CN103946957B - 使用铝烷基的前驱物的金属薄膜沉积 - Google Patents
使用铝烷基的前驱物的金属薄膜沉积 Download PDFInfo
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- CN103946957B CN103946957B CN201280054152.9A CN201280054152A CN103946957B CN 103946957 B CN103946957 B CN 103946957B CN 201280054152 A CN201280054152 A CN 201280054152A CN 103946957 B CN103946957 B CN 103946957B
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- alane
- amine
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- 239000002243 precursor Substances 0.000 title claims abstract description 17
- 229910000086 alane Inorganic materials 0.000 title claims description 73
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims description 69
- 230000008021 deposition Effects 0.000 title claims description 45
- 238000000034 method Methods 0.000 claims abstract description 88
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 150000001412 amines Chemical class 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 13
- 150000005309 metal halides Chemical class 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 7
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 5
- 125000000468 ketone group Chemical group 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims description 51
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000010408 film Substances 0.000 claims description 21
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 21
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 claims description 11
- 229910004537 TaCl5 Inorganic materials 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 8
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910001510 metal chloride Inorganic materials 0.000 claims description 5
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001509 metal bromide Inorganic materials 0.000 claims description 3
- 229910001511 metal iodide Inorganic materials 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 claims description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims 1
- 206010011224 Cough Diseases 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 52
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052737 gold Inorganic materials 0.000 abstract description 8
- 239000010931 gold Substances 0.000 abstract description 8
- -1 aluminium alkane Chemical class 0.000 abstract description 6
- 239000004411 aluminium Substances 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 2
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 72
- 239000000376 reactant Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000010936 titanium Substances 0.000 description 20
- 230000004048 modification Effects 0.000 description 19
- 238000012986 modification Methods 0.000 description 19
- 238000000746 purification Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 239000003708 ampul Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910052756 noble gas Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000000427 thin-film deposition Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 150000002835 noble gases Chemical class 0.000 description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- HJBWJAPEBGSQPR-UHFFFAOYSA-N DMCA Natural products COC1=CC=C(C=CC(O)=O)C=C1OC HJBWJAPEBGSQPR-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- 229910016859 Lanthanum iodide Inorganic materials 0.000 description 1
- 229910014323 Lanthanum(III) bromide Inorganic materials 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229910010038 TiAl Inorganic materials 0.000 description 1
- 229910010386 TiI4 Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- KYKBXWMMXCGRBA-UHFFFAOYSA-K lanthanum(3+);triiodide Chemical compound I[La](I)I KYKBXWMMXCGRBA-UHFFFAOYSA-K 0.000 description 1
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- GCPVYIPZZUPXPB-UHFFFAOYSA-I tantalum(v) bromide Chemical compound Br[Ta](Br)(Br)(Br)Br GCPVYIPZZUPXPB-UHFFFAOYSA-I 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
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
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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 System
- H01L21/28556—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 System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
- H01L21/28562—Selective deposition
-
- 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
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- 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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
Abstract
本发明提供沉积纯金属和铝合金金属薄膜的方法。某些方法包括使基板表面与第一前驱物和第二前驱物接触,该第一前驱物包含铝前驱物,该铝前驱物选自二甲基铝氢化物、配位于胺的铝烷和具有由式(I)或(II)表示的结构的化合物,其中R为C1‑C6烷基,而该第二前驱物包含金属卤化物。其他的方法涉及使基板按顺序地曝露于第一前驱物和第二前驱物,该第一前驱物包含如上所述的铝前驱物,而该第二前驱物包含Ti(NR'2)4或Ta(NR'2)5,其中R'为烷基、烯基、炔基、酮基或醛基。
Description
技术领域
本发明的实施例大体而言涉及薄膜沉积,具体而言涉及使用金属卤化物和铝烷基(alane-based)的前驱物的薄膜沉积。
背景技术
在基板表面上沉积薄膜是多种产业中的重要工艺,这些产业包括半导体处理、扩散阻挡涂层和用于磁性读/写头的介电质。尤其,在半导体产业中,小型化要求原子等级的薄膜沉积控制,以在高纵横比的结构上产生保形的(conformal)涂层。
一种用于沉积薄膜的方法是原子层沉积(ALD)。大多数的ALD工艺是基于二元的反应序列,该二元的反应序列中两个表面反应每个按顺序发生。由于这些表面反应是按顺序的,故两个气相反应物未互相接触,而且可能形成和沉积颗粒的气相反应会受到限制。虽然ALD往往比传统的化学气相沉积(CVD)产生更保形的薄膜,但ALD的现有技术工艺已经是对于沉积金属氧化物和金属氮化物薄膜最有效的。虽然已经开发了几种可有效沉积元素钌和其他后过渡金属的工艺,但一般的用于沉积纯金属的ALD工艺仍不足以成功地被商业化使用。
特定而言,钛(Ti)和钽(Ta)的纯金属薄膜在集成电路制造工艺中有许多关键的应用。这样的应用包括作为钨、铝和铜衬垫,以及金属栅极材料。然而,许多这些纯金属必须使用等离子气相沉积(PVD)、等离子增强化学气相沉积(PECVD)或等离子增强原子层沉积(PEALD)来沉积。这些方法会有不良阶梯覆盖或由等离子引起的基板损坏的问题。因此,需要有新的沉积化学品和方法,该新的沉积化学品和方法是商业上可行且无先前使用方法的缺点,特别是在元素金属薄膜的区域。本发明通过提供新颖的方法解决了这个问题,该新颖的方法经过特别设计和优化,以避免其他方法相关的问题。
发明内容
本发明的一个方面涉及一种沉积薄膜的方法。以下列出各种实施例。应了解到,以下列出的实施例不仅可以如以下所列出的那样来组合,而且还可以以依据本发明范围的其他适当组合来组合。
在实施例1中,该方法包括使基板表面与第一前驱物和第二前驱物接触,该第一前驱物包含铝前驱物,该铝前驱物选自二甲基铝氢化物、配位于胺的铝烷和具有由下式表示的结构的化合物:
其中R为C1-C6烷基,而该第二前驱物包含金属卤化物。
实施例2包括对实施例1的修改,其中R为甲基。
实施例3包括对实施例1或2的修改,其中该配位于胺的铝烷包括二甲基乙基胺铝烷(dimethylethylamine alane)、三乙基胺铝烷(triethylamine alane)、三甲基胺铝烷(trimethylamine alane)或甲基吡咯烷铝烷(methylpyrrolidine alane)。
实施例4包括对实施例1至3任一者的修改,其中使该基板表面与该第一前驱物和该第二前驱物接触是按顺序地发生。
实施例5包括对实施例1-4任一者的修改,其中该金属选自钛(Ti)、钽(Ta)、锆(Zr)、镧(La)、铈(Ce)、硅(Si)、锗(Ge)、W(钨)和铪(Hf)。
实施例6包括对实施例1-5任一者的修改,其中该第二前驱物包含金属氯化物、金属碘化物或金属溴化物。
实施例7包括对实施例1-6任一者的修改,其中该金属氯化物选自TiCl4和TaCl5。
实施例8包括对实施例1-7任一者的修改,其中使用过量的胺。
实施例9包括对实施例1-8任一者的修改,其中该第一前驱物包含二甲基铝氢化物而该第二前驱物包含TiCl4。
实施例10包括对实施例1-9任一者的修改,其中沉积是在约23℃至约300℃的温度下进行。
实施例11包括对实施例1-10任一者的修改,其中该沉积出的薄膜包含纯金属。
实施例12包括对实施例1-11任一者的修改,其中该沉积出的薄膜包含金属合金。
实施例13包括对实施例1-12任一者的修改,实施例13进一步包括在氢气或等离子处理中退火。
实施例14涉及一种沉积薄膜的方法,该方法包括使基板曝露于第一前驱物和第二前驱物,该第一前驱物包含铝前驱物,该铝前驱物选自二甲基铝氢化物、配位于胺的铝烷和具有由下式表示的结构的化合物:
其中R为C1-C6烷基,而该第二前驱物包含Ti(NR'2)4或Ta(NR'2)5,其中R'为C1-C4烷基、烯基、炔基、酮基或醛基。
实施例15涉及对实施例14的修改,其中R为甲基。
实施例16涉及对实施例14或15的修改,其中该第二前驱物包含Ti(NMe2)4或Ta(NMe2)5。
实施例17包括对实施例14-16任一者的修改,其中沉积是在约50℃至约150℃的温度下进行。
实施例18包括对实施例14-17任一者的修改,其中使用过量的胺。
实施例19包括对实施例14-18任一者的修改,其中该配位于胺的铝烷包含二甲基乙基胺铝烷、三乙基胺铝烷、三甲基胺铝烷或甲基吡咯烷铝烷。
实施例20涉及一种沉积薄膜的方法,该方法包括使基板表面按顺序地与第一前驱物和第二前驱物接触,该第一前驱物包含二甲基乙基胺铝烷、三乙基胺铝烷、三甲基胺铝烷或甲基吡咯烷铝烷,该第二前驱物包含TiCl4或TaCl5。
附图说明
图1A-B图示了依据本发明的一个或多个实施例所沉积的薄膜的XPS组成分析。
具体实施方式
在描述本发明的一些例示性实施例之前,应了解到,本发明并不限于以下描述中所提出的结构或工艺步骤的细节。本发明能够有其他的实施例,而且可以各种方式实施或进行本发明。
本文中使用的“基板”是指任何形成于基板上的基板或材料表面,在制造工艺的过程中薄膜处理是在该基板上进行。举例来说,上面可以进行处理的基板表面包括诸如硅、氧化硅、应变硅、绝缘体上硅(SOI)、掺杂碳的硅氧化物、氮化硅、掺杂的硅、锗、砷化镓、玻璃、蓝宝石之类的材料,以及任何其他的材料,诸如金属、金属氮化物、金属合金以及其他的导电材料,视应用而定。基板包括但不限于半导体晶片。可使基板进行预处理工艺,以抛光、蚀刻、还原、氧化、羟化、退火和/或烘烤基板表面。除了直接在基板本身的表面上进行薄膜处理之外,在本发明中也可以在形成于基板上的下层上进行任何所揭示的薄膜处理步骤,如以下更详细揭示的,并且术语“基板表面”意在包括如上下文所指的这种下层。
本文中使用的“纯金属薄膜”是指本质上只含有一种金属的薄膜。在某些实施例中,这样的金属包括钛(Ti)、钽(Ta)、锆(Zr)、镧(La)、铪(Hf)或铈(Ce)。在某些实施例中,纯金属薄膜也可以包含杂质,尤其是小于5%的量的不需要的元素。在某些实施例中,纯金属薄膜可包含一些铝。
依据本发明的各种实施例,提供了与纯金属和铝金属合金的沉积有关的方法。因此,本发明的一个方面涉及沉积薄膜的方法,该方法包括使基板表面与第一和第二前驱物接触,该第一前驱物包含铝前驱物,而该第二前驱物包含金属卤化物。在一个或多个实施例中,该铝前驱物可以选自二甲基铝氢化物、配位于胺的铝烷和具有由下式表示的结构的化合物:
其中R为C1-C6烷基,而该第二前驱物包含金属卤化物。
本发明的各种实施例涉及使用配位于胺的铝烷(氢化铝或AlH3)前驱物。铝烷是不稳定的化合物,但可以通过配位于胺而稳定。这种前驱物可以由式AlH3-NR3表示。这些前驱物可以依据以下方程式1来合成:
LiAlH4+NR3-HCl→AlH3-NR3+H2+LiCl(方程式1)
这样的胺的实例包括但不限于:二甲基乙基胺(DMA)、三乙基胺(TEA)、三甲基胺(TMA)和N-甲基吡咯烷。因此,相应的铝烷前驱物可以是二甲基乙基胺-铝烷(DMEAA)、三乙基胺-铝烷(TEAA)、三甲基胺-铝烷(TMAA)和N-甲基吡咯烷-铝烷(NPA)。因此,在具体的实施例中,配位于胺的铝烷包括二甲基乙基胺铝烷、三乙基胺铝烷、三甲基胺铝烷或甲基吡咯烷铝烷。
在某些其他的实施例中,可以使用其他的铝前驱物。这种铝前驱物包括二甲基铝氢化物(DMAH)。使用这种铝前驱物的实施例可被用于较高的温度。
另在其他的实施例中,合适的铝前驱物包括具有下式表示的结构那些:
其中R为任何的C1-C6烷基。在具体的实施例中,R为甲基。
依据本发明的各种实施例,金属卤化物也被用来作为前驱物。可以依据所需的金属薄膜选择金属。在一个实施例中,该金属选自第3族、第4族和第5族过渡金属。在具体实施例中,该金属选自钛(Ti)、钽(Ta)、锆(Zr)、镧(La)、铪(Hf)、铈(Ce)、硅(Si)、锗(Ge)和钨(W)。在特定的实施例中,该金属为Ti或Ta。在其他的实施例中,该卤化物选自Cl、I和Br,使得该第二前驱物包含金属氯化物、金属碘化物或金属溴化物。因此,几个合适的金属卤化物前驱物的非限制性实例包括TaCl5、TaBr5、TaI5、TiCl4、TiBr4、TiI4、LaCl3、LaBr3、LaI3。在特定的实施例中,该金属卤化物前驱物为TiCl4或TaCl5。在其他的实施例中,使用第14族的金属,例如Si和Ge。
本发明的另一个方面涉及沉积薄膜的方法,该方法包括使基板曝露于第一前驱物和第二前驱物,该第一前驱物包含配位于胺的铝烷,而该第二前驱物包含Ti(NR'2)4或Ta(NR'2)5,其中R'为烷基、烯基、炔基、酮基或醛基。在这个方面的一个变体中,该基板表面可以按顺序地或大致上按顺序地曝露于该第一前驱物和该第二前驱物。在另一个变体中,该曝露可以是同时或大致同时的。在特定的实施例中,R'为C1-C4,并且在非常具体的实施例中,R'为C1-C4烷基。在特定的实施例中,该第二前驱物包含Ti(NMe2)4或Ta(NMe2)5。获得这种前驱物的方法的一个实例可以通过将TaCl5与LiNR2在溶剂的存在下反应而获得,以得到Ta(NR'2)5,并带有氯化锂副产物。该合成可以由以下方程式2表示:
TaCl5+5LiNR2→Ta(NR'2)5+5LiCl(方程式2)
工艺温度是工艺的重要部分,而且是有关是否沉积纯金属相较于(versus)合金的因素之一。虽然不希望受到任何特定理论的限制,但据认为铝烷前驱物会减少金属卤化物而去除卤化物,因而留下纯金属。在较高的温度下,铝烷前驱物将会分解,这可能会导致铝掺入薄膜中。在较低的温度下,铝烷前驱物不会分解,而将会沉积纯金属。合金相较于纯金属沉积的具体温度范围可能会随着所使用的铝烷前驱物而改变。因此,在需要纯金属时,可将腔室或基板加热,使得沉积可以在低于约300℃的温度下发生。在其他的实施例中,沉积可以在低于约100℃的温度下发生。在一个实施例中,沉积是在约50℃至约300℃的温度范围内进行,而在甚至更具体的实施例中,沉积是在从约50℃至约150℃的温度范围内进行。在需要铝合金金属之处,该工艺可在高于约300℃的温度下进行。然而,在其他的实施例中,合金沉积可在低至约150℃、100℃或75℃的温度下发生。
还可以通过使用胺的多少来控制沉积薄膜中的铝含量。在一个实施例中,使用过量的胺。过量的胺是指相对于铝烷为多于一个的摩尔当量。在某些实施例中,可以使用胺作为载气,该载气将对应于大于99:1的比。使用用于携带铝烷的过量胺可以用来作为降低薄膜中的铝浓度的方法。过量的胺也可以增强阶梯覆盖率并提高沉积温度。在前驱物包含配位于胺的铝烷的一些实施例中,过量的胺可以是铝烷所配位的胺。因此,举例来说,当铝烷前驱物为DMEAA时,可以使用过量的DMEA。另一种适合的过量使用的胺包括二甲基环己基(DMCA)胺。
在一个实施例中,薄膜使用化学气相沉积工艺来沉积。在这样的工艺中,可将基板同时或大致上同时曝露于铝烷前驱物和金属卤化物二者。
在另一个实施例中,薄膜是使用原子层沉积(ALD)工艺所沉积。因此,在一个实施例中,基板表面与第一前驱物和第二前驱物接触是按顺序地或大致上按顺序地发生。在更具体的实施例中,该方法包括金属卤化物曝露、然后净化、然后曝露于配位于胺的铝烷、然后另一次净化。在ALD工艺的例示性实施例中,在第一半反应中使第一化学前驱物(“A”),例如TiCl4或TaCl5脉冲化或流动到基板表面。通常通过排空泵抽出和/或通过流动的惰性净化气体来去除过量的反应物和反应副产物。然后将共反应物或前驱物“B”(例如配位于胺的铝烷)输送到表面,其中该第一半反应的前驱物与来自“B”共反应物的新配位体进行反应,产生交换的副产物。“B”共反应物也与下层的反应性物种形成自饱和键,以提供饱和的第二半反应。通常利用第二净化期间来去除未使用的反应物和反应副产物。然后可再次流入“A”前驱物、“B”共反应物和净化气体。持续表面交替地曝露于反应物“A”和“B”,直至达到所需的薄膜厚度,对于大多数预期的应用,该所需的薄膜厚度将大约在5nm至40nm的范围中,并且更具体地是在10nm至30nm(100埃至300埃)的范围中。应了解到,“A”、“B”和净化气体可以同时流动,而且基板和/或气体流动喷嘴可以摆动,使得基板视需要按顺序地被曝露于A气体、净化气体和B气体。
前驱物和/或反应物可以处于气体状态或蒸汽状态,或其他可用于气相沉积工艺的物质状态。在净化过程中,通常将惰性气体引入处理腔室,以净化反应区域或以其他方式从反应区域去除任何残余反应性化合物或副产物。或者,净化气体可在整个沉积工艺中连续地流动,使得在前驱物和共反应物的脉冲之间的时间延迟期间只有净化气体流动。
因此,在一个或多个实施例中,可以使用“A”反应物和“B”反应物的交替脉冲或流动来沉积薄膜,例如在脉冲化的前驱物和共反应物的多个循环脉冲输送中,例如A脉冲、B脉冲、A脉冲、B脉冲、A脉冲、B脉冲、A脉冲、B脉冲。如上所述,取代脉冲化反应物,这些气体可以同时从气体输送头或喷嘴流动,而且可以移动基板和/或气体输送头,使得基板按顺序地曝露于这些气体。
当然,上述的ALD循环仅为各式各样的ALD工艺循环的例示,其中所沉积的层是由前驱物和/或共反应物的交替层所形成。
本文中所使用的沉积气体或处理气体是指单一气体、多种气体、含有等离子的气体、一种或多种气体和/或一种或多种等离子的组合。沉积气体可以含有至少一种用于气相沉积工艺的反应性化合物。该反应性化合物在气相沉积工艺的过程中可以处于气体、等离子、蒸汽的状态。同样地,工艺可以含有净化气体或载体气体,并且不含反应性的化合物。
本文中所使用的“基板表面”是指任何形成于基板上的基板或材料表面,在制造工艺的过程中薄膜处理是在该基板上进行。举例来说,上面可以进行处理的基板表面包括诸如硅、氧化硅、应变硅、绝缘体上硅(SOI)、掺杂碳的硅氧化物、氮化硅、掺杂的硅、锗、砷化镓、玻璃、蓝宝石之类的材料,以及任何其他的材料,诸如金属、金属氮化物、金属合金和其他的导电材料,视应用而定。在基板表面上的阻挡层、金属或金属氮化物包括钛、氮化钛、氮化钨、钽和氮化钽、铝、铜或任何其他的导体或可用于装置制造的导电或不导电的阻挡层。基板可以具有各种的尺寸,如直径200mm或300mm的晶片,以及矩形或方形的窗玻璃片。可以使用本发明实施例的基板包括但不限于半导体晶片,诸如结晶硅(例如Si<100>或Si<111>)、氧化硅、应变硅、锗硅、掺杂的或未掺杂的多晶硅、掺杂的或未掺杂的硅晶片、III-V族材料诸如GaAs、GaN、InP等以及图案化或未图案化的晶片。可使基板进行预处理工艺,以抛光、蚀刻、还原、氧化、羟化、退火和/或烘烤基板表面。
由于本发明的实施例提供沉积或形成薄膜的方法,故在气相沉积工艺的过程中处理腔室构造成使基板曝露于顺序的气体和/或等离子。处理腔室可包括A和B反应物的单独供应,伴随载体气体、净化气体和惰性气体的任何供应,该惰性气体诸如与各反应物和气体的气体入口流体连通的氩气和氮气。可以通过适合的流量控制器来控制每个入口,该流量控制器如与中央处理单元(CPU)通信的质量流量控制器或体积流量控制器,以允许每个到基板的反应物的流动进行如本文中所述的ALD工艺。中央处理单元可以是任何形式的计算机处理器之一者,该计算机处理器可用于工业设定,以控制各腔室和子处理器。CPU可以耦接到存储器,并且该CPU可以是一个或多个容易买到的存储器,诸如随机存取存储器(RAM)、只读存储器(ROM)、快闪存储器、光盘、软盘、硬盘或任何其他形式的本地或远程数字储存器。可将支持电路耦接到该CPU,从而以常规的方式支持该CPU。这些电路包括缓存、电源、时钟电路、输入/输出电路系统、子系统和类似物。
在一个或多个实施例中,用于工艺的各种气体可以被脉冲化而进入入口、经过气体通道、来自各种孔或出口和进入中央通道。在一个或多个实施例中,可以按顺序或大致按顺序地脉冲化沉积气体以到达喷洒头且通过喷洒头。或者,如上所述,这些气体可以同时或大致同时地流经气体供应喷嘴或气体供应头,而且可以移动该基板和/或该气体供应头,使基板按顺序或大致按顺序地曝露于这些气体。
在上述方法的一些实施例中,基板表面是与DMAH和TiCl4接触。在进一步的实施例中,使用过量的胺。在一个或多个实施例中,基板表面是与铝烷胺和TiCl4接触。
本发明的另一个方面涉及用于在基板上沉积薄膜以进行依据上述任一实施例的工艺的设备。在一个实施例中,该设备包括用于在基板上原子层沉积薄膜的沉积腔室。该腔室包含用于支撑基板的处理区域。该设备包括前驱物入口,该前驱物入口与金属卤化物或Ti(NR'2)4或Ta(NR'2)5前驱物的供应流体连通,其中R'为烷基、烯基、炔基、酮基或醛基。该设备还包括反应物气体入口,该反应物气体入口与前驱物的供应流体连通,该前驱物包含配位于胺的铝烷,如上所讨论。该设备进一步包括与净化气体流体连通的净化气体入口。该设备可以进一步包括真空端口,该真空端口用于从沉积腔室去除气体。该设备可以进一步包括辅助气体入口,该辅助气体入口用于供应一种或多种辅助气体(如惰性气体)到沉积腔室。该沉积可以进一步包括用于通过辐射和/或电阻热量加热基板的工具。
在一些实施例中,在本文所述方法的过程中使用来沉积或形成光阻材料的等离子系统和处理腔室或系统可以实施于、或系统的任一者上,这些系统均可向位于加州圣克拉拉的应用材料公司(Applied Materials,Inc.,located in Santa Clara,Calif.)取得。ALD处理腔室的详细描述可在共同受让的美国专利第6,878,206号、第6,916,398号以及第7,780,785号中找到。
ALD工艺提供处理腔室或沉积腔室可以在从约0.01托至约100托范围内的压力下进行加压,例如从约0.1托至约10托,以及更具体地从约0.5托至约5托。
输送“A”前驱物至基板表面
可以使基板曝露于“A”前驱物气体或蒸汽,该“A”前驱物气体或蒸汽是由载体气体(例如氮气或氩气)通过可处于液体形式的前驱物的安瓿所形成。可以加热该安瓿。可以以任何适当的流动速率输送该“A”前驱物气体,该适合的流动速率是在从约10sccm至约2,000sccm的范围内,例如从约50sccm至约1,000sccm,并且在特定的实施例中是从约100sccm至约500sccm,例如约200sccm。可以使该基板曝露于含金属的“A”前驱物气体一段时间,该段时间在从约0.1秒至约10秒的范围内,例如从约1秒至约5秒,在具体的实例中,为约2秒。一旦前驱物已经吸附于基板表面上所有反应性的表面部分,则停止“A”前驱物气体的流动。在一些实施例中,该表面立即被反应性的前驱物“A”饱和,使得额外的曝露无法产生额外的沉积。
第一次净化
在停止“A”前驱物气体的流动之后,可使基板和腔室进行净化步骤。可以以从约10sccm至约2,000sccm范围内的流动速率将净化气体注入处理腔室,例如从约50sccm至约1,000sccm,并且在具体的实例中,从约100sccm至约500sccm,例如约200sccm。净化步骤去除处理腔室内任何过量的前驱物、副产物及其他污染物。净化步骤可以进行在约0.1秒至约8秒范围内的一段时间,例如从约1秒至约5秒,而且在具体的实例中从约4秒。该载体气体、该净化气体、该沉积气体或其他的处理气体可含有氮气、氢气、氩气、氖气、氦气或上述气体的组合。在一个实例中,该载体气体包含氮气。
输送“B”前驱物至基板表面
在第一次净化之后,可将该基板活性位点曝露于“B”前驱物气体或蒸汽,该“B”前驱物气体或蒸汽是由载体气体(例如氮气或氩气)通过“B”反应物的安瓿所形成。可以加热该安瓿。可以以任何适当的流动速率输送该“B”反应物气体,该适当的流动速率是在从约10sccm至约2,000sccm的范围内,例如从约50sccm至约1,000sccm,并且在特定的实施例中是约200sccm。可以使该基板曝露于该“B”反应物气体一段时间,该段时间在从约0.1秒至约8秒的范围内,例如从约1秒至约5秒,在具体的实例中,为约2秒。一旦“B”已经吸附于先前步骤中沉积的“A”前驱物上并立即与该“A”前驱物反应,则可停止“B”反应物气体的流动。
第二次净化
在停止“B”共反应物气体的流动之后,可使基板和腔室进行净化步骤。可以以约10sccm至约2,000sccm范围内的流动速率将净化气体注入处理腔室,例如从约50sccm至约1,000sccm,并且在具体的实例中,从约100sccm至约500sccm,例如约200sccm。净化步骤去除处理腔室内任何过量的前驱物、副产物及其他污染物。净化步骤可以进行从约0.1秒至约8秒范围内的一段时间,例如从约1秒至约5秒,在具体的实例中从约4秒。该载体气体、该净化气体、该沉积气体或其他的处理气体可含有氮气、氢气、氩气、氖气、氦气或上述气体的组合。在一个实例中,该载体气体包含氮气。该“B”前驱物气体也可以处于等离子的形式,且该等离子是从该工艺腔室的远端产生。
因此,本发明的一个非常特定的实施例涉及沉积Ta或Ti薄膜的方法。该方法包括按顺序地使基板表面与第一和第二前驱物接触,该第一前驱物包含二甲基乙基胺铝烷、三乙基胺铝烷、三甲基胺铝烷或甲基吡咯烷铝烷,而该第二前驱物包含TiCl4或TaCl5。
在某些实施例中,沉积薄膜还可以接受后处理工艺。这样的工艺包括减少薄膜中的任何杂质。在某些具体的实施例中,处理可以在原位进行,即不破坏真空。在甚至更具体的实施例中,减少薄膜中的杂质包括在氢气中退火或通过使该薄膜曝露于等离子处理而退火。
依据本发明的一个或多个实施例沉积的薄膜可以使用于集成电路制造工艺中。例如,包含纯钛或钽的薄膜可以用来作为钨、铝或铜衬垫。在其他的实施例中,薄膜可以用作为金属栅极材料。与先前已知的、沉积这种薄膜的方法(经常使用基于等离子的方法)相对比,依据本发明的各种实施例的薄膜提供良好的阶梯覆盖率且无使用等离子的损伤效应。
实例
实例1
使用TiCl4和二甲基乙基胺铝烷来生产薄膜。该工艺涉及使基板表面曝露于TiCl4,然后为第一次净化、曝露于二甲基乙基胺铝烷、然后为另一次净化。沉积温度在约50℃至约150℃的范围内。曝露时间的范围在从约1秒至约30秒之间。使用X射线光电子光谱法来测定薄膜的元素组成,该元素组成的曲线图请见图1A-B。测定的元素组成如下表1所示。
表1:整体(bulk)TiAl薄膜中的平均浓度(原子%)
从表1和图1A-B中可以看出,该薄膜明显地含有很少的碳、氯或氮。这是一个令人惊讶的结果,因为大多数的ALD薄膜会导致具有碳和/或氮的薄膜沉积。虽然不希望受限于任何特定的理论,但据认为铝烷有助于减少薄膜中的氯,以沉积铝。
实例C1
使用标准的PVD技术沉积TiAl薄膜。该薄膜被认为是比较性的,因为该薄膜是使用PVD而非本文所述的ALD技术所沉积。下表2对来自实例1和C1的薄膜性质进行比较。
表2:与PVD比较
如表2中所见,关于电阻率、密度、碳含量和功函数,两种薄膜表现出相似的性质。然而,PVD薄膜公知是沉积相对非保形的薄膜,特别是针对于某些应用。这样的应用包括在FinFET装置中作为功函数金属。相比之下,以本文所述方法沉积的薄膜提供了相对保形的薄膜且适用于这样的应用。
实例2
使用实例1的方法生产另四个薄膜。改变前驱物的摩尔比,以在所沉积的薄膜中获得不同的Ti/Al比率。这些薄膜示于下表3中。
表3:薄膜调整
Ti/Al比率 | 电阻率(mW-cm) | 厚度(A) |
0.30 | 64 | 249 |
0.33 | 71 | 210 |
0.40 | 130 | 227 |
0.44 | 198 | 219 |
0.53 | 230 | 183 |
如表3所示,可以改变通过本文中所述的方法所沉积的薄膜,以控制金属/铝比率。因此,薄膜的电阻率(以及功函数值)可以随着Ti/Al比率的改变而改变。应当指出,虽然薄膜的电阻率和厚度之间可能有一定的相关性,但在表3中提供的厚度是通常可比较的。
贯穿本说明书提及的“一个实施例”、“某些实施例”、“一个或多个实施例”或“实施例”是指关于该实施例所描述的特定特征、结构、材料或特性被包括在本发明的至少一个实施例中。因此,贯穿本说明书各处出现的短语如“在一个或多个实施例中”、“在某些实施例中”、“在一个实施例中”或“在实施例中”不一定是指本发明的相同实施例。此外,可以在一个或多个实施例中以任何适合的方式组合特定的特征、结构、材料或特性。
虽然已经参照特定的实施例描述了本文中的发明,但应了解到,这些实施例仅是对本发明的原理和应用的说明。对于本领域技术人员而言,在不偏离本发明的精神和范围下对本发明的方法和设备作出的各种修改和变化将是显而易见的。因此,本发明意在包括在所附权利要求书及其等同物范围内的修改和变化。
Claims (20)
1.一种沉积薄膜的方法,所述方法包括使基板表面与第一前驱物和第二前驱物接触,所述第一前驱物包含铝前驱物,所述铝前驱物选自二甲基铝氢化物、配位于胺的铝烷和具有由下式表示的结构的化合物:
其中R为C1-C6烷基,而所述第二前驱物包含金属卤化物。
2.如权利要求1所述的方法,其中R为甲基。
3.如权利要求1所述的方法,其中所述配位于胺的铝烷包括二甲基乙基胺铝烷、三乙基胺铝烷、三甲基胺铝烷或甲基吡咯烷铝烷。
4.如权利要求1所述的方法,其中使所述基板表面与第一前驱物和第二前驱物接触是按顺序发生。
5.如权利要求1所述的方法,其中所述金属选自Ti、Ta、Zr、La、Ce、Si、Ge、W和Hf。
6.如权利要求1所述的方法,其中所述第二前驱物包含金属氯化物、金属碘化物或金属溴化物。
7.如权利要求6所述的方法,其中所述金属氯化物选自TiCl4和TaCl5。
8.如权利要求1所述的方法,其中使用过量的胺。
9.如权利要求8所述的方法,其中所述第一前驱物包含二甲基铝氢化物,而所述第二前驱物包含TiCl4。
10.如权利要求1所述的方法,其中沉积是在23℃至300℃的温度下进行。
11.如权利要求1所述的方法,其中所沉积出的薄膜包含纯金属。
12.如权利要求1所述的方法,其中所沉积出的薄膜包含金属合金。
13.如权利要求1所述的方法,所述方法进一步包括在氢气或等离子处理中退火。
14.一种沉积薄膜的方法,所述方法包括使基板曝露于第一前驱物和第二前驱物,所述第一前驱物包含铝前驱物,所述铝前驱物选自二甲基铝氢化物、配位于胺的铝烷和具有由下式表示的结构的化合物:
其中R为C1-C6烷基,而所述第二前驱物包含Ti(NR'2)4或Ta(NR'2)5,
其中R'为C1-C4烷基、烯基、炔基、酮基或醛基。
15.如权利要求14所述的方法,其中R为甲基。
16.如权利要求14所述的方法,其中所述第二前驱物包含Ti(NMe2)4或Ta(NMe2)5。
17.如权利要求14所述的方法,其中所述沉积是在50℃至150℃的温度下进行。
18.如权利要求14所述的方法,其中使用过量的胺。
19.如权利要求18所述的方法,其中所述配位于胺的铝烷包括二甲基乙基胺铝烷、三乙基胺铝烷、三甲基胺铝烷或甲基吡咯烷铝烷。
20.一种沉积薄膜的方法,所述方法包括使基板表面按顺序地与第一前驱物和第二前驱物接触,所述第一前驱物包含二甲基乙基胺铝烷、三乙基胺铝烷、三甲基胺铝烷或甲基吡咯烷铝烷,而该第二前驱物包含TiCl4或TaCl5。
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US8927059B2 (en) | 2015-01-06 |
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WO2013070702A1 (en) | 2013-05-16 |
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