107134125 A TW107134125 A TW 107134125A TW 201928098 A TW201928098 A TW 201928098A
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- dielectric
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- 239000000758 substrate Substances 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 96
- 238000000151 deposition Methods 0.000 title claims abstract description 77
- 239000004065 semiconductor Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000004381 surface treatment Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims description 191
- 239000002184 metal Substances 0.000 claims description 191
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 239000010408 film Substances 0.000 claims description 47
- 239000002243 precursor Substances 0.000 claims description 47
- 238000002161 passivation Methods 0.000 claims description 39
- 230000008021 deposition Effects 0.000 claims description 36
- 239000010409 thin film Substances 0.000 claims description 33
- 229910052721 tungsten Inorganic materials 0.000 claims description 28
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 26
- 239000010937 tungsten Substances 0.000 claims description 26
- 239000003638 chemical reducing agent Substances 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012964 benzotriazole Substances 0.000 claims description 6
- 229910000077 silane Inorganic materials 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 5
- 238000010943 off-gassing Methods 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 150000001350 alkyl halides Chemical class 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000078 germane Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910019800 NbF 5 Inorganic materials 0.000 claims description 2
- 229910004529 TaF 5 Inorganic materials 0.000 claims description 2
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims description 2
- VXGHASBVNMHGDI-UHFFFAOYSA-N digermane Chemical compound [Ge][Ge] VXGHASBVNMHGDI-UHFFFAOYSA-N 0.000 claims description 2
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 claims description 2
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 claims description 2
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 4
- 229910021529 ammonia Inorganic materials 0.000 claims 2
- LNDHQUDDOUZKQV-UHFFFAOYSA-J molybdenum tetrafluoride Chemical compound F[Mo](F)(F)F LNDHQUDDOUZKQV-UHFFFAOYSA-J 0.000 claims 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 claims 1
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 claims 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims 1
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- 238000010926 purge Methods 0.000 description 9
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
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- 125000000217 alkyl group Chemical group 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
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- 230000004888 barrier function Effects 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 6
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000001259 photo etching Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000010953 base metal Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
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- 150000003509 tertiary alcohols Chemical class 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
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- 239000010936 titanium Substances 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000579895 Chlorostilbon Species 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
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- 125000003172 aldehyde group Chemical group 0.000 description 2
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- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
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- 238000005498 polishing Methods 0.000 description 2
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- 235000019260 propionic acid Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000005019 vapor deposition process Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- 125000003158 alcohol group Chemical group 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-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
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
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- 125000001650 tertiary alcohol group Chemical group 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0209—Pretreatment of the material to be coated by heating
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
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Abstract
本發明揭露一種用於在包含一第一電介質表面和一第二金屬表面的基材上選擇性沉積金屬薄膜的方法。該方法可包括:暴露該基材於一鈍化劑、在該第二金屬表面上進行一表面處理、及在相對於所述第二金屬表面的該第一電介質表面上選擇性沉積該金屬薄膜。本發明亦揭露包含使用本發明的方法選擇性沉積一金屬薄膜之半導體裝置結構。
Description
本發明通常有關在基材上選擇性沉積一金屬薄膜的方法,尤其是揭露用於在相對於一金屬表面的一電介質表面上選擇性沉積一金屬薄膜的方法。本發明亦有關包括一選擇性沉積金屬薄膜的半導體裝置結構。
在某些應用中,可能想要僅在基材的某些區域上沉積一金屬薄膜。通常,藉由沉積一連續金屬薄膜而且隨後使用光蝕刻和蝕刻步驟來圖案化金屬薄膜而實現此區別結果。這種光蝕刻和蝕刻製程可能耗時和昂貴,而且無法提供許多應用的所需精度。一可能的解決方案是使用選擇性沉積製程,因此僅在想要的區域中沉積一金屬薄膜,因此消除需要後續圖案化步驟。用於半導體裝置結構的選擇性沉積製程可採用多種形式,包括但沒有限於電介質表面上選擇性電介質沉積(DoD)、金屬表面上的選擇性電介質沉積(DoM)、電介質表面上選擇性金屬沉積(MoD)和金屬表面上的選擇性金屬沉積(MoM)。
電介質表面上選擇性金屬沉積(MoD)的重要性是提供無需複雜圖案化和蝕刻步驟而在電介質表面上方選擇性沉積金屬薄膜的方法。一用於在電介質表面上方製造包含選擇性金屬的基材之常用方法可包括在基材的整個表面上方覆蓋沉積一金屬薄膜,覆蓋金屬表面和電介質表面兩者,而且隨後形成一光蝕刻遮罩層(或如果需要,一雙圖案化遮罩層)在覆蓋金屬薄膜的表面上方,其中所述遮罩層設置在要保留金屬薄膜的區域上方。基材然後暴露於一金屬蝕
刻製程,諸如一濕蝕刻或一乾蝕刻,這將從未被光蝕刻遮罩覆蓋的基材暴露區域除去金屬薄膜。隨後的製程可除去殘留的光蝕刻遮罩,因此形成一包含設置在電介質表面上方的金屬薄膜之基材。然而,此用於在電介質表面上方形成金屬薄膜的製程(即是,覆蓋沉積)是複雜、耗時、成本過高,而且僅隨著裝置特徵件尺寸在先進技術領域減小,這製程會變得更複雜。因此,需要用於在相對於一金屬表面的一電介質表面上選擇性沉積金屬薄膜的方法,而且尤其是,用於電介質表面上選擇性沉積鎢薄膜的方法。
提供的本發明內容是以簡化形式說明概念方案。在以下本發明示例實施例的實施方式中將更詳細描述這些概念。本發明內容沒有要確認專利標的關鍵性特徵或必要特徵,且沒有要限制專利標的之範疇。
在某些實施例中,提供用於在包含一第一電介質表面和一第二金屬表面的基材上選擇性沉積金屬薄膜之方法。該方法可包括暴露該基材於一鈍化劑;在該第二金屬表面上進行一表面處理;及在相對於該第二金屬表面的所述第一電介質表面上選擇性沉積該金屬薄膜。
為概述本發明之目的及相較於先前技術所達成之優點,本發明之某些目的及優點已描述於以上本說明書中。當然,應明瞭無須所有該等目的或優點皆可根據本發明之任何特定具體例來達成。因此,例如,熟習該項技藝者將明白,本發明可採取實現或最佳化如本說明書所教示或建議的一優點或一群優點的方式加以具體實施或實現,而無需實現如本說明書所教示或建議的其他目的或優點。
這些實施例的全部都在本說明書揭露本發明的範疇內。熟習該項技藝者將可從下列連同參考附圖的特定實施例詳細描述而更瞭解這些及其他實施例,本發明並沒有受限於所揭露的任何特定實施例。
100‧‧‧方法
120‧‧‧將基材提供於第一反應室中而且將該基材加熱到一處理溫度110將基材釋氣
130‧‧‧暴露該基材於一鈍化劑
140‧‧‧在第二金屬表面上進行一表面處理
150‧‧‧將該基材轉移到一第二反應室,而且將該基材加熱到一處理溫度
160‧‧‧選擇性沉積一金屬薄膜在相對於所述第二金屬表面的該第一電介質
表面上
200‧‧‧半導體結構
202‧‧‧基材
204‧‧‧圖案化電介質層
206‧‧‧金屬層
208‧‧‧選擇性金屬薄膜
300‧‧‧半導體裝置結構
302‧‧‧金屬觸點
304‧‧‧層間電介質
304'‧‧‧層間電介質的其餘部分
306‧‧‧半導體裝置結構
308‧‧‧接觸孔
310‧‧‧金屬表面
312‧‧‧半導體裝置結構
314‧‧‧選擇性金屬薄膜
316‧‧‧半導體裝置結構
318‧‧‧低電阻接觸插塞
320‧‧‧平坦面
雖然本說明書總結特別指出及明確主張被視為本發明實施例的專利申請項,但是可從本發明實施例的某些實例描述及連同參考附圖可更容易確定本發明實施例的優點,在附圖中:圖1為示意說明根據本發明之實施例之示例性選擇性沉積方法的製程流程圖。
圖2示意說明包括根據本發明之實施例所沉積一選擇性金屬薄膜的半導體結構之掃描式電子顯微鏡(Scanning Electron Microscopy,SEM)截面圖;
圖3A、3B、3C和3D示意說明製造包含根據本發明之實施例所沉積一選擇性金屬薄膜的半導體裝置結構之方法。
雖然下面揭露某些實施例和實例,但熟習該項技藝者將瞭解,本發明超出本發明的具體揭露的實施例及/或用途及其明顯修改和等效物。因此,所揭露本發明的範疇並沒有受到下面描述的特定揭露實施例的限制。
本說明書提供的示意說明沒有意味著任何特定材料、結構或裝置的實際視圖,而是僅為針對描述本發明的實施例之理想化表示。
如本說明書的使用,術語「基材」可意指使用或可在其上形成一裝置、一電路或一薄膜的任何基底材料或多個材料。
如本說明書的使用,術語「鈍化劑」可意指任何化學物質,當其施加到材料表面時,採取至少減少其化學活性的方式改變材料的表面。
如本說明書的使用,術語「鈍化層」可意指設置在表面上方的任何材料層或部分材料層,其採取減少其化學活性的方式改變表面。
如本說明書的使用,術語「金屬表面」可意指包括金屬成份的表面,包括但沒有限於金屬表面、金屬氧化物表面、金屬矽化物表面、金屬氮化
物表面和金屬碳化物表面。
如本說明書的使用,術語「原子層沉積(Atomic Layer Deposition,ALD)」可意指在處理室中進行沉積循環而較佳地複數個連續沉積循環之氣相沉積製程。通常,在每個循環期間,前驅物被化學吸附到一沉積表面(例如,一基材表面或一先前沉積的底層表面,諸如來自一先前ALD循環的材料),形成一單層或亞單層(Sub-monolayer),其不容易與其他前驅物起反應(即是,自限性反應)。此後,如需要,一反應物(例如,另一前驅物或反應氣體)隨後可引入處理室而用於將所述化學吸附的前驅物轉換成在沈積表面上的所需材料。通常,此反應物能夠與前驅物進一步反應。此外,亦可在各循環期間在轉化經化學吸附之前驅體之後利用沖洗步驟自處理室移除過量前驅體及/或自處理腔室移除過量反應物及/或反應副產物。此外,如本文中所使用之術語「原子層沉積」在用前驅體組合物、反應氣體及沖洗(例如惰性載劑)氣體之交流脈衝執行時還意欲包括由相關術語指示之製程,諸如「化學氣相原子層沉積」、「原子層磊晶法(ALE)」、分子束磊晶法(MBE)、氣體源MBE或有機金屬MBE及化學束磊晶法。
如本說明書的使用,術語「膜」和「薄膜」可意指藉由本說明書揭露的方法沉積的任何連續或非連續結構和材料。例如,「膜」和「薄膜」可包含2D材料、奈米棒、奈米管、或奈米顆粒或甚至部分或全部分子層或部分或整個原子層或原子及/或分子簇。「膜」和「薄膜」可包含具有針孔的材料或層,但仍然是至少部分連續。
本發明的實施例可包括用於在基材上選擇性沉積一金屬薄膜的方法,而且尤其是,用於在相對於一金屬表面(即是,在介電選擇性沉積製程上的金屬)的一電介質表面上選擇性沉積金屬薄膜的方法。如本發明的實施例的非限制性示例所示,可在相對於一金屬表面的一電介質表面上選擇性沉積鎢薄膜。
本說明書描述的選擇性沉積製程可無需其他光蝕刻及/或蝕刻步
驟而用於在電介質表面上選擇性沉積一金屬薄膜。因此,本說明書描述的選擇性沉積製程藉由減少光蝕刻遮罩階段及/或蝕刻階段的次數而簡化裝置製造製程。此外,藉由消除金屬表面上沉積某些不想要金屬薄膜,在一電介質表面上選擇性沉積金屬薄膜的能力可改善裝置效能。
在電介質沉積製程上的選擇性金屬可能應用包括在相對於金屬表面的電介質表面上選擇性沉積鎢(W)。例如,一普通半導體裝置結構可包括由蝕刻在一介電薄膜(諸如氧化矽)中以露出基層金屬的接觸孔組成的一金屬接觸結構。一阻障金屬,諸如(例如),氮化鈦(TiN)薄膜可沉積在接觸孔的側壁以及在基層金屬兩者上,而且一高電阻鎢(W)成核層沉積在該氮化鈦薄膜上。最後,使用低電阻率鎢(W)的接觸插塞完成接觸結構。然而,在此接觸結構中,由在基層金屬接觸表面上存在的氮化鈦阻障金屬和高電阻鎢成核層明顯增加接觸的電阻率。針對鎢沉積而在介電製程上利用一選擇性金屬,可除去氮化鈦阻障層,而且鎢可直接沉積在介電孔的側壁上。在這製程中,沒有氮化鈦或高電阻率鎢沉積在基層金屬上,而且一低電阻率鎢可緊接沉積在該接觸孔中,因此降低電接觸電阻。
一選擇性沉積製程可包括在相對於一第二表面的一第一表面上沉積更大量材料。例如,對於在介電選擇性沉積製程上的金屬而言,所述選擇性沉積製程可在相對於一第二金屬表面的一第一電介質表面上沉積更大量的金屬薄膜。在本發明的某些實施例中,該沉積製程的選擇性可表示為在第一表面上形成的材料相對於所組合第一和第二表面上形成的材料量之比率。例如,如果選擇性沉積製程在一第一電介質表面上沉積10nm的鎢而且在一第二金屬表面上沉積1nm的鎢,則所述選擇性沉積製程將被認為具有90%的選擇性。在某些實施例中,本說明書揭露方法的選擇性可高於約80%、高於約90%、高於約95%、或甚至高於約100%。在某些實施例中,沉積製程的選擇性為至少約80%,這對
於某些特定應用可為足夠選擇性。在一些情況下,選擇性為至少約50%,其選擇性可足以用於一些特定應用。
圖1示意說明本發明之方法的非限制性示例實施例,其示意說明用於在相對於一第二金屬表面的一第一電介質表面上選擇性沉積金屬薄膜之選擇性沉積方法100。該選擇性沉積方法100可從包括將該基材提供於第一反應室中而且將該基材加熱到一處理溫度的製程步驟110繼續。
更具體係,在本發明的某些實施例中,該基材可包括一平面基材或一圖案化基材。圖案化基材可包括含有形成在該基材表面中或其上的半導體裝置結構之基材,例如,該等圖案化基材可包括部分製造的半導體裝置結構,諸如電晶體和記憶體元件。該基材可包括一第一電介質表面和一第二金屬表面,換句話說,該基材的表面可包括複數個第一電介質表面和複數個第二金屬表面。
在本發明的某些實施例中,所述第一電介質表面可包含一低介電常數材料,即是一低k材料,其可被定義為一介電常數小於約4.0的絕緣體。在某些實施例中,該低k材料的介電常數可小於約3.5、或小於約3.0、或小於約2.5、或甚至小於約2.3。在某些實施例中,所述第一電介質表面可包含一第一含矽表面。例如,所述第一電介質表面可包含氧化矽、氮化矽、碳化矽、氮氧化矽、或其混合物之至少一者。在本發明的某些實施例中,所述第一電介質表面可包括含有彼此連接孔之多孔材料。
在某些實施例中,所述第二金屬表面可包含一元素金屬,諸如(例如)銅(Cu)、鈷(Co)、鎳(Ni)、或鎢(W)。在某些實施例中,所述第二金屬表面可包含一純金屬、一金屬氧化物、一金屬氮化物、一金屬矽化物、一金屬碳化物、或其混合物之至少一者。在某些實施例中,所述第二金屬表面可包括一含金屬材料的俱生氧化物(Native oxide)。在某些實施例中,所述第二金屬表面可包含一
過渡金屬。例如,所述過渡金屬可包含Ti、V、Cr、Mn、Nb、Mo、Ru、Rh、Pd、Ag、Au、Hf、Ta、W、Re、Os、Ir或Pt之一或多者。
選擇性沉積方法100可從將基材裝載到一適宜的第一反應室之製程步驟110繼續。所述第一反應室可構成用於進行選擇性沉積方法100的全部或一部分的其餘製程步驟。在本發明的某些實施例中,所述第一反應室可構成選擇性將基材釋氣(即是,製程步驟120),而且暴露該基材於一鈍化劑(即是,製程步驟130)。然而,在本發明的其他實施例中,所述第一反應室可構成進行包括選擇性沉積方法100的所有製程步驟。
能夠在電介質表面上選擇性沉積一金屬薄膜的反應器及其相關的反應室可用於進行選擇性沉積方法100。這種反應器包括ALD反應器、以及具有適宜設備的CVD反應器、及用於提供前驅物的構件。根據某些實施例,一噴灑頭式反應器可使用。根據某些實施例,一諸如電漿增強型ALD反應器的電漿反應器可使用。電漿可直接緊鄰或遠離或鄰近基材。根據某些實施例,可使用一熱反應器,即是非電漿反應器,諸如熱ALD反應器。
可使用的適宜反應器和相關反應室的實例包括商用的單基材(或單晶片)沉積設備,諸如可購自位於美國亞利桑那州鳳凰城的ASM America,Inc.公司和位於荷蘭阿爾梅勒市的ASM EuropeB.V.公司的Pulsar®反應器(諸如Pulsar® 2000和Pulsar® 3000和Pulsar® XP ALD)、和EmerALD® XP和EmerALD®反應器。其他商用反應器包括來自商標名為Eagle® XP和XP8的ASM Japan K.K.公司(位於日本東京)。在某些實施例中,所述反應器為一空間式ALD反應器,其中基材在製程過程會移動或旋轉。
在某些實施例中,可使用一批式反應器。適宜的批式反應器包括但沒有限於商標名稱A400和A412 PLUS的ASM Europe B.V.公司(位於荷蘭阿爾梅勒市)提供的商用Advance® 400系列反應器。在某些實施例中,可使用一直立
批式反應器,其中船形器件在製程期間會旋轉,諸如A412。因此,在某些實施例中,晶圓在製程期間轉動。在其他實施例中,批式反應器包括一小批式反應器,其構成容納10個或更少晶圓、8個或更少晶圓、6個或更少晶圓、4個或更少晶圓、或2個晶片。在使用一批式反應器的某些實施例中,晶圓與晶圓的均勻性小於3%(1σ)、小於2%、小於1%或甚至小於0.5%。
本說明書描述的沉積方法可選擇性在連接一組合設備工具(Cluster tool)的反應器或反應空間中進行。在一組合設備工具中,因為每個反應空間是專屬於一類型製程,使得可保持每個模塊中的反應空間的溫度恆定,而且相較於每次運行前的基材需被加熱到處理溫度的反應器可改善生產量。另外,在群集工具中,可減少在基板之間將反應空間泵至期望製程壓力值之時間。
在本發明的某些實施例中,一獨立反應器可具有一裝載鎖。在此情況下,不必然要在每次運行之間冷卻反應空間。
一旦將該基材裝載到所述第一反應室內,可將該基材加熱到一適宜處理溫度。在本發明的某些實施例中,選擇性沉積方法100的製程步驟110可包括將該基材加熱到大於250℃、或大於300℃、或大於350℃、或甚至大於400℃的溫度。在本發明的某些實施例中,可將該基材加熱到約250℃的溫度。在本發明的某些實施例中,可將該基材加熱到約250℃的溫度。
選擇性沉積方法100可從選擇性製程步驟120繼續,其中該基材經歷一釋氣處理。在本發明的某些實施例中,該基材的釋氣可包括將該基材加熱到高於250℃的溫度持續大於約1分鐘、或大於約5分鐘、或甚至大於約10分鐘的時段。可進行該基材的釋氣以從該基材的表面除去不想要的物質,例如,可進行釋氣製程以從該基材除去濕氣。
一旦該基材經歷選擇性釋氣製程,選擇性沉積方法100可從製程步驟130繼續,其中該基材暴露於一鈍化劑。在本發明的某些實施例中,暴露該
基材於一鈍化劑可包括暴露該基材於一烷基鹵化矽烷(Alkylhalosilane),其中所述烷基鹵化矽烷可具有通式Xy-Si-R4-y,其中R是一烴類(Hydrocarbon),諸如(例如),一烷基(例如,C1-C3烷基),X是一鹵化物(Halide),諸如(例如),氯(Cl)或氟(F),而且y是從1至3、從1至2、或1的整數。在某些實施例中,暴露該基材於一鈍化劑可包括暴露該基材於具有通式(NRII 2)y-Si-RI 4-y的化學劑,其中RII是一C1-C5烷基,RI是一烴類,諸如(例如),一C1-C3烷基,而且y是從1至3、從1至2、或1的整數。在本發明的某些實施例中,暴露該基材於一鈍化劑可包括暴露該基材於三甲(二甲氨基)矽烷(Trimethyl(dimethylamino)silane)。在某些實施例中,暴露該基材於一鈍化劑可包括使該鈍化劑以約大於1sccm、或約大於5sccm、或約大於25sccm、或約大於50sccm、或約大於100sccm、或甚至約大約500sccm的流率流入所述第一反應室。
暴露該基材於一鈍化劑的製程可在大於約250℃、或大於約300℃、或大於約350℃、或甚至大於約400℃的基材溫度下進行。在本發明的某些實施例中,暴露該基材於一鈍化劑的製程可在約250℃的溫度下進行。在本發明的某些實施例中,暴露該基材於一鈍化劑可進行持續大於1秒、或大於30秒、或大於1分鐘、或大於2分鐘、或甚至大於5分鐘的時段。在某些實施例中,暴露該基材於一鈍化劑可進行持續約15秒的時段。在本發明的某些實施例中,當暴露該基材於鈍化劑時,所述第一反應室內的壓力可小於10Torr、或小於5Torr、或甚至小於2Torr。在本發明的某些實施例中,當暴露該基材於鈍化劑時,所述第一反應室內的壓力可介於1Torr和760Torr之間。
一旦該基材已被暴露於鈍化劑,可從所述第一反應室除去任何殘餘的鈍化劑,例如,可利用真空從所述第一反應室除去任何殘餘的鈍化劑及/或可使用一吹掃氣體(例如,氮氣或氬氣)「沖洗」所述第一反應室。
選擇性沉積方法100可從製程步驟140繼續,其包括在該基材的所
述第二金屬表面上進行一表面處理。例如,當所述第二金屬表面包含一實質元素金屬表面時,則可利用所述第二金屬表面的表面處理來清潔及/或還原所述第二金屬表面,使得一純元素金屬在基材表面上。如一非限制性示例實施例所示,所述第二金屬表面可包含一銅表面,而且所述表面處理可用於清潔及/或還原銅表面成一純元素銅表面。
在本發明的某些實施例中,所述第二金屬表面可使用一鈍化層覆蓋或至少部分被覆蓋,其中該鈍化層可降低基層第二金屬表面的活性。例如,所述第二金屬表面可包含銅,而且銅可實質使用包含苯并三唑(Benzotriazole,BTA)或一苯并三唑衍生物的鈍化層覆蓋。例如,苯并三唑衍生物可包括具有取代苯并三唑,其具有一羥基(Hydroxy)取代的苯環(Benzene ring);諸如甲氧基(Methoxy)和乙氧基(Ethoxy)的烷氧基(Alkoxy);氨基(Amino);硝基(Nitro);諸如甲基(methyl)、乙基(Ethyl)和丁基(Butyl)的烷基(Alkyl);諸如氟、氯、溴和碘的鹵素。因此,在本發明的某些實施例中,所述第二金屬表面可為至少部分被使用含有苯并三唑的一鈍化層覆蓋,而且可進行表面處理以從所述第二金屬表面的表面除去苯并三唑,例如,從銅金屬的表面。
在本發明的某些實施例中,從所述第二金屬表面除去鈍化層可包括將該鈍化層暴露於一反應物,諸如(例如),甲酸(HCOOH)、乙酸(CH3COOH)、或丙酸(CH3CH2COOH)之至少一者。在某些實施例中,該反應物可包含一醇類(Alcohol)。在某些實施例中,該反應物可包括一醛類(Aldehyde)。在某些實施例中,該反應物可具有選自由醇類(-OH)、醛類(-CHO)、和羧酸(-COOH)組成的群組之至少一官能基。
在沒有受到操作的任何特定理論或模式的限制之下,侵蝕及/或除去鈍化層的製程可包括藉由使用反應物來還原該鈍化層的一或多個成份,使得可從基材表面除去該鈍化層的至少一部分。在某些實施例中,可使用包含羧
酸(Carboxylic acid)的反應物來侵蝕及/或除去該鈍化層。該鈍化層和羧酸之間的反應可產生一或多個揮發性副產物,其可容易從基材表面轉移而且從反應空間除去。例如,羧酸可還原形成部分鈍化層的氧化銅,使得所述氧化銅可復原到其元素狀態。
在本發明的某些實施例中,侵蝕及/或除去鈍化層可不包括還原該鈍化層的一或多個成份。例如,反應物可與該鈍化層的一或多個成份相互作用以侵蝕及/或除去該鈍化層,而不會或實質不會還原該鈍化層的任何成份。
含有至少一醇基的反應物可選自伯醇(Primary alcohol)、仲醇(Secondary alcohol)、叔醇(Tertiary alcohol)、多羥基醇(Polyhydroxy alcohol)、環醇(Cyclic alcohol)、芳醇(Aromatic alcohol)和醇類的其他衍生物組成的群組。
在某些實施例中,伯醇可具有連接至一個碳原子的-OH基,其中該碳原子係鍵結另一碳原子,尤其是根據通式(I)的伯醇:R1-OH (I)
其中R1是直鏈或支鏈C1-C20烷基或烯基,諸如(例如),甲基(Methyl)、乙基(Ethyl)、丙基(Propyl)、丁基(Butyl)、戊基(Pentyl)、或己基(Hexyl)。在本發明的非限制性示例實施例中,伯醇可包含甲醇(Methanol)、乙醇(Ethanol)、丙醇(Propanol)、丁醇(Butanol)、2-甲基丙醇(2-methyl propanol)、或2-甲基丁醇(2-methyl butanol)。
在某些實施例中,仲醇可具有連接一個碳原子的-OH基,其中該碳原子係鍵結兩個其他碳原子。尤其是,仲醇可具有通式(II):
其中每個R1是獨立選自直鏈或支鏈C1-C20烷基和烯基,諸如(例如),甲基、乙基、丙基、丁基、戊基、或己基的群組。如本發明的一非限制性實例實施例所示,第二醇可包含2-丙醇(2-propanol)、或2-丁醇(2-butanol)。
在某些實施例中,叔醇可具有連接一個碳原子的-OH基,其中該碳原子係鍵結三個其他碳原子。尤其是,叔醇可具有通式(III):
其中每個R1為獨立選自直鏈或支鏈C1-C20烷基和烯基,諸如(例如)甲基、乙基、丙基、丁基、戊基、或己基的群組。如本發明的一非限制性實例實施例所示,叔醇可包含三級丁醇(Tert-butanol)。
在某些實施例中,諸如(例如)二醇(Diol)和三醇(Triol)的多羥基醇具有如前述的伯醇、仲醇及/或叔醇基。多羥基醇的實例包括但沒有限於乙二醇(Ethylene glycol)和甘油(Glycerol)。
在某些實施例中,環醇具有連接至少一碳原子的-OH基,其為1至10環之一部分、或介於5-6個碳原子之間。
在某些實施例中,芳醇具有至少一-OH基,其連接至一苯環或側鏈中的一碳原子。
在某些實施例中,含有至少一醛基(-CHO)的反應物選自具有通式(IV)的化合物、具有通式(V)的烷烴化合物、和醛類(Aldehyde)的其他衍生物組成的群組。
因此,在某些實施例中,反應物可包含具有通式(IV)的醛類:R3-CHO (IV)
其中R3為選自氫和直鏈或支鏈C1-C20烷基和諸如(例如)甲基、乙基、丙基、丁基、戊基、或己基的烯基組成的群組。在某些實施例中,R3為選自由甲基或乙基組成的群組。根據通式(IV)的化合物之實例是甲醛(Formaldehyde)、乙醛(Acetaldehyde)和丁醛(Butyraldehyde)。
在某些實施例中,反應物為具有通式(V)的醛類:
OHC-R4-CHO (V)
其中R4是直鏈或支鏈C1-C20飽和或不飽和烴。或者,醛基可彼此直接鍵結(R4是不存在)。
在某些實施例中,含有至少一-COOH基的反應物為選自由通式(VI)的化合物、多羧酸(Polycarboxylic acid)、和羧酸(Carboxylic acid)的其他衍生物組成的群組。
因此,在某些實施例中,反應物為具有通式(VI)的羧酸;R5-COOH (VI)
其中R5是氫或直鏈或支鏈C1-C20烷基或烯基,諸如(例如)甲基、乙基、丙基、丁基、戊基、或己基。在某些實施例中,R5可為一直鏈或支鏈C1-C3烷基或烯基。根據通式(VI)的化合物的非限制性實例實施例可包括甲酸(Formic acid)、丙酸(Propanoic acid)、或乙酸(Acetic acid)。
在某些實施例中,反應物顯現出想要的蒸氣壓,使得反應物可在沒有加熱反應物的情況下而揮發。在某些實施例中,這種反應物僅包含一羧基(-COOH)。在某些實施例中,這種反應物可包含二羧酸(Dicarboxylic acid)。在某些實施例中,這種反應物不是一檸檬酸(Citric acid)。
在某些實施例中,可先對反應物加熱揮發反應物,然後將所述揮發的反應物傳遞到基材表面。在某些實施例中,這種反應物包含二羧酸,其包含乙二酸(Oxalic acid)。
在某些實施例中,從所述第二金屬表面除去鈍化層可包括將鈍化劑暴露於甲酸持續大於1秒、或大於25秒、或大於30秒、或大於1分鐘、或大於2分鐘、或甚至大於5分鐘的時段。在本發明的某些實施例中,從所述第二金屬表面除去鈍化層可包括將該基材加熱到大於20℃、或大於100℃、或大於150℃、或大於250℃、或大於300℃、或大於350℃、或甚至大於400℃的溫度。在某些
實施例中,從所述第二金屬表面除去鈍化層可包括將該基材加熱到約250℃的溫度。
在本發明的某些實施例中,進行所述第二金屬表面的表面處理可還原所述第二金屬表面。在某些實施例中,表面處理可除去可能存在所述第二金屬表面上的任何俱生氧化物。在某些實施例中,表面處理可除去可能存在所述第二金屬表面上的任何烴層(Hydrocarbon layer)。在某些實施例中,表面處理可在所述第二金屬表面上提供活性位(Active site)。
所述第二金屬表面的表面處理可採取例如使用諸如甲酸(Formic acid)的化學物或使用電漿的多種方法之任一者來完成。例如,可使用含氫電漿或諸如H-電漿或NH3電漿的化學基(Radical)來清潔基材表面。在某些實施例中,鹽酸(Hydrochloric acid,HCl)處理可當作表面處理方法使用。在某些實施例中,所述第二金屬表面處理製程可包括暴露該基材於例如甲酸的一處理反應物。其他第二金屬表面處理方法亦可能;在任何特定情況下使用的特殊表面處理方法可基於各種因素來選擇,諸如材料和沈積條件,例如包括基材表面上的材料類型。
選擇性沉積方法100可從製程步驟150繼續,其中將該基材轉移到一第二反應室,而且將該基材加熱到一想要的處理溫度。在本發明的某些實施例中,所述第一反應室和所述第二反應室可包括相同的反應室,而且在此實施例中,該基材可不經歷一轉移製程,即是,選擇性沉積方法100在單一反應室中進行。在替代實施例中,所述第一反應室和所述第二反應室可包括不同反應室,而且該基材可從所述第一反應室轉移到所述第二反應室。在某些實施例中,所述第一反應室和所述第二反應室可包括一組合設備工具,其中該基材從所述第一反應室轉移到所述第二反應室可在沒有暴露於環境大氣的受控環境下進行。在某些實施例中,所述第二反應室可包括一構成用於沉積製程的反應室,諸如(例
如),一原子層沉積室或一化學氣相沉積室。
一旦將基材轉移到所述第二反應室,將該基材加熱到一想要的處理溫度。在本發明的某些實施例中,可在第二反應室中將該基材加熱到一想要的沉積溫度。在某些實施例中,可將該基材加熱到大於約50℃、或大於約100℃、或大於約150℃、或大於約200℃、或大於約250℃、或大於約300℃、或大於約350℃、或甚至大於約400℃的沉積溫度。在本發明的某些實施例中,可將基材加熱到約50℃的溫度。
選擇性沉積方法100可從製程步驟160繼續,其中選擇性沉積一金屬薄膜在相對於所述第二金屬表面的該第一電介質表面上。在本發明的某些實施例中,選擇性沉積製程可包括一循環沉積製程,諸如(例如),原子層沉積或循環化學氣相沉積之一者。
一循環沉積製程的非限制性示例實施例可包括ALD,其中ALD是基於通常自限性反應,藉此反應物的循序和交替脈衝用於沉積每沉積週期約材料的一原子(或分子)單層。沉積條件和前驅物通常會被選擇提供自飽和反應,使得一反應物的吸收層留下不會與相同反應物的氣相反應物起反應的一表面末端。接著使基板與不同反應物接觸,該不同反應物與先前終端反應以實現持續沉積。因此,交替脈衝反應物的每個循環週期通常留下不超過約想要材料的一單層。然而,如前述,熟習該項技藝者將明白,在一或多個ALD循環週期中,例如,如果儘管製程的交替本質而如果發生某些氣相反應,則可沉積一個以上的材料單層。
在用於沉積金屬薄膜的ALD型製程中,一沉積循環可包括暴露該基材於一第一反應物;從反應空間除去任何未反應的第一反應物和反應副產物;及暴露該基材於一第二反應物,然後經歷一第二除去步驟。第一反應物可包含一含金屬前驅物,諸如一含鎢前驅物,而且該第二反應物可包含一還原劑
前驅物。
前驅物可透過諸如氬氣(Ar)或氮氣(N2)的惰性氣體而分離,以防止反應物間的氣相反應而且能夠自飽和表面反應。然而,在某些實施例中,可移動基材以分別接觸一第一氣相反應物和一第二氣相反應物。因為反應是自飽和,使得可不需要嚴格的基材溫度控制和精確的前驅物劑量控制。。然而,基材溫度最好是不會使入射氣體物質凝結成單層,或不會在基材表面上分解。在基材接觸下一活性化學物之前,諸如藉由吹掃反應空間或藉由移動基材,從基材表面除去過量的化學物和反應副產物(如果有的話)。藉由一惰性吹掃氣體可有效將不想要的氣體分子從反應空間排出。吹掃製程中可利用真空泵輔助。
在某些實施例中,循環沉積製程用於選擇性沉積金屬薄膜在基材上,而且所述循環沉積製程可為一ALD類型製程。在某些實施例中,循環沉積可為一混合ALD/CVD或循環CVD製程例如,在某些實施例中,相較於一CVD製程,ALD製程的沉積或生長率可能較低。增加生長率的一方法可為在比通常用於ALD製程的較高基材溫度下操作的方法,造成一化學氣相沉積製程,但仍然利用循序引入物或前驅物,這種製程可稱為循環CVD。
根據本發明的某些實施例,ALD製程用於選擇性沉積一金屬薄膜在基材的電介質表面上,諸如一積體電路工件。在某些實施例中,每個ALD循環週期可包括兩不同沉積步驟或階段。在沉積循環的第一階段(金屬階段)中,需要沉積的基材表面係接觸一第一氣相反應物,其包含含有氣相反應物的至少一金屬,其被化學吸附到基材表面上,在基材表面上形成沒有超過約反應物質的一單層。在沉積循環的一第二階段(還原階段),需要沉積的基材表面係接觸一第二氣相反應物,其包含至少一還原劑前驅物,其與先前化學吸附的物質起反應,以在基材的電介質表面上選擇性形成一金屬薄膜。
在某些實施例中,所述含金屬前驅物(在本說明亦稱為「金屬化
合物」)可包含一金屬。在某些實施例中,該金屬可包含一過渡金屬。在本發明的某些實施例中,該金屬可選自下列組成的群組:Ti、Co、V、Cr、Mn、Nb、Mo、Ru、Rh、Pd、Ag、Hf、Ta、W、Re、Os、Ir和Pt。在某些實施例中,所述含金屬前驅物可包含Co、Ru、W、Ta、Nb、Ti、Mo、或V之至少一者。在某些實施例中,所述含金屬前驅物包含鎢(W)。
在本發明的某些實施例中,所述含金屬前驅物可包含一金屬鹵化物(F、Cl、Br、I)。在某些實施例中,所述含金屬前驅物可包含一過渡金屬鹵化物。例如,如一非限制性示例實施例所示,所述含金屬前驅物可包含WF6、TaF5、NbF5、TiF4、MoFx或VFx之至少一者。在本發明的某些實施例中,所述含金屬前驅物可包含六氟化鎢(Tungsten hexafluoride)(WF6)。
在某些實施例中,暴露該基材於含有氣相反應物的至少一金屬可包括對在基材上方的金屬前驅物進行脈衝持續介於約0.01秒和約60秒、介於約0.05秒和約10秒、或介於約0.1秒和約5.0秒之間的時段。此外,在基材上方進行金屬前驅物脈衝期間,所述金屬前驅物的流率可小於1000sccm、或小於500sccm、或小於250sccm、或小於100sccm、或甚至小於50sccm。
過量的金屬前驅物和反應副產物(如果有的話)可從基材表面將除去,例如藉由使用惰性氣體泵排(Pumping)。例如,在本發明的某些實施例中,所述方法可包括一吹掃循環週期,其中可在小於約2.0秒的時段吹掃該基材表面。過量的金屬前驅物和任何反應副產物可藉由一泵排系統產生的真空輔助將其除去。
在沉積循環的第二階段(還原階段)中,該基材接觸含有至少一還原劑前驅物的一第二氣相反應物。在本發明的某些實施例中,含有蒸氣反應物的所述至少一還原劑可包含氫氣(H2)、甲矽烷(SiH4)、二矽烷(Si2H6)、三矽烷(Si3H8)、鍺烷(GeH4)、二鍺烷(Ge2H6)、或二硼烷(B2H6)之至少一者。在某些實施
例中,所述至少一還原劑可包含一電漿,諸如(例如),一含有原子氫、氫離子和氫基的氫電漿。在某些實施例中,該還原劑前驅物可包含具有普通實驗式SixH(2x+2)的較高序化矽烷。在某些實施例中,該還原劑前驅物可包含具有普通實驗式GexH(2x+2)的較高序化鍺酸(Germane)。
在某些實施例中,暴露該基材於還原劑氣相反應物可包括對基材上方的還原劑前驅物(例如,二矽烷)進行脈衝持續介於約0.01秒和約60秒、介於約0.05秒和約10秒、或介於約0.1秒和約5.0秒之間的時段。在對該基材上方的還原劑前驅物進行脈衝期間,該還原劑前驅物的流率可小於1000sccm、或小於500sccm、或小於250sccm、或小於100sccm、或甚至小於50sccm。
含有一還原劑反應物的第二氣相反應物可與留在基材上的含金屬分子起反應。在某些實施例中,該還原劑前驅物能夠還原留在基材上的含金屬分子,以在該基材的電介質表面上形成一選擇性元素金屬。在本發明的某些實施例中,該選擇性元素金屬可包含鎢(W)。
如果有任何的過量第二來源化學物和反應副產物,則可將其從該基材表面將其除去,例如,藉由一吹掃氣體脈衝及/或由泵排系統產生的真空。吹掃氣體最好為任何惰性氣體,諸如但沒有限於氬(Ar)、氮(N2)、或氦(He)。如果介入吹掃(即是,吹掃氣體脈衝)或其他反應物除去步驟,則通常考慮一階段緊接另一階段。
在沉積一選擇性金屬薄膜的想要厚度之前,基材為交替接觸第一氣相反應物(即是,含金屬前驅物)和第二氣相反應物(即是,還原劑前驅物)的沉積循環可重複兩或多次。應明白,在本發明的某些實施例中,基材接觸第一相反應物和第二氣相反應物的順序可使得該基材首先接觸第二氣相反應物,然後接觸第一氣相反應物。此外,在某些實施例中,循環沉積製程可包含該基材接觸第一氣相反應物(即是,含金屬前驅物)一或多次,然該基材接觸第二氣相反應
物(即是,還原劑前驅物)一或多次,而且同樣地,可替代性包括該基材接觸第二氣相反應物接觸一或多次,然後該基材接觸第一氣相反應物一或多次。此外,本發明的某些實施例可包含非電漿反應物,例如,所述第一和第二氣相反應物實值為不是離子化活性物質。在某些實施例中,所述第一和第二氣相反應物實值為不是離子化活性物質、受激物質或自由基物質。例如,所述第一氣相反應物和所述第二氣相反應物兩者可包含非電漿反應物,以防止離子化損壞基層基材和由此產生的相關缺陷。
本說明書描述中,利用一含金屬前驅物和一還原劑前驅物在該基材的電介質表面上形成一選擇性金屬薄膜的循環沉積方法可在具有一加熱基材的ALD或CVD沉積系統中進行。例如,在某些實施例中,方法可包括將該基材加熱到介於約50℃和約150℃的溫度,或甚至將該基材加熱到介於約50℃和約120℃的溫度。當然,任何特定循環沉積製程(諸如(例如),一ALD反應)的適宜溫度窗域將取決於表面末端和有關的反應物種類。在本說明書,溫度是隨著所要使用的前驅物而變化,而且通常為約700℃或低於該溫度。在某些實施例中,針對氣相沉積製程的沉積溫度通常為在約50℃或高於該溫度,而且在某些實施例中,沉積溫度是介於約50℃和約250℃之間,而且在某些實施例中,沉積溫度是介於約50℃和約200℃之間。在某些實施例中,沉積溫度是低於約500℃、低於約400℃或低於約300℃。在某些情況下,例如,如果在製程中使用添加反應物或還原劑,沉積溫度則可低於約200℃、低於約150℃或低於約100℃。在某些情況下,沉積溫度可高於約20℃、高於約50℃和高於約75℃。在本發明的某些實施例中,沉積溫度(即是,沉積期間的基材溫度)為約50℃。
在某些實施例中,在電介質表面上選擇性金屬薄膜的生長速率可為從約0.005Å/週期至約20Å/週期、從約0.05Å/週期至約10Å/週期、從約0.1Å/週期至約10Å/週期、從約1Å/週期至約5Å/週期。在某些實施例中,該薄膜的生長
速率為高於約0.01Å/週期、高於約0.05Å/週期、高於約0.1Å/週期、高於約0.5Å/週期、高於約1Å/週期、高於約1.5Å/週期。在某些實施例中,該薄膜的生長速率為小於約20Å/週期、小於約10Å/週期、小於約5Å/週期。在本發明的某些實施例中、W金屬薄膜的生長速率為約1.5Å/週期。
在其他實施例中,根據本發明的實施例所沉積的選擇性金屬薄膜可包含小於約20氧原子%、小於約10氧原子%、小於約5氧原子%、或甚至小於約2氧原子%。在進一步實施例中,該等選擇性金屬薄膜可包含小於約10氫原子%、或小於約5氫原子%、或小於約2氫原子%、或甚至小於約1氫原子%。在仍然進一步實施例中,該等選擇性金屬薄膜可包含小於約10碳原子%、或小於約5碳原子%、或小於約2碳原子%、或小於約1碳原子%、或甚至小於約0.5碳原子%。在本說明書描述的實施例中,可利用盧瑟福背散射法(Rutherford backscattering,RBS)決定元素的原子濃度。
在本發明的某些實施例中,選擇性沉積的金屬薄膜可沉積在三維結構上。在某些實施例中,金屬薄膜的階梯覆蓋率可等於或大於約50%、或大於約80%、或大於約90%、或大於約95%、或大於約98%、或大於約99%、或具有高於約2、高於約5、高於約10、高於約25、高於約50、或甚至高於約100的縱橫比(高度/寬度)的較大結構。
在某些實施例中,根據本說明書描述的某些實施例所沉積的選擇性金屬薄膜可具有大於約20nm、大於約30nm、大於約40nm、大於約50nm、大於約60nm、大於約100nm、大於約250nm、大於約500nm、或較大的厚度。在某些實施例中,根據本說明書描述的某些實施例所沉積的選擇性金屬薄膜可具有小於約50nm、小於約30nm、小於約20nm、小於約15nm、小於約10nm、小於約5nm、小於約3nm、小於約2nm、或甚至小於約1nm的厚度。
在本發明的某些實施例中,選擇性沉積製程可在相對於一第二金
屬表面的一第一電介質表面上沉積較大量的金屬薄膜。在某些實施例中,本說明書揭露方法的選擇性可大於約80%、大於約90%、大於約95%、或甚至大於約100%。在某些實施例中,沉積製程的選擇性為至少約80%,這對於某些特定應用可為足夠選擇性。在某些情況下,該選擇性是至少約為50%,這對於某些特定應用可為足夠選擇性。
如本發明的選擇性沉積方法的非限制性示例實施例,圖2示意說明包含根據本發明的實施例所沉積一選擇性金屬薄膜的半導體結構200的掃描式電子顯微鏡截面圖。更具體係,圖2示意說明包含一基材202、一圖案化電介質層204和一設置在該圖案化電介質層206的金屬層之半導體結構200。在此非限制性示例結構中,該基材202為一矽基材,該圖案化電介質層204為一具有介電常數2.55的低k介電材料,而且設置在該圖案化電介質層206的金屬層為銅。該半導體結構200亦包含該選擇性金屬薄膜208,其包含鎢(W),其僅設置在所述低k電介質材料的表面上而且不是在設置在該圖案化電介質薄膜204內的銅金屬206的表面上。
本說明書揭露的沉積製程所沉積的選擇性金屬薄膜可用於各種環境,諸如用於形成半導體裝置結構。熟習該項技藝者應明白,本說明書描述的製程可適用於許多環境,包括但沒有限於裝置接觸結構。
如一非限制性示例所示,圖3A-3D示意說明製造包含根據本發明的實施例所沉積一選擇性金屬薄膜的半導體裝置結構之方法。應注意,圖3A-3D的示意說明僅說明半導體裝置結構的一選擇部分,即是,接觸結構,而且不包括完整製造的裝置結構的所有特徵件,諸如(例如),支撐基材(例如,一矽基材)和有源裝置結構(例如,電晶體結構)。
更具體係,圖3A示意說明包含一金屬觸點302的半導體裝置結構300之一部分,在某些實施例中,其可包含一銅金屬。設置在該金屬觸點302上
方是一層間電介質304,其可包含二氧化矽(SiO2)或氮化矽(SiN)。該層間電介質用於隔離相鄰金屬線(未示出)並降低不想要的電容耦合。
為了互連該金屬觸點302與附加的金屬化層級,需要暴露金屬觸點302的一部分而且利用一低電阻金屬填充物(Metal fill)來互連不同的互連層。更具體係,圖3B示意說明包含金屬接點302和層間電介質的其餘部分304'之半導體裝置結構306。該半導體裝置結構306亦包括一接觸孔308,其可在暴露基層金屬接點之前藉由蝕刻該層間電介質304的一部分形成,因此暴露金屬表面310。
請即參考圖3C製造根據本發明之實施例之半導體裝置結構的方法,其中圖3C示意說明包括金屬接點302、層間電介質的其餘部分304'、接觸孔308和選擇性金屬薄膜314的半導體裝置結構312。如圖3C所示,選擇性金屬薄膜314(例如,一鎢(W)薄膜)直接設置在其餘的層間電介質304'上方,而不是設置在所述金屬觸點310上方。
接觸結構的製造可完全利用具一低電阻接觸插塞填充接觸孔的其餘部分完成,如圖3D的半導體裝置結構316所示。如圖3D所示,接觸孔的其餘部分填充一低電阻接觸插塞318,其中在某些實施例可包括一低電阻鎢(W)接觸插塞。在本發明的某些實施例中,可使用本發明的方法沉積低電阻接觸插塞318,或者(可替代性),可使用化學氣相沉積(CVD)來沉積所述低電阻接觸插塞318。可進一步處理該半導體裝置結構316以形成一平坦面320,例如,可對該結構進行半導體裝置結構的上表面的拋光或化學機械拋光之一或多者,藉此形成平坦面320。可進一步處理該半導體裝置結構316以增添包含一或多個附加層間電介質層和金屬化層的附加金屬連接層。
因此,本發明的實施例包括一包含使用本說明書揭露的方法沉積一金屬薄膜之半導體裝置結構。在某些實施例中,該半導體裝置結構可包含一直接設置在電介質表面上方的鎢薄膜。在某些實施例中,該半導體裝置結構可
包括一接觸結構,該接觸結構包含一層間電介質和一銅接點,其中該銅接點未直接接觸一阻障金屬,即是,該銅接點的表面不含一阻障金屬,諸如(例如),一氮化鈦(TiN)阻障金屬。在本發明的其他實施例中,該接點金屬(例如,一銅接點)未被一鎢(W)成核層(即是,一高電阻鎢(W)成核層)所覆蓋。因此,本發明的實施例可用於製造由一銅接點、一選擇性鎢薄膜和一鎢觸點插塞所組成的接觸結構。在某些實施例中,本發明的實施例所形成的接觸結構可具有小於1000Ohm.cm2、或小於500Ohm.cm2、或小於350Ohm.cm2、或小於200Ohm.cm2、或甚至小於100Ohm.cm2的電阻率。
前述本發明的示例實施例沒有限制本發明的範疇,因為這些實施例僅是本發明的實施例的實例,其是由文後申請專利範圍及其合法的等同請求項所定義。任何等效具體例意欲處於本發明之範疇內。實際上,除了本說明書所示和所述之類以外,熟習該項技藝者可從描述更明白本發明的各種修改,諸如所述元件的替代可用組合。這些修改和實施例亦在文後申請專利範圍的範疇內。
Claims (20)
- 一種用於在包含一第一電介質表面和一第二金屬表面的基材上選擇性沉積金屬薄膜的方法,該方法包括:暴露該基材於一鈍化劑;在該第二金屬表面上進行一表面處理;及在相對於所述第二金屬表面的該第一電介質表面上選擇性沉積該金屬薄膜。
- 如請求項1所述之方法,其中在該第二金屬表面上進行一表面處理更包括從該第二金屬表面除去一鈍化層。
- 如請求項1所述之方法,其中暴露該基材於一鈍化劑而且在該第二金屬表面上進行一表面處理是在大於約250℃的基材溫度下進行。
- 如請求項1所述之方法,其更包括先對該基材釋氣,然後暴露該基材於所述鈍化劑。
- 如請求項4所述之方法,其中使該基材釋氣更包括在大於約250℃的溫度下使該基材釋氣持續大於約15秒的時段。
- 如請求項1所述之方法,其中該鈍化劑包含一烷基鹵化矽烷。
- 如請求項1所述之方法,其中該鈍化劑包含三甲(二甲胺基)矽烷。
- 如請求項1所述之方法,其中暴露該基材於一鈍化劑更包括暴露該基材於一鈍化劑持續大於15秒的時段。
- 如請求項1所述之方法,其中該鈍化層包含苯并三唑、或一苯并三唑衍生物。
- 如請求項2所述之方法,其中從所述第二金屬表面除去該鈍化層包括暴露該鈍化層於甲酸。
- 如請求項10所述之方法,其中該第二金屬表面包含一氧化銅, 而且暴露該鈍化層於甲酸從而將該氧化銅還原成銅。
- 如請求項1所述之方法,其中暴露該基材於一鈍化劑而且在該第二金屬表面上進行一表面處理是在一第一反應室中進行,而且選擇性沉積該金屬薄膜是在一第二反應室中進行。
- 如請求項1所述之方法,其中選擇性沉積該金屬薄膜包括進行一或多個循序沉積循環,每個沉積循環包括該基材交替接觸一含金屬前驅物與一還原劑前驅物。
- 如請求項1所述之方法,其中選擇性沉積該金屬薄膜更包括將該基材加熱到大於約50℃的溫度。
- 如請求項11所述之方法,其中該含金屬前驅物包含六氟化鎢(WF6)、五氟化鉭(TaF5)、五氟化鈮(NbF5)、四氟化鈦(TiF4)、氟化鉬(MoFx)、或氟化釩(VFx)中之至少一者。
- 如請求項11所述之方法,其中該還原劑前驅物包含氫氣(H2)、氫氣(H2)電漿、氨氣(NH3)電漿、氨氣(NH3)、甲矽烷(SiH4)、二矽烷(Si2H6)、三矽烷(Si3H8)、鍺烷(GeH4)、二鍺烷(Ge2H6)、或二硼烷(B2H6)中之至少一者。
- 如請求項1所述之方法,其中該金屬薄膜包括鎢(W)。
- 如請求項1所述之方法,其中該選擇性大於約90%。
- 一種半導體裝置結構,其包含如請求項1所述之方法所沉積的該金屬薄膜。
- 如請求項19所述之半導體裝置結構,其中該金屬薄膜包含一設置在電介質表面上方的鎢薄膜。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI744804B (zh) * | 2019-08-29 | 2021-11-01 | 南韓商秀博瑞殷股份有限公司 | 薄膜形成用生長抑制劑,利用該生長抑制劑的薄膜形成方法以及由此製造的半導體基板 |
TWI744803B (zh) * | 2019-09-25 | 2021-11-01 | 南韓商秀博瑞殷股份有限公司 | 薄膜製造方法及薄膜製造裝置 |
CN116351662A (zh) * | 2023-03-31 | 2023-06-30 | 浙江大学 | 一种聚合物薄膜区域选择性沉积的方法 |
CN116351662B (zh) * | 2023-03-31 | 2024-05-17 | 浙江大学 | 一种聚合物薄膜区域选择性沉积的方法 |
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US20210296130A1 (en) | 2021-09-23 |
KR20190039642A (ko) | 2019-04-15 |
US20190109009A1 (en) | 2019-04-11 |
TW202307244A (zh) | 2023-02-16 |
US11094546B2 (en) | 2021-08-17 |
TWI781229B (zh) | 2022-10-21 |
US20200013626A1 (en) | 2020-01-09 |
US10403504B2 (en) | 2019-09-03 |
TWI819806B (zh) | 2023-10-21 |
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